INPRINTING

Abstract

 The present invention is directed to a method for reversible color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, it relates to a method for reversible color inprinting an outer surface of a synthetic or non-synthetic polar-polymer material, and it relates to an article comprising at least one colored synthetic or non-synthetic polar-polymer material color inprinted by said method.

Description

FIELD OF THE INVENTION

[0001] The present invention relates to a method for reversible color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, it relates to a method for reversible color inprinting an outer surface of a synthetic or non-synthetic polar-polymer material, and it relates to an article comprising at least one colored synthetic or non-synthetic polar-polymer material color inprinted by said method.

BACKGROUND OF THE INVENTION

[0002] In the polymer industry it is frequently necessary for an article manufactured from polymers to have a range of properties. Amongst others, a specific color of the article may be desired.

[0003] The optical properties of products are increasingly coming to the fore. The coloring of plastics is of central importance for the appearance of plastic products and their change in the course of their life.

[0004] The coloring of plastics to colored polymer components is usually achieved by using color master batches, colored micro granules, so-called dry liquid colors or liquid colors. Colored polymer components can for example be produced from color master batch concentrates blended into a polymer prior to molding or extruding or pre-colored polymers via melt blending/ compounding. The selection of one coloring method over the other may vary based on economics, secondary operations and specific requirements of the end application.

[0005] When coloring with a master batch, in an upstream step, the pigment or colorizing agent is first dispersed or dissolved in a polymeric carrier with the addition of dispersants and if necessary or required further additives. In order to achieve a fine and homogeneous distribution of the pigments or dyes, twin-screw extruders are often used to produce the master batches. Separate master batches are required for each different color and - depending on the carrier selected and the final application - for the different plastics that are to be colored with the master batch. This leads to an inefficient process, especially with small batch sizes and frequent color changes.

[0006] The most common method used by plastics processors is the use of concentrated pigments dispersed into a polymer carrier resin by molding process. During molding the master batch is let down into natural resin as it is feed into the extruder at a predefined ratio to achieve the desired color.

[0007] The processing of the master batches also has major disadvantages for the plastics processor. On the one hand this is connected with a complex storage of different color master batches, on the other hand frequent color changes on the extrusion or injection molding machine lead to an inefficient process due to material losses, cleaning processes and downtimes.

[0008] The selection of the color pigment depends, among other things, on the desired color, the polymer carrier to be used, the application and the associated requirements, but also on the further processing conditions at the plastics processor- e.g. conventional injection molding or hot runner technology. Hot runner technology is characterized by the fact that the gate system is heated separately from the rest of the mold in order to maintain the flowability of the plastic melt at a constant level. The melt and thus also the colorants are exposed to a higher thermal load which further restricts the choice of pigments.

[0009] Due to the different temperature loads, the available selection of color pigments is reduced as the temperature rises. In the case of polyolefins (polyethylene PE/ polypropylene PP) this number amounts to approx. 70 different colorants, in the case of polyamide (PA) only up to 50 colorants can be used and in the case of polyphenylene sulfide (PPS) only less than 10 colorants are available which meet the processing conditions.

[0010] There are various method of coloring co-polyester, co-polycarbonates, acrylonitrile-butadiene-styrene, polyamide, polyurethane, polyalkyl(meth)acrylate and copolymers thereof.

[0011] All these methods do not work efficient for the colorization of polar polymer materials comprising a substantial content of non-polar polymers, such as polyalkylenes, polyethylene (PE), polypropylene (PP), polybutylene (PB), polystyrene or mixtures thereof.

[0012] Further, there is a need to speed up the colorization time for coloring polar polymer materials comprising co-polyester, co-polycarbonates, acrylonitrile-butadiene-styrene, polyamide, polyurethane, polyalkyl(meth)acrylate, allyldiglycol carbonate, styrene copolymers or mixtures thereof, or in addition non-polar polymers, such as polyalkylenes, polyethylene (PE), polypropylene (PP), polybutylene (PB) or mixtures thereof.

[0013] The plastic parts, foils, etc. produced in this way can only be recycled at great expense after application (end-of-life). Especially for colored polymer articles recycling may be connected to separating the articles according to their color, in order to achieve high quality recycled material. These decolorization processes may be oxidation or reduction process, wherein the used dyes are decolorized by chemical modifying the dye such as destroying the chromophores such as the conjugated double-bond system. This has the drawback that the destroyed dye compounds remain in the polymer material and the used oxidation or reduction agents are very aggressive and used in high amounts, which is not environmentally friendly.

[0014] Since the current processes are expensive and complex and so far lead to unsatisfactory results, many plastics cannot be reused in the same way and "down cycling" takes place. The unsorted plastics are melted together and processed to dark, mostly brown or black colored regranulates. New plastic products can only be produced to a very limited extent from this type of dyed recycling material. The regranulates are therefore often only processed into inferior products such as garbage bags, pallets, et cetera.

[0015] Recyclers may counter this with the addition of other colorants such as titanium dioxide. However, this impairs the physical properties and processability of the plastics, which further restricts their range of application. In particular, further recycling is made much more difficult because additional colorants are added with each cycle, further impairing the physical properties of the polymer.

[0016] Accordingly, there is a need for a method for reversible dye inprinting a pattern into the surface of a synthetic or non-synthetic polar-polymer material, especially polar-polymer material containing a substantially content of non-polar polymers, whereby the synthetic or non-synthetic polar-polymer material can be decolorized by removing the dyes from the color imprinted polymer material and whereby the dye does not necessarily have to be destroyed and can thus also be reused.

[0017] Plastic objects, in particular plastic containers, are labelled to indicate their contents or for advertising purposes or other purposes. Depending on the size, application or purpose of labelling containers, self-adhesive labels, shrink sleeves, wrap-around or other types of labels are used. Although numerous technologies have been developed to separate the label material from the material of the plastic object in the recycling process a practical complete separation of the label material and the ability of reuse is not sufficiently provided yet.

SUMMARY OF THE INVENTION

[0018] It is an object of the invention to provide a method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular for reversibly color inprinting a pattern into the outer surface, which comprises for example the reversibly color inprinting a pattern into an outwardly outer surface and/or the reversibly color inprinting a pattern into an inwardly outer surface, such as in the case of a container, of a synthetic or non-synthetic polar-polymer material, and an article comprising at least one colored synthetic or non-synthetic polar-polymer material color imprinted therein a pattern by said method.

[0019] The object is solved by the features of the independent claim. Preferred embodiments are described by the features of the dependent claims.

[0020] Thus, the object is solved by a method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular into the outer surface of the synthetic or non-synthetic polar-polymer material, comprising the step:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent;

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition solution has a temperature below 30 °C or is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0021] According to a further preferred embodiment the area of the outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended pattern is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C and then contacted with the coloring composition solution; and wherein the coloring composition solution has a temperature below 30 °C or is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0022] The term "inprinting" as used in the specification differs from the commonly used terminology inprinting in that the coloring agent - also named dye - migrates into the plastic through a printing process after application and does not remain on the surface, for example by a binder.

[0023] The term "solution" as used according to the present invention encompasses a true solution, a suspension, a colloid solution, an emulsion or a dispersion.

[0024] The true solution is a homogenous mixture, while a suspension, colloid solution, emulsion or dispersion are heterogeneous mixtures of two or more phases. Another difference between these three types of solution is that the true solution can be transparent, while the colloidal solution can be translucent and the suspension can be opaque.

[0025] The synthetic or non-synthetic polar-polymer material may comprise a mixture of different components. The synthetic or non-synthetic polar-polymer material may comprise at least one synthetic or non-synthetic polar-component. Polar in this context may mean that the component shows an enhanced polarity compared to a component that exclusively consist of C-atoms and H-atoms.

[0026] The method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material or synthetic or non-synthetic polar-polymer layer is that such a pattern, for example a label or barcode or any other type of decor or information, cannot be removed by typical consumer handling, because the color agent or dye is encapsulated in and under the outer surface of the synthetic or non-synthetic polar-polymer material or synthetic or non-synthetic polar-polymer layer.

[0027] The basic idea of method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material is to use at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol or about ≥ 250 g/mol to about ≤ 550 g/mol.

[0028] Without being bond to a specific theory the inventors assume that the organic aromatic coloring agent may have the ability to migrate into the synthetic or non-synthetic polar-polymer material and therefore coloring the synthetic or non-synthetic polar-polymer material. A migration of the organic aromatic coloring agent into the synthetic or non-synthetic polar-polymer material may also allow a migration of the organic aromatic coloring agent out of the colored synthetic or non-synthetic polar-polymer material. Therefore a decoloring of the colored material may be possible. In order to enable a migration as unhindered as possible, the organic aromatic coloring agent preferably has a rather planar structure and may comprise at least one free rotation center outside the planar structure. Further in case of ligands and/or remnants which may be spatially or sterically demanding, the ligands and/or remnants may be as freely movable as possible around a center of rotation. This may give the organic aromatic coloring agent the ability to adapt its shape to the environment given by the matrix of the synthetic or non-synthetic polar-polymer material. Preferably the organic aromatic coloring agent may not comprise a spiro-center and/or the organic aromatic coloring agent may not comprise a large moiety that is rotation-impaired. In this context a large moiety that is rotation impaired may mean that the molecular weight of this rotation impaired moiety is about 350 g/mol +/- 10%.

[0029] Furthermore, a coloring composition solution may comprise at least one dispersing agent for dispersing the organic aromatic coloring agent in the aqueous solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution. The organic aromatic coloring agent may only be partially soluble in the aqueous solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution. The dispersing agent may enhance the stability of the coloring composition solution by distributing the organic aromatic coloring agent in the phase of the aqueous solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution.

[0030] In addition, the coloring composition solution optionally may comprise at least one solubilizer. The solubilizer may enhance the solubility of the organic aromatic coloring agent in the aqueous solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution. The amount of molecularly solved organic aromatic coloring agent may be enhanced by the solubilizer. Therefore, the solubilizer may improve the result of the coloring process. Furthermore, the solubilizer can improve the wettability of the surface to be printed or, in extreme cases, slightly swell or dissolve it what further improves the result of the coloring process.

[0031] During the coloring process the heated outer surface that corresponds to the intended pattern to be colorized by inprinting of the synthetic or non-synthetic polar-polymer material is exposed to the heated coloring composition solution, wherein the outer surface, a defined area of the outer surface or the area that corresponds to the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition solution is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0032] According to another preferred embodiment the synthetic or non-synthetic polar-polymer having a Mw about ≥ 1000 g/mol, the synthetic or non-synthetic polar-oligomer having a Mw about ≥ 600 g/mol and < 1000 g/mol, and the polar-additive having a Mw about ≥ 70 and < 600 g/mol may each comprise at least about ≥ 5 wt.-% of heteroatoms, wherein the weight % is calculated based on the individual weights of the synthetic or non-synthetic polar-polymer, the synthetic or non-synthetic polar-oligomer, and the polar-additive, respectively. In this context a heteroatom may be any atom excluding C-atoms and H-atoms. Preferably, the heteroatom may be selected from the group comprising: N, O, F, Cl, Br, I, S, and P. Furthermore, preferably the synthetic or non-synthetic polar-polymer having a Mw about ≥ 1000 g/mol, the synthetic or non-synthetic polar-oligomer having a Mw about ≥ 600 g/mol and < 1000 g/mol, and the polar-additive having a Mw about ≥ 70 and < 600 g/mol may each comprise at least about ≥ 5 wt.-% and preferably < 70 wt.-% of heteroatoms comprising N, O, P, S, halogene.

[0033] The polarity of the synthetic or non-synthetic polar-polymer material may enhance the ability of the organic aromatic coloring agent to migrate into the synthetic or non-synthetic polar-polymer material. According to this in an another embodiment the synthetic or non-synthetic polar-polymer material that is colored may comprise at least about ≥ 0.5 wt.-% of the synthetic or non-synthetic polar-component, preferably about ≥ 5 wt.-% of the synthetic or non-synthetic polar-component, and further preferred about ≥ 10 wt.-% of the synthetic or non-synthetic polar-component, in addition preferred about ≥ 15 wt.-% of the synthetic or non-synthetic polar-component, also preferred about ≥ 20 wt.-% of the synthetic or non-synthetic polar-component, or about ≥ 30 wt.-% and about ≤ 100 wt.-% of the synthetic or non-synthetic polar-component, wherein the weight % is calculated based on the total weight of the synthetic or non-synthetic polar-polymer material.

[0034] According to another embodiment the synthetic or non-synthetic polar-polymer material that is colored may comprise at least about ≥ 0.5 wt.-% to about ≤ 99.5 wt.-% of a synthetic or non-synthetic non-polar polymer, preferably about ≥ 5 wt.-% of the synthetic or non-synthetic non-polar polymer, and further preferred about ≥ 10 wt.-% of the synthetic or non-synthetic non-polar polymer, in addition preferred about ≥ 15 wt.-% of the synthetic or non-synthetic non-polar polymer, also preferred about ≥ 20 wt.-% of the synthetic or non-synthetic non-polar polymer, or about ≥ 30 wt.-% to about ≤ 90 wt.-%, or about ≥ 35 wt.-% to about ≤ 85 wt.-%, or about ≥ 40 wt.-% to about ≤ 80 wt.-%, or about ≥ 45 wt.-% to about ≤ 75 wt.-%, or about ≥ 50 wt.-% to about ≤ 75 wt.-%, or about ≥ 55 wt.-% to about ≤ 70 wt.-%, or about ≥ 60 wt.-% to about ≤ 65 wt.-%, wherein the weight % is calculated based on the total weight of the synthetic or non-synthetic polar-polymer material.

[0035] The migration capability of the organic aromatic coloring agent into the synthetic or non-synthetic polar-polymer material may also be influenced by the morphology of the synthetic or non-synthetic polar-polymer and/or the synthetic or non-synthetic polar-oligomer. It may be possible that the synthetic or non-synthetic polar-polymer and/or the synthetic or non-synthetic polar-oligomer may show a mixed morphology having a mixture of crystalline phases, semicrystalline phases and amorphous phases. To achieve a homogeneous color inprinting the synthetic or non-synthetic polar-polar material should be finally, uniformly/homogeneously distributed in the synthetic or non-synthetic polar-polymer material.

[0036] According to a further preferred embodiment the method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material comprises the steps:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent;

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition solution has a temperature below 30 °C or is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C, wherein the organic aromatic coloring agent is encapsulated, preferably encapsulated in and under the outer surface of the synthetic or non-synthetic polar-polymer material, in the synthetic or non-synthetic polar-polymer material by cooling down and the encapsulated organic aromatic coloring agent is releasable out of the synthetic or non-synthetic polar-polymer material by heat treatment of the colorized surface of the synthetic or non-synthetic polar-polymer material and exposing to a polar medium.

[0037] According to a further preferred embodiment, wherein the polar medium is a polar decoloring agent. The polar decoloring agent may be selected from the group comprising:

• at least one synthetic and/or not-synthetic polar-polymer having a Mw of about ≥ 1000 g/mol, and/or
• at least one synthetic and/or not-synthetic polar-oligomer having a Mw of about ≥ 600 g/mol and about < 1000 g/mol, and/or
• at least one synthetic and/or not-synthetic polar-additive having a Mw of about ≥ 70 and about < 600 g/mol, wherein

the synthetic and/or not-synthetic polar-additive is solid at 23 °C and selected different to the organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol.

[0038] According to a further preferred embodiment the method for reversible color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material comprises the steps:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent;

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition solution has a temperature below 30 °C or is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C; and wherein the temperature difference between the heated surface of the synthetic or non-synthetic polar-polymer material and the heated coloring composition solution is about ≤ 20 °C, preferably about ≤ 15 °C or about ≤ 10 °C or about ≤ 5 °C.

[0039] According to a further preferred embodiment the method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material comprises the steps:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent,

wherein the agent is liquid at 23 °C, preferably the agent is a composition that is liquid at 23 °C, wherein the liquid agent or liquid agent composition is a true solvent, colloid solution, emulsion, dispersion or suspension;
wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C and then contacted with the coloring composition; and wherein the coloring composition solution is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0040] According to a further preferred embodiment the method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material comprises the steps:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent,
  wherein the agent is liquid at 23 °C, preferably the agent is a composition that is liquid at 23 °C, wherein the liquid agent or liquid agent composition is a true solvent, colloid solution, emulsion, dispersion or suspension; and
  wherein the agent is selected from the group comprising a C₁ to C₁₅ alcohol, C₂ to C₂₀ organic acid, C₃ to C₆ ketone, C₃ to C₅ aldehyde, C₁ to C₆ alkyl, C₃ to C₆ ester, alkylene glycol alkyl ether, glycol alkyl ether, glycol and glycol oligomers (e.g. PEG 200), glycol ether, ethanol, glycerol, acetone, formic acid, acetic acid, dimethylformamide, dimethylsulfoxide, acetyltributylcitrate, carboxymethylcellulose (CMC), fluorocarbons, fluorine derivates, silicones, hydrocarbons, alkylphosphates, buffers (such as acetic acid/Na-acetate), water or a mixture thereof, preferably the agent is selected from the group comprising glycol and glycol oligomers, ethanol, propanol, isopropanol, amyl alcohol (pentanol isomers), glycerol, acetone, methylethylketone, acetyltributylcitrate, tributylphosphate (defoamer), n-butyl acid ester, diethylenglycol-n-butyl-ether, water or mixture thereof;

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0041] According to a further preferred embodiment the method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material comprises the steps:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent,
  wherein the agent is liquid at 23 °C, preferably the agent is a composition that is liquid at 23 °C, wherein the liquid agent or liquid agent composition is a true solvent, colloid solution, emulsion, dispersion or suspension; and
  wherein the agent is selected from the group comprising a:
  • n-butylacetat; or
  • a mixture of glycerol, propanol, and water; or
  • a mixture of ethanol, amyl alcolhol, carboxymethylcellulose (CMC), tributylphosphate and water to 100%; or
  • ethanol, dimethylformamid, tributylphosphate and water; or
  • n-butylacetate, diethylenglycol-mono-n-butylether, tributylphosphate and water, or
  • acetyltributylcitrat, diethylenglycol-mono-n-butylether, tributylphosphate and water; and

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0042] According to a further preferred embodiment the method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material comprises the steps:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent,
  wherein the agent is liquid at 23 °C, preferably the agent is a composition that is liquid at 23 °C, wherein the liquid agent or liquid agent composition is a true solvent, colloid solution, emulsion, dispersion or suspension; and
• in addition at least one dispersing agent, at least one carrier agent, and/or optional at least one additive, wherein the dispersing agent, the carrier agent, and the optional additive are different in its chemical formula to the coloring agent, different to the synthetic or non-synthetic polar-polymer material and different to the agent that is liquid at 23 °C; and

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0043] According to a further preferred embodiment the method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material comprises the steps:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent,
  wherein the agent is liquid at 23 °C, preferably the agent is a composition that is liquid at 23 °C, wherein the liquid agent or liquid agent composition is a true solvent, colloid solution, emulsion, dispersion or suspension; and
• in addition at least one dispersing agent, preferably the dispersing agent is selected from the group comprising at least one:
  • anionic tenside, preferably selected from polyphosphates, polyacrylates, aromatic sulfonates, esters with ethoxylate groups, esters with sulfonate groups, fatty acid-based polymers with an anionic group, salts of polycarboxylic acids, ethoxylates, thiourea dioxide;
  • cationic tenside, preferably selected from quaternary ammonium compounds, fatty acid-polymers with a cationic group per molecule;
  • non-ionic tenside, preferably selected from aromatic esters and hydrocarbons, aromatic and non-aromatic carboxylic acid esters, ethyl acrylate, fatty acid esters, ethoxylated fatty acid, poly oxyethylated compounds derived from sorbitol and oleic acid, polymers that are fatty acid-based with a non-ionic group per molecule, acrylate-copolymers, acrylate/styrene copolymers, fatty acid derivatives, polyalkoxylate;
  • polyurethane (PUR) polymers and/or polyacrylate polymers, preferably linear or branched polyurethane (PUR) polymers and/or polyacrylate polymers, more preferred the polyurethane (PUR) polymer and/or polyacrylate polymer have a MW of 5000 to 30000 g/mol; and

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0044] According to a further preferred embodiment the method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material comprises the steps:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

• at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,
• at least one agent that is not an organic aromatic coloring agent,
  wherein the agent is liquid at 23 °C, preferably the agent is a composition that is liquid at 23 °C, wherein the liquid agent or liquid agent composition is a true solvent, colloid solution, emulsion, dispersion or suspension; and
• in addition at least one carrier agent, wherein the carrier agent is preferably selected from the group comprising aromatic esters such as benzoic acid or phthalic acid esters, polyphenylether, phenoles, aromatic alcohols, aromatic ketones, aryl halides, such as halogenized benzene, halogenized toluene; N-alkylphthalimide, methylnaphthaline, diphenyle, diphenylethere, naphtholether, oxybiphenyle, o-vanilline, coumarin and/or mitxtures thereof; and

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

[0045] According to a further preferred embodiment the method for reversibly color inprinting a pattern into a synthetic or non-synthetic polar-polymer material, in particular the outer surface of the synthetic or non-synthetic polar-polymer material, comprises at least one synthetic or non-synthetic polar-component, wherein the synthetic or non-synthetic polar-component comprises

• at least one synthetic or non-synthetic polar-polymer having a Mw about ≥ 1000 g/mol; and/or
• at least one composition of a non-polar-polymer having a Mw about ≥ 1000 g/mol containing
• at least one synthetic or non-synthetic polar-polymer having a Mw about ≥ 1000 g/mol, and/or
• at least one synthetic or non-synthetic polar-oligomer having a Mw about ≥ 600 g/mol and < 1000 g/mol, and/or
• at least one polar-additive having a Mw about ≥ 70 and < 600 g/mol, wherein the polar-additive is selected different to the organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol.

[0046] According to a further preferred embodiment the synthetic or non-synthetic polar-polymer having a Mw about ≥ 1000 g/mol, the synthetic or non-synthetic polar-oligomer having a Mw about ≥ 600 g/mol and < 1000 g/mol, and the polar-additive having a Mw about ≥ 70 and < 600 g/mol each comprises at least about ≥ 5 wt.-% of heteroatoms, wherein the weight % is calculated based on the individual weights of the synthetic or non-synthetic polar-polymer, the synthetic or non-synthetic polar-oligomer, and the polar-additive.

[0047] According to a further preferred embodiment the synthetic or non-synthetic polar-polymer material that is colored by inprinting a pattern comprises at least about ≥ 0.5 wt.-% of the synthetic or non-synthetic polar-component, preferably about ≥ 5 wt.-% of the synthetic or non-synthetic polar-component, and further preferred about ≥ 10 wt.-% of the synthetic or non-synthetic polar-component, in addition preferred about ≥ 15 wt.-% of the synthetic or non-synthetic polar-component, also preferred about ≥ 20 wt.-% of the synthetic or non-synthetic polar-component, or about ≥ 30 wt.-% and about ≤ 100 wt.-% of the synthetic or non-synthetic polar-component, wherein the weight % is calculated based on the total weight of the synthetic or non-synthetic polar-polymer material.

[0048] According to a further preferred embodiment, wherein

a) the synthetic or non-synthetic polar-polymer comprises an amorphous phase of at least about ≥ 10 vol.-%, preferably about ≥ 30 vol.-%, more preferably about ≥ 50 vol.-% and about ≤ 100 vol.-%, wherein the volume % is calculated on the total volume of the synthetic or non-synthetic polar-polymer; and/or

b) the synthetic or non-synthetic polar-oligomer comprises an amorphous phase of at least about ≥ 10 vol.-%, preferably about ≥ 30 vol.-%, more preferably about ≥ 50 vol.-% and about ≤ 100 vol.-%, wherein the volume % is calculated on the total volume of the synthetic or non-synthetic polar-oligomer.

[0049] The volume % of the amorphous phase of the synthetic or non-synthetic polar-polymer and/or the synthetic or non-synthetic polar-oligomer may be determined by light microscopy, light scattering, X-ray diffraction, electron microscopy, electron diffraction, and/or neutron scattering, wherein light microscopy is preferred.

[0050] The migration capability of the organic aromatic coloring agent into the synthetic or non-synthetic polar-polymer material may also be influenced by a free volume of the synthetic or non-synthetic polar-polymer and/or the synthetic or non-synthetic polar-oligomer. It may be advantage to the result of the coloring process when the synthetic or non-synthetic polar-polymer and/or the synthetic or non-synthetic polar-oligomer trap a large amount of interconnected free volume in the glassy state.

[0051] The free volume may be determined by positron annihilation spectroscopy and more preferably by positron annihilation lifetime spectroscopy. These are non-destructive spectroscopy techniques for studying voids and defects in solids. The measurement data may be interpreted according to the concept of free volume given by Simha and Boyer.

[0052] With regard to the synthetic or non-synthetic polar-polymer and the synthetic or non-synthetic polar-oligomer:

a) the synthetic or non-synthetic polar-polymer may be selected from the group comprising synthetic or non-synthetic polar-homopolymers, synthetic or non-synthetic polar-copolymers, and/or synthetic or non-synthetic polar-terpolymers; and/or

b) the synthetic or non-synthetic polar-oligomer may be selected from the group comprising synthetic or non-synthetic polar-homo oligomers, synthetic or non-synthetic polar-cooligomers, and/or synthetic or non-synthetic polar-teroligomers.

[0053] A homopolymer or a homo oligomer may be a polymer or an oligomer that contains only a single type of repeat unit. A copolymer or a cooligomer may be a polymer or an oligomer that contains two types of repeat units. A terpolymer or a teroligomer may be a polymer or an oligomer that contains three types of repeat units. With regard to the copolymer, the cooligomer, the terpolymer, and the teroligomer the different types of repeat units may be organized along the backbone in different ways. There may be a controlled arrangement of the different repeat units, a statistical distribution of the different repeat units, and/or a longer sequence of one specific repeat unit alternating a longer sequence of a different specific repeat unit.

[0054] Preferably the two different types of repeat units in the copolymer or the cooligomer are organized in blocks such that the copolymer or the cooligomer is a block copolymer or block cooligomer. More preferably the first type of repeat unit is non-polar and preferably comprises only C and H atoms. Preferably the second type of repeat unit is polar and comprises more than 5 wt.-% of heteroatoms based on the total weight of the repeat unit, wherein a heteroatom is any atom excluding C and H. These block copolymers and block oligomers may have the advantage that the migration of the organic aromatic coloring agent into the synthetic or non-synthetic polar-polymer material is enhanced due to the formation of micelles and kind of channels in the synthetic or non-synthetic polar-polymer material. Therefore, using these block copolymers and/or block cooligomers may lead to a more homogenous coloring of the synthetic or non-synthetic polar-polymer material. These block copolymers and block oligomers may be produced by (living) radical polymerization and or radical oligomerization and/or by using coordinative polymerization methods with metal complex catalysts.

[0055] According to a further preferred embodiment wherein

a) the synthetic or non-synthetic polar-polymer comprises an amorphous phase of at least about ≥ 10 vol.-%, preferably about ≥ 30 vol.-%, more preferably about ≥ 50 vol.-% and about ≤ 100 vol.-%, wherein the volume % is calculated on the total volume of the synthetic or non-synthetic polar-polymer; and/or

b) the synthetic or non-synthetic polar-oligomer comprises an amorphous phase of at least about ≥ 10 vol.-%, preferably about ≥ 30 vol.-%, more preferably about ≥ 50 vol.-% and about ≤ 100 vol.-%, wherein the volume % is calculated on the total volume of the synthetic or non-synthetic polar-oligomer.

[0056] According to a further preferred embodiment, wherein

a) the synthetic or non-synthetic polar-polymer has, above the glass-transition temperature Tg, a free volume, in the range of about ≥ 1 vol.-% to 25 %, preferably about ≥ 2 % to about ≤ 20 %, further preferred about ≥ 2.2 % to about ≤ 15 %, based on the total volume of the synthetic or non-synthetic polar-polymer material; and/or

b) the synthetic or non-synthetic polar-oligomer has, above the glass-transition temperature Tg, a free volume in the range of about ≥ 1 % to 25 %, preferably about ≥ 2 % to about ≤ 20 %, further preferred about ≥ 2.2 % to about ≤ 15 %, based on the total volume of the synthetic or non-synthetic polar-oligomer material.

[0057] In this context according to a further preferred embodiment the glass-transition temperature T_g of the synthetic or non-synthetic polar-polymer may be in the range of about ≥ - 75°C to about ≤ 160°C, preferably about ≥ -50°C to about ≤ 120°C, further preferred about ≥ 0°C to about ≤ 115°C.

[0058] The glass transition may be the gradual and reversible transition in amorphous regions of the synthetic or non-synthetic polar-polymer from a hard and relatively brittle state into a viscous or rubbery state as the temperature is increased. The glass transition temperature T_g of the synthetic or non-synthetic polar-polymer may be determined by differential scanning calorimetry (DSC), which is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature.

[0059] The glass transition temperature T_g of the synthetic or non-synthetic polar-polymer may be determined according to the following standards: DIN 51007 (Thermal Analysis - Differential Thermal Analysis and Differential Scanning Calorimetry - General Principles), ASTM E 474, ASTMD 3418, DIN EN ISO 11357-1 (Plastics - Differential Scanning Thermal Analysis Part 1: General principles. (2008)), ISO 11357-2 (Plastics - Differential Scanning Calorimetry Part 2: Determination of the glass transition temperature. (1999)), ISO / DIS 11357-3 (Plastics - Differential Scanning Calorimetry Part 3: Determination of the melting and crystallization temperature and the melting and crystallization enthalpy. (2009)), ISO 11357-4(Plastics - Differential Scanning Thermal Analysis (DSC) Part 4: Determination of specific heat capacity. (2005)).

[0060] The glass transition temperature T_g of the synthetic or non-synthetic polar-polymer may be determined using a Mettler Toledo DSC 3+ differential calorimeter, a sample amount of 10 +/-1 mg, nitrogen as purge gas, and the following settings: 1. Heating: -40 °C to 280 °C with 20 °C/min, Hold: 3 minutes at 200 °C, Cooling: 280 °C to -40 °C at 10 °C/min, Hold: 5 minutes at - 20 °C, 2. Heating: -40 °C to 300 °C at 20 °C/min.

[0061] According to a further preferred embodiment, wherein the glass-transition temperature Tg of the synthetic or non-synthetic polar-polymer is in the range of about ≥ -75°C to about ≤ 160°C, preferably about ≥ -50°C to about ≤ 120°C, further preferred about ≥ 0°C to about ≤ 115°C.

[0062] According to a further preferred embodiment, wherein

a) the synthetic or non-synthetic polar-polymer is selected from the group comprising synthetic or non-synthetic polar-homopolymers, synthetic or non-synthetic polar-copolymers, and/or synthetic or non-synthetic polar-terpolymers; and/or

b) the synthetic or non-synthetic polar-oligomer is selected from the group comprising synthetic or non-synthetic polar-homo oligomers, synthetic or non-synthetic polar-cooligomers, and/or synthetic or non-synthetic polar-teroligomers; and/or

c) the synthetic or non-synthetic polar-polymer is selected from a water-swellable crosslinked polymer matrix, wherein the matrix comprises a water-soluble polymer and a polymer latex in a weight ratio of 1:1 to 10:1, preferred from 1 : 1 to 5 : 1 and more preferred from 1 : 1 to 3 : 1 which are crosslinked.

Synthetic or non-synthetic polar-polymer or mixture

[0063] According to a further preferred embodiment, wherein the synthetic or non-synthetic polar-polymer or mixture thereof is a synthetic or non-synthetic polar-homo polymers, synthetic or non-synthetic polar-copolymers, and/or synthetic or non-synthetic polar-terpolymers, further preferred the synthetic or non-synthetic polar-polymer or mixture thereof is selected from the group:

• polyacrylate with methyl (polymethylacrylate), ethyl (polyethylacrylate), propyl (polypropylacrylate), or butyl (polybutylacrylate),
• polymethacrylate with methyl (polymethylmathacrylate), ethyl (polyethylmethacrylate), propyl (polypropylmethacrylate), or butyl (polybutylmethacrylate),
• copolymers of acrylic and methacrylic esters including, among others, tert. - Butyl (meth)acrylate, pentyl(meth)acrylate and 2-ethylhexyl(meth)acrylate; (Meth)acrylates derived from unsaturated alcohols, preferably oleyl(meth)acrylate, 2-propynyl(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate;
• aryl(meth)acrylate polymers, preferably benzyl(meth)acrylate polymers or phenyl(meth)acrylate polymers, the aryl radicals each being unsubstituted or up to four times substituted;
• cycloalkyl(meth)acrylates polymers, preferably 3-vinylcyclohexyl(meth)acrylate polymers, bornyl (meth)acrylate polymers;
• hydroxylalkyl (meth)acrylates polymers, preferably 3- hydroxypropyl (meth)acrylate polymers, 3,4- dihydroxybutyl(meth)acrylate polymers, 2-hydroxyethyl(meth)acrylate polymers, 2-hydroxypropyl(meth)acrylate polymers;
• glycol di(meth)acrylates polymers, preferably 1,4-butanediol (meth)acrylate polymers;
• (meth)acrylates of ether alcohols polymers, preferably tetrahydrofurfuryl (meth)acrylate polymers, vinyloxyethoxyethyl(meth)acrylate polymers;
• polymers of amides and nitriles of the (meth)acrylic acid, preferably N-(3-dimethylaminopropyl)(meth)acrylamide polymers, N-(diethylphosphono)(meth)acrylamide polymers, 1 -methacryloylamido-2-methyl-2-propanol polymers;
• polymers of sulfur-containing methacrylates, preferably ethylsulfinylethyl(meth)acrylate, 4-thiocyanatobutyl(meth)acrylate polymers, ethylsulfonylethyl(meth)acrylate polymers, thiocyanatomethyl(meth)acrylate polymers, methylsulfinylmethyl(meth)acrylate polymers, bis((meth)acryloyloxyethyl)sulfide polymers;
• polyhydric (meth)acrylates, preferably trimethyloylpropanetri(meth)acrylate polymers;
• acrylonitrile polymers;
• vinyl ester polymers, preferably vinyl acetate polymers;
• styrene polymers, substituted styrenes polymers with an alkyl substituent in the side chain, preferably α-methylstyrene and α -ethylstyrene, substituted styrenes polymers with an alkyl substituent on the ring, preferably vinyl toluene, and p-methylstyrene, halogenated styrene polymers, preferably monochlorostyrene polymers, dichlorostyrene polymers, tribromostyrene polymers and tetrabromostyrene polymers;
• heterocyclic vinyl polymers, preferably 2-vinylpyridine polymers, 3-vinylpyridine polymers, 2-methyl-5-vinylpyridine polymers, 3-ethyl-4-vinylpyridine polymers, 2,3-dimethyl-5-vinylpyridine polymers, vinylpyrimidine polymers, vinylpiperidine polymers, 9-vinylcarbazole polymers, 3-vinylcarbazole polymers, 4-vinylcarbazole polymers, 1-vinylimidazole polymers, 2-methyl-l-vinylimidazole polymers, N-vinylpyrrolidone polymers, 2-vinylpyrrolidone polymers, N-vinylpyrrolidine polymers, 3-vinylpyrrolidine polymers, N-vinylcaprolactam polymers, N-vinylbutyrolactam polymers, vinyl oxolane polymers, vinyl furan polymers, vinyl thiophene polymers, vinylthiolane polymers, vinylthiazoles and hydrogenated vinylthiazoles polymers, vinyloxazoles and hydrogenated vinyloxazoles;
• polymers of vinyl and isoprenyl ethers;
• maleic acid polymers, preferably maleic anhydride polymers, methyl maleic anhydride polymers, maleimide polymers, methyl maleimide; and
• dienes polymers, preferably divinylbenzene polymers;
• copolymers of ethylene and propylene with acrylic esters, preferably polyethylen-block-copolymethylmethacrylate, polypropylen-block-co-polymethylmethacrylat;
• aliphatic and/or aromatic polyesters, preferably, hydroxyl-functional dendritic polyesters, polycaprolactone, polyethylenterephthalate (PET), polytrimethylenterephthalate (PTT), polybutylenterephthalate (PBT), glycolized polyglycolterephthaltate (G-PET), amorphous polyethylenterephthalate (A-PET), polyethylenfuranoate (PEF), polyethylennaphthylate (PEN), polyesters of terephthalic acid, polyspiro-diol-terephthalate, polypentaspiroglycol-terephthalate (PSG), polycyclohexylenedimethylene-terephthalate, polyester based copolymer including a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4-(hydroxymethyl)cyclohexylmethyl-4' -(hydroxymethyl)cyclohexane carboxylate, polyester based copolymer including a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4,4-(oxybis(methylene)bis) cyclohexane methanol;
• polycarbonate (PC), 2,2-Bis-(4-hydroxyphenyl)-propan (Bisphenol A) polycarbonate, 2,2-Bis-(4-hydroxyphenyl)-butan (Bisphenol B) polycarbonate, 1,1-Bis(4-hydroxyphenyl)cyclohexan (Bisphenol C) polycarbonate, 2,2'-Methylendiphenol (Bisphenol F) polycarbonate, 2,2-Bis(3,5-dibrom-4-hydroxyphenyl)propan (Tetrabrombisphenol A) polycarbonate und 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propan (Tetramethylbisphenol A) polycarbonate, bisphenol S polycarbonate, dihydroxydiphenylsulfid polycarbonate, tetramethylbisphenol A polycarbonate, 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) polycarbonate, 1,1,1-Tris(4-hydroxyphenyl)-ethane (THPE) polycarbonate;
• aliphatic polyamide (PA), preferably PA 6 based on polycaprolactam, PA 6.6 based on 6,6-hexamethylendiamin and adipic acid, PA 6.66 based on caprolactam, co-poymer of hexamethylendiamin and adipic acid, PA 66.610 based on hexamethylendiamin, copolymer of adipic acid and sebaic acid, PA 4.6, PA10, PA 12 and PA copolymers;
• polyurethane (PU),
• polar-copolymere, maleic anhydride-olefin copolymer;
• polyalkylenoxide, polyalkylene block copolymer, propylenoxide-ethylenoxide copolymer, (m)ethylene acrylate-maleic anhydride copolymer;
• polar-terpolymere, preferably reactive terpolymers of ethylene, acrylic ester and maleic anhydride, or ethylene, methacrylic ester and maleic anhydride, or ethylene, acrylic esters and glycidyl methacrylate, or ethylene, methacrylic esters and glycidyl methacrylate, or ethylene, (meth)acrylic esters and methyl (methyl(meth)acrylate), ethyl (ethy(meth)acrylate), propyl (propyl(meth)acrylate), or butyl (butyl(meth)acrylate), polyamide, polyester-polyamides, or butyl (butyl(meth)acrylate), polyether-polyamide copolymers;
• polar polymer blends, preferably polycarbonate/polyethylenterephthalate blends (PC/PET blends), polycarbonate/polybutyleneterephthalate blends (PC/PBT blends), blends of polycyclohexylene dimethylene terephthalate copolymer, blends of poly(butylene-adipate-terephthalate);
• polyacrylnitril and polyacrylnitril-copolymers, preferably poly acrylonitrile butadiene styrene (ABS), poly styrene-acrylonitrile;
• polystyrene and polystyrene copolymers, preferably styrene/butadiene co-polymer (SBR), poly styrene-isoprene-styrene (SIS), poly(glycidyl methacrylate) grafted sulfonamide based polystyrene resin with tertiary amine;
• ethylene-vinyl acetate;
• polyether, preferably polyethyleneglycol, polyethyleneglycol with at least one fatty acid coupled to the polyethyleneglycol, terminating functional groups such NH₂-terminated polyethers;
• functionalized polyacrylamide polymers, copolymers and terpolymers, preferably poly(2-acrylamido-2-aminopropionicacid) (polyAMPA), poly(2-acrylamido-2-amino propane sulfonic acid), poly(N-isopropylacylamide (polyPNIPAM); poly (amidoamine-co-acrylic acid) copolymer, poly(N,N-dimethylacrylamide-co-sodium acrylate), poly(acrylamide-co-sodium acrylate)/poly(ethylene glycol) semi-IPN, poly(acrylamide-co-sodium 4-styrenesulfonate), poly(acrylamide-co-sodium 4-styrenesulfonate)/poly(ethylene glycol) semi-IPN, poly(acrylamide-co-sodium methacrylate), poly(acrylamide-co-sodium methacrylate)/poly(ethylene glycol) semi-IPN, and/or poly(N-isopropylacrylamide-co-acrylic acid) andpoly(acrylamide-co-acrylic acid;
• poly(ether sulfones)/poly(ethyleneimine) (PES/PEI);
• polyvinylpyrrolidone, preferably poly(N-vinyl-2-pyrrolidone), poly(N-vinyl-2-pyrrolidone-co acrylonitrile) treated with hydroxylamine-hydrochloride
• polyvinyl alcohol;
• poly(1-naphthylamine)-camphorsulphonic acid.

[0064] Other synthetic or non-synthetic polar-polymer of amorphous copolyester that can be used are known under the tradename Akestra 90, 100 and 110. The above named synthetic or non-synthetic polar-polymers may be used alone or in a mixture of two or more.

[0065] With regard to hydroxyl-functional dendritic polyesters that can be suitable used as a polar polymers, these molecules may be produced using polyalcohol cores, hydroxy acids and technology based on captive materials. The dendritic structures may be formed by polymerization of the particular core and 2,2-dimethylol propionic acid (Bis-MPA). The base products that may be obtained are hydroxyl-functional dendritic polyesters. They may be fully aliphatic and may consist only of tertiary ester bonds. They may provide excellent thermal and chemical resistance. Extensive branching also improves reactivity, lowers viscosity and results in balanced mechanical properties. The hydroxyl-functional dendritic polyesters may be known under the trade name Boltorn^®. The following dendritic polymers may be used as non-limiting examples: Boltorn^® H20 16 terminal hydroxyl groups, nominal molecular weight of 1750 g/mol, Boltorn^® H2004 6 terminal hydroxyl groups, nominal molecular weight of 3100 g/mol, Boltorn^® H311 23 terminal hydroxyl groups, nominal molecular weight of 5300 g/mol, Boltorn^® P500 Formulated bimodal product with terminal hydroxyl groups, nominal molecular weight 1800 g/mol, Boltorn^® P1000 formulated bimodal product with terminal hydroxyl groups, nominal molecular weight 1500 g/mol, Boltorn^® U3000 modified with unsaturated fatty acid, nominal molecular weight 6500 g/mol, Boltorn^® W3000 modified with non-ionic groups and unsaturated fatty acid, nominal molecular weight 10000 g/mol.

[0066] With regard to the polyester based copolymers that can be suitable used as a polar polymers, these may further include but not limited to a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4-(hydroxymethyl)cyclohexylmethyl-4'-(hydroxymethyl)cyclohexane carboxylate represented by the following chemical formula 1 and a residue derived from 4,4-(oxybis(methylene)bis) cyclohexane methanol represented by the following chemical formula 2.

[0067] The compounds of chemical formula 1 and 2 can be copolymerized with aromatic dicarboxylic acid may be one or more selected from a group consisting of terephthalic acid, dimethyl terephthalate, cyclic dicarboxylic acid, isophthalic acid, adipic acid, azelaic acid, naphthalene dicarboxylic acid, and succinic acid.

[0068] The diol-derived residue of the copolymers may further include a residue derived from one or more other diols selected from a group consisting of 1,4-cyclohexane dimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), ethylene glycol, and diethylene glycol. A content of the diol derived residues of the residue derived from 4-(hydroxymethyl)cyclohexylmethyl 4'-(hydroxymethyl)cyclohexane carboxylate, the residue derived from 4,4-(oxybis(methylene)bis) cyclohexane methanol, and other diol-derived residues may be about 10 to 80 mol% based on 100 mol% of the dicarboxylic acid co-monomer.

[0069] The synthetic or non-synthetic polar-polymer may also comprise the polyester based copolymers used in a mixture with polyethylene terephthalate (PET). The mixture may consist of 1 to 99 wt.-% of PET and 1 to 99 wt.-% of the polyester based copolymers, in order that both components add up to 100 wt.-%. Additionally or alternatively the compounds according to chemical formulas 1 and 2 may be used as co-monomers together with a further diol-component, e.g. ethylene glycol, in the preparation of the polyester based copolymers.

[0070] The polyester based copolymer may be prepared by reacting the dicarboxylic acid including the aromatic dicarboxylic acid with the diol including 4-(hydroxymethyl)cyclohexylmethyl 4'-(hydroxymethyl)cyclohexane carboxylate represented by chemical formula 1 and 4,4-(oxybis(methylene)bis) cyclohexane methanol represented by chemical formula 2 to perform an esterification reaction and a polycondensation reaction. In this case, other diols such as 1,4-cyclohexane dimethanol, ethylene glycol, diethylene glycol, or the like, as described above may be further reacted, such that a polyester based copolymer further including other diol-derived residues may be prepared.

[0071] With regard to the polyether, these may comprise but not limited to compounds that contain at least one polyethyleneglycol moiety and at least one fatty acid moiety coupled to the polyethyleneglycol moiety. The polyethyleneglycol moiety may contain 10 to 25 ethyleneglycol repeating units. The fatty acid moieties may be saturated or unsaturated and may contain 10 to 30 carbon atoms, preferably 16 to 22 carbon atoms. Examples of these fatty acid moieties are oleate, laureate, stearate, palmitate and ricinoleate. A specific preferred example may be ethoxylated sorbitan ester.

[0072] The ethoxylated sorbitan ester comprises a sorbitan group which is substituted by four polyethylene glycol substituents. The ethoxylated sorbitan ester may preferably comprise 14 to 26 ethylene glycol repeating units, preferably 16 to 24 ethylene glycol repeating units, more preferably between 18 and 22 repeating units. At least one of the ethylene glycol substituents in the ethoxylated sorbitan ester is connected via an ester bond to a fatty acid moiety. Preferably, at least two of the ethylene glycol substituents in the ethoxylated sorbitan ester are connected via an ester bond to a fatty acid moiety; more preferably at least three of the ethylene glycol substituents are connected via an ester bond to a fatty acid moiety. The fatty acid moieties may be saturated or unsaturated and may contain 10 to 30 carbon atoms, preferably 16 to 22 carbon atoms.

[0073] Examples of these fatty acid moieties are oleate, laureate, stearate and palmitate. Most preferred are ethoxylated sorbitan esters comprising four polyethylene glycol substituents and wherein the ester comprises between 18 and 22 ethylene glycol repeating units and wherein three of the ethylene glycol substituents are connected to oleate, laurate or stearate groups.

[0074] Examples of ethoxylated sorbitan esters that can be used as polar-polymer are polyoxyethylene (20) sorbitane monolaurate, polyoxyethylene (20) sorbitane dilaurate, polyoxyethylene (20) sorbitane trilaurate, polyoxyethylene (20) sorbitane mono-oleate, polyoxyethylene (20) sorbitane di-oleate, polyoxyethylene (20) sorbitane tri-oleate, polyoxyethylene (20) sorbitane monostearate, polyoxyethylene (20) sorbitane distearate, polyoxyethylene (20) sorbitane tristearate, and polyoxyethylene (20) sorbitan monooleate, also known as Polysorbate 80 and E433.

Synthetic or non-synthetic polar-oligomer or mixture

[0075] According to a further preferred embodiment, wherein the synthetic or non-synthetic polar oligomer or mixture thereof is selected from the group comprising:

• oligoacrylate with methyl (oligomethylacrylate), ethyl (oligoethylacrylate), propyl (oligopropylacrylate), or butyl (oligobutylacrylate),
• oligomethacrylate with methyl (oligomethylmathacrylate), ethyl (oligoethylmethacrylate), propyl (oligopropylmethacrylate), or butyl (oligobutylmethacrylate),
• cooligomers of acrylic and methacrylic esters including, among others, tert. - Butyl (meth)acrylate, pentyl(meth)acrylate and 2-ethylhexyl(meth)acrylate; (Meth)acrylates derived from unsaturated alcohols, preferably oleyl(meth)acrylate, 2-propynyl(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate;
• aryl(meth)acrylates oligomers, preferably benzyl(meth)acrylate oligomers or phenyl(meth)acrylate oligomers, the aryl radicals each being unsubstituted or up to four times substituted;
• cycloalkyl(meth)acrylates oligomers, preferably 3-vinylcyclohexyl(meth)acrylate oligomers, bornyl (meth)acrylate oligomers;
• hydroxylalkyl (meth)acrylates oligomers, preferably 3- hydroxypropyl (meth)acrylate oligomers, 3,4- dihydroxybutyl(meth)acrylate oligomers, 2-hydroxyethyl(meth)acrylate oligomers, 2-hydroxypropyl(meth)acrylate oligomers;
• glycol di(meth)acrylates oligomers, preferably 1,4-butanediol (meth)acrylate oligomers;
• (meth)acrylates of ether alcohols oligomers, preferably tetrahydrofurfuryl (meth)acrylate oligomers, vinyloxyethoxyethyl(meth)acrylate oligomers;
• oligomers of amides and nitriles of the (meth)acrylic acid, preferably N-(3-dimethylaminopropyl)(meth)acrylamide oligomers, N-(diethylphosphono)(meth)acrylamide oligomers, 1-methacryloylamido-2-methyl-2-propanol oligomers;
• oligomers of sulfur-containing methacrylates, preferably ethylsulfinylethyl(meth)acrylate, 4-thiocyanatobutyl(meth)acrylate oligomers, ethylsulfonylethyl(meth)acrylate oligomers, thiocyanatomethyl(meth)acrylate oligomers, methylsulfinylmethyl(meth)acrylate oligomers, bis((meth)acryloyloxyethyl)sulfide oligomers;
• oligohydric (meth)acrylates, preferably trimethyloylpropanetri(meth)acrylate oligomers;
• acrylonitrile oligomers;
• vinyl ester oligomers, preferably vinyl acetate oligomers;
• styrene oligomers, substituted styrenes oligomers with an alkyl substituent in the side chain, preferably α-methylstyrene and α -ethylstyrene, substituted styrenes oligomers with an alkyl substituent on the ring, preferably vinyl toluene, and p-methylstyrene, halogenated styrene oligomers, preferably monochlorostyrene oligomers, dichlorostyrene oligomers, tribromostyrene oligomers and tetrabromostyrene oligomers;
• heterocyclic vinyl oligomers, preferably 2-vinylpyridine oligomers, 3-vinylpyridine oligomers, 2-methyl-5-vinylpyridine oligomers, 3-ethyl-4-vinylpyridine oligomers, 2,3-dimethyl-5-vinylpyridine oligomers, vinylpyrimidine oligomers, vinylpiperidine oligomers, 9-vinylcarbazole oligomers, 3-vinylcarbazole oligomers, 4-vinylcarbazole oligomers, 1-vinylimidazole oligomers, 2-methyl-1-vinylimidazole oligomers, N-vinylpyrrolidone oligomers, 2-vinylpyrrolidone oligomers, N-vinylpyrrolidine oligomers, 3-vinylpyrrolidine oligomers, N-vinylcaprolactam oligomers, N-vinylbutyrolactam oligomers, vinyl oxolane oligomers, vinyl furan oligomers, vinyl thiophene oligomers, vinylthiolane oligomers, vinylthiazoles and hydrogenated vinylthiazoles oligomers, vinyloxazoles and hydrogenated vinyloxazoles;
• oligomers of vinyl and isoprenyl ethers;
• maleic acid oligomers, preferably maleic anhydride oligomers, methyl maleic anhydride oligomers, maleimide oligomers, methyl maleimide; and
• dienes oligomers, preferably divinylbenzene oligomers;
• cooligomers of ethylene and propylene with acrylic esters, preferably oligoethylen-block-cooligomethylmethacrylate, oligopropylen-block-co-oligomethylmethacrylat;
• aliphatic and/or aromatic oligoesters, preferabl, hydroxyl-functional dendritic oligoesters, preferably oligocaprolactone, oligoethylenterephthalate (PET), oligotrimethylenterephthalate (PTT), oligobutylenterephthalate (PBT), glycolized oligoglycolterephthaltate (G-PET), amorphes oligoethylenterephthalate (A-PET), oligoethylenfuranoate (PEF), oligoethylennaphthylate, oligoesters of terephthalic acid, oligospiro-diol-terephthalate, oligopentaspiroglycol-terephthalate (PSG), polycyclohexylenedimethylene-terephthalate, oligoester based cooligomer including a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4-(hydroxymethyl)cyclohexylmethyl-4'-(hydroxymethyl)cyclohexane carboxylate, oligester based cooligomer including a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4,4-(oxybis(methylene)bis) cyclohexane methanol;
• oligocarbonate (PC), 2,2-Bis-(4-hydroxyphenyl)-propan (Bisphenol A) oligocarbonate, 2,2-Bis-(4-hydroxyphenyl)-butan (Bisphenol B) oligocarbonate, 1,1-Bis(4-hydroxyphenyl)cyclohexan (Bisphenol C) oligocarbonate, 2,2'-Methylendiphenol (Bisphenol F) oligocarbonate, 2,2-Bis(3,5-dibrom-4-hydroxyphenyl)propan (Tetrabrombisphenol A) oligocarbonate und 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propan (Tetramethylbisphenol A) oligocarbonate, bisphenol S oligocarbonate, dihydroxydiphenylsulfid oligocarbonate, tetramethylbisphenol A oligocarbonate, 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) oligocarbonate, 1,1,1-Tris(4-hydroxyphenyl)-ethane (THPE) oligocarbonate;
• aliphatic oligoamide (PA), preferably PA 6 based on oligocaprolactam, PA 6.6 based on 6,6-hexamethylendiamin and adipic acid, PA 6.66 based on caprolactam, co-poymer of hexamethylendiamin and adipic acid, PA 66.610 based on hexamethylendiamin, cooligomer of adipic acid and sebaic acid, PA 4.6, PA10, PA 12 and PA cooligomers;
• oligourethane (PU),
• polar-cooligomere, maleic anhydride-olefin cooligomer;
• oligoalkylenoxide, oligoalkylene block cooligomer, propylenoxide-ethylenoxide cooligomer, (m)ethylene acrylate-maleic anhydride cooligomer;
• polar-teroligomere, preferably reactive teroligomers of ethylene, acrylic ester and maleic anhydride, or ethylene, methacrylic ester and maleic anhydride, or ethylene, acrylic esters and glycidyl methacrylate, or ethylene, methacrylic esters and glycidyl methacrylate, or ethylene, (meth)acrylic esters and methyl (methyl(meth)acrylate), ethyl (ethy(meth)acrylate), propyl (propyl(meth)acrylate), or butyl (butyl(meth)acrylate), oligoamide, oligoester-oligoamides, or butyl (butyl(meth)acrylate), oligoether-oligoamide cooligomers;
• polar oligomer blends, preferably oligocarbonate/oligoethylenterephthalate blends (PC/PET blends), oligocarbonate/oligobutyleneterephthalate blends (PC/PBT blends), blends of oligocyclohexylene dimethylene terephthalate cooligomer, blends of oligo(butylene-adipate-terephthalate);
• oligoacrylnitril and oligoacrylnitril-cooligomers, preferably oligo acrylonitrile butadiene styrene (ABS), oligo styrene-acrylonitrile;
• oligostyrene and oligostyrene cooligomers, preferably styrene/butadiene co-oligomer (SBR), oligo styrene-isoprene-styrene (SIS), oligo(glycidyl methacrylate) grafted sulfonamide based oligostyrene resin with tertiary amine;
• ethylene-vinyl acetate;
• oligoether, preferably oligoethyleneglycol, oligoethyleneglycol with at least one fatty acid coupled to the oligoethyleneglycol, oligoether with terminating functional groups, preferbyl NH₂-terminated oligoethers,
• functionalized oligoacrylamide oligomers, cooligomers and teroligomers, preferably oligo(2-acrylamido-2-aminopropionicacid) (oligoAMPA), oligo(2-acrylamido-2-amino propane sulfonic acid), oligo(N-isopropylacylamide (oligoPNIPAM); oligo (amidoamine-co-acrylic acid) co-oligomer, oligo(N,N-dimethylacrylamide-co-sodium acrylate), oligo(acrylamide-co-sodium acrylate)/oligo(ethylene glycol) semi-IPN, oligo(acrylamide-co-sodium 4-styrenesulfonate), oligo(acrylamide-co-sodium 4-styrenesulfonate)/oligo(ethylene glycol) semi-IPN, oligo(acrylamide-co-sodium methacrylate), oligo(acrylamide-co-sodium methacrylate)/oligo(ethylene glycol) semi-IPN, and/or oligo(N-isopropylacrylamide-co-acrylic acid) andoligo(acrylamide-co-acrylic acid;
• oligo(ether sulfones)/oligo(ethyleneimine) (PES/PEI);
• oligovinylpyrrolidone, preferably oligo(N-vinyl-2-pyrrolidone), oligo(N-vinyl-2-pyrrolidone-co-acrylonitrile) treated with hydroxylamine-hydrochloride
• oligovinyl alcohol;
• oligo(1-naphthylamine)-camphorsulphonic acid.

[0076] With regard to the oligoester based cooligomers that can be suitable used as a polar oligomers, these may further include but not limited to a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4-(hydroxymethyl)cyclohexylmethyl-4'-(hydroxymethyl)cyclohexane carboxylate represented by the following chemical formula 1 and a residue derived from 4,4-(oxybis(methylene)bis) cyclohexane methanol represented by the following chemical formula 2.

[0077] The compounds of chemical formula 1 and 2 can be cooligomerized with aromatic dicarboxylic acid may be one or more selected from a group consisting of terephthalic acid, dimethyl terephthalate, cyclic dicarboxylic acid, isophthalic acid, adipic acid, azelaic acid, naphthalene dicarboxylic acid, and succinic acid.

[0078] The diol-derived residue of the cooligomers may further include a residue derived from one or more other diols selected from a group consisting of 1,4-cyclohexane dimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexane dimethanol, 1,3-cyclohexane dimethanol, 2,2-dimethylpropane-1,3-diol (neopentyl glycol), ethylene glycol, and diethylene glycol. A content of the diol derived residues of the residue derived from 4-(hydroxymethyl)cyclohexylmethyl 4'-(hydroxymethyl)cyclohexane carboxylate, the residue derived from 4,4-(oxybis(methylene)bis) cyclohexane methanol, and other diol-derived residues may be about 10 to 80 mol% based on 100 mol% of the dicarboxylic acid co-monomer.

[0079] The synthetic or non-synthetic polar-oligomer may also comprise the oligoester based cooligomers used in a mixture with oligoethylene terephthalate (PET). The mixture may consist of 1 to 99 wt.-% of PET and 1 to 99 wt.-% of the oligoester based cooligomers, in order that both components add up to 100 wt.-%. Additionally or alternatively the compounds according to chemical formulas 1 and 2 may be used as co-monomers together with a further diol-component, e.g. ethylene glycol, in the preparation of the oligoester based cooligomers.

[0080] The oligoester based cooligomer may be prepared by reacting the dicarboxylic acid including the aromatic dicarboxylic acid with the diol including 4-(hydroxymethyl)cyclohexylmethyl 4'-(hydroxymethyl)cyclohexane carboxylate represented by chemical formula 1 and 4,4-(oxybis(methylene)bis) cyclohexane methanol represented by chemical formula 2 to perform an esterification reaction and a oligocondensation reaction. In this case, other diols such as 1,4-cyclohexane dimethanol, ethylene glycol, diethylene glycol, or the like, as described above may be further reacted, such that a oligoester based cooligomer further including other diol-derived residues may be prepared.

[0081] With regard to the oligoether these may comprise but not limited to compounds that contains at least one oligoethyleneglycol moiety and at least one fatty acid moiety coupled to the oligoethyleneglycol moiety. The oligoethyleneglycol moiety may contain 8 or 9 ethyleneglycol repeating units.

[0082] The fatty acid moieties may be saturated or unsaturated and may contain 10 to 30 carbon atoms, preferably 16 to 22 carbon atoms.

[0083] Examples of these fatty acid moieties are oleate, laureate, stearate, palmitate and ricinoleate. Examples of compound that contain at least one polyethyleneglycol moiety and at least one fatty acid moiety coupled to the polyethyleneglycol moiety include PEG 300 di-oleate, PEG 300-distearate, PEG 400 dioleate, PEG 400 distearate, PEG 400 monooleate, PEG 400 monoricinoleate, PEG 400 monostearate.

[0084] A specific preferred example may be ethoxylated sorbitan oligoester. The ethoxylated sorbitan oligoester comprises a sorbitan group which is substituted by four oligoethylene glycol substituents. The ethoxylated sorbitan ester may preferably comprise 14 to 26 ethylene glycol repeating units, preferably 16 to 24 ethylene glycol repeating units, more preferably between 18 and 22 repeating units. At least one of the ethylene glycol substituents in the ethoxylated sorbitan ester is connected via an ester bond to a fatty acid moiety. Preferably, at least two of the ethylene glycol substituents in the ethoxylated sorbitan ester are connected via an ester bond to a fatty acid moiety; more preferably at least three of the ethylene glycol substituents are connected via an ester bond to a fatty acid moiety. The fatty acid moieties may be saturated or unsaturated and may contain 10 to 30 carbon atoms, preferably 16 to 22 carbon atoms.

[0085] Examples of these fatty acid moieties are oleate, laureate, stearate and palmitate. Most preferred are ethoxylated sorbitan esters comprising four oligoethylene glycol substituents and wherein the ester comprises between 18 and 22 ethylene glycol repeating units and wherein three of the ethylene glycol substituents are connected to oleate, laurate or stearate groups.

Polar-additive and mixtures thereof

[0086] The polar additive may be solid at 23 °C. The polar additive may not be a colorizing agent. The polar additive may be solid at 23 °C and is not a colorizing agent. The polar additive may be solid at 23 °C and is not a colorizing agent, is selected different from the dispersing agent and is selected different from the solubilizer.

[0087] In connection to the polar-additive and according to an another embodiment the polar-additive having a Mw about ≥ 70 and < 600 g/mol may be selected from the group comprising aliphatic acids CH₃-[CH₂]_n-COOH acids (n about ≥ 3), amino acids, carboxylic acid amide, hydroxyl acids, fatty acids, aliphatic or aliphatic/aromatic aldehydes and ketones, esters, pentaerythritol, pentaerythritol dimers, pentaerythritol trimers, pentaerythritol ester, and preferably carboxylic acid ester, benzoic acid esters comprising benzylbenzoat or phenylbenzoat, phenylether, alcohols and polyvalent alcohols, preferably glycerine, amines, wherein the polar-additive is selected different to the organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol or ≥ 250 g/mol to about ≤ 550 g/mol; and preferably the polar-additive having a Mw about ≥ 100 and < 600 g/mol is containing a heteroatom selected from N, O, S and/or halogene. Preferably, halogens may be selected from the group comprising Cl, Br and I.

[0088] The polar-additive and according to an another embodiment the polar-additive having a Mw about ≥ 70 and < 600 g/mol may be selected from the group comprising ester of montanic acids with multifunctional alcohols. The montanic acids contained in raw montan wax are straightchain, unbranched monocarboxylic acids with a chain length in the range of C₂₈-C₃₂. As a result of the long chain these montanic acids have a high thermostability and a low volatility as well as a low tendency to migration. A powder thereof is used as lubricant and dispersing agent in a wide variety of polymers like PVC, PS, PBT, PA, PDM, PC, TPU.

[0089] Phosphoglycerides that can be suitable used are composed of glycerol esterified with two fatty acids on two of the hydroxy groups (OH groups). To one of the third, terminal OH groups is bound a phosphate group. This phosphate group is in turn esterified with different alcohols.

[0090] The carboxylic acid amide may comprise a compound according to formula C₂H₄(NHC(O)R³)₂, wherein R³ is a fatty acid moiety comprising 10-17 carbon atoms. The fatty acid moieties may be saturated or unsaturated. When the amount of carboxylic acid amide is too high the colored polar-polymer material may show blooming. Blooming i.e. discolorations may be caused by phase separation of the material's components. It may be caused by incompatibilities of the polar-additive with the polar-polymer and/or with the polar-polymer material.

[0091] Pentaerythritol may comprise a compound according to formula C(CH₂OR)₄, wherein R may be H, or wherein R may be a fatty acid moiety comprising 5-8 carbon atoms. The fatty acid moieties can be saturated or unsaturated. R may be also another moiety like ether, amide and/or urethane. As Pentaerythritol Perstorp Charmor PM 40 may be used.

[0092] Furthermore the polar additive may be an ether. Ether these may comprise but not limited to compounds that contains at least one ethyleneglycol moiety and at least one fatty acid moiety coupled to the ethyleneglycol moiety.

[0093] Examples of compound that contains at least one ethyleneglycol moiety and at least one fatty acid moiety coupled to the polyethyleneglycol moiety include PEG 300-monostearate, PEG 400 monolaurate.

[0094] The carboxylic acid ester may comprise a compound according to the following chemical formula 3:

wherein R¹ is an alkyl group comprising 1-20 carbon atoms and Z is hydrogen or a group according to the formula C(O)R², wherein R² is an alkyl group comprising 1-20 carbon atoms. R¹ may be the same or different and is an alkyl group comprising 1-20 carbon atoms, preferably 1-15 carbon atoms, more preferably 1-10 carbon atoms. R² is an alkyl group comprising 1-20 carbon atoms, preferably 1-10 carbon atoms, more preferably 1-5 carbon atoms. Non-limiting examples of the carboxylic acid ester are triethylcitrate, tributylcitrate, trihexylcitrate, acetyltributylcitrate (ATBC; R¹ = C₄H₉, Z = CH₃CO), propanoyltributylcitrate, acetyltrihexylcitrate and butanoyltriethylcitrate.

[0095] Furthermore, as polar-additive 4-(hydroxymethyl)cyclohexylmethyl-4'-(hydroxymethyl)cyclohexane carboxylate represented by the chemical formula 1, 4,4-(oxybis(methylene)bis) cyclohexane methanol represented by the chemical formula 2, and mixtures thereof may be used:

[0096] As already mentioned above, the synthetic or non-synthetic polar-polymer material that is colored may comprise a composition of a non-polar-polymer having a Mw about ≥ 1000 g/mol. In connection to this non-polar-polymer having a Mw about ≥ 1000 g/mol and according to an another embodiment the non-polar-polymer may be selected from the group of polyalkylene polymers, polyalkylene copolymers, polyakylene block copolymers. The non-polar-polymer may be preferably selected from of polymeric aliphatic or aromatic hydrocarbons, preferably polyalkylene polymers, polyalkylene co- and terpolymer with random or block-structure; and more preferred from polyethylen (PE), polypropylene (PP), polybutene (PB), polystyrene, polyisobutylene, polybutadiene, polyisoprene. Preferably the non-polar-polymer may have a wt.-% of heteroatoms below 5 wt.-% with respect to the mass of the non-polar-polymer.

[0097] According to a further preferred embodiment, wherein the non-polar-polymer is selected from the group of polyalkylene polymers, polyalkylene copolymers, polyakylene block copolymers; the non-polar-polymer is preferably selected from polymeric aliphatic or aromatic hydrocarbons, preferably polyalkylene polymers, polyalkylene co- and terpolymer with random or block-structure; and more preferred from polyethylen (PE), polypropylene (PP), polybutene (PB), polystyrene, polyisobutylene, polybutadiene, polyisoprene.

Organic aromatic coloring agent

[0098] It can be preferred that the organic aromatic coloring agent is not a chemical reactive dye. That means, if the coloring agent is not a chemical reactive dye, such organic aromatic coloring agent doesn't covalently bond to a component of the polymer material that is colorized by the organic aromatic coloring agent. The advantage is that this kind of organic aromatic coloring dye, which are not a chemical reactive dye, if used, the colored article can be decolorized by a decoloring method described herein. In this context forming no chemical covalent bond means that the organic aromatic coloring agent does not form a covalent sigma bond, covalent double bound, covalent triple bond or any other chemical covalent bond with the synthetic or non-synthetic polar-polymer material or with a component of the synthetic or non-synthetic polar polymer material.

[0099] The organic aromatic coloring agent for example gets adsorbed and/or absorbed to the polar-polymer component.

[0100] The organic aromatic coloring agent may have a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, preferably the organic aromatic coloring agent has a molecular weight Mw in the range of about ≥ 270 g/mol to about ≤ 450 g/mol, and more preferably the organic aromatic coloring agent has a molecular weight Mw in the range of about ≥ 285 g/mol to about ≤ 400 g/mol.

[0101] According to a further preferred embodiment, wherein the organic aromatic coloring agent in form of a powder may have an average particle diameter of about ≥ 50 nm to about ≤ 0.5 µm, preferably an average particle diameter of about ≥ 500 nm to about ≤ 2 µm.

[0102] According to a further preferred embodiment, wherein the organic aromatic coloring agent in form of a powder may have a particle size D₁₀ of about ≥ 300 nm and about ≤ 0.75 µm, preferaply the organic aromatic coloring agent has a particle size D₅₀ of about ≥ 450 nm and about ≤ 1.5 µm, and further preferred the organic aromatic coloring agent has a particle size D₁₀₀ of about ≥ 1 µm and about ≤ 3 µm.

[0103] The particle size is measured by sieving for separating particles of different sizes. Depending upon the size of particles to be separated, a sieve stack of sieves with different types of holes are used. A sieve stack consists of several sieves with increasing aperture size stacked upon each other and the sample is placed on the uppermost sieve. The stack is clamped to a sieve shaker and set into vibration for usually 5 to 10 minutes, preferably 10 minutes. As a result, the particles are distributed to the sieves in the stack as fractions according to their size. Ideally, the particles pass the smallest possible sieve aperture with their smallest projection surface.

[0104] Another method to measure the particle size can be done by means of laser diffraction according to ISO 8130-13:2001 and EN ISO 8130-13:2010. In particular the particle size can be measured with a static laser light analysis, also called laser diffraction, particle size is measured indirectly by detecting intensity distributions of laser light scattered by particles at different angles. Dynamic light scattering is based on the Brownian motion of particles in suspensions. Smaller particles move faster, larger particles move more slowly. The light scattered by these particles contains information about the diffusion speed and thus about the size distribution. The particle size determined is a hydrodynamic diameter. The Stokes-Einstein equation describes the relationship between particle size, diffusion rate, temperature and viscosity:

[0105] The organic aromatic coloring agent may absorb light in the visible spectrum; therefore it may appear to be colored for a human observer. Furthermore it may also be possible that the organic aromatic coloring agent absorbs light in the UV or in the infrared region of the electromagnetic spectrum. In this case the organic aromatic coloring agent may not appear to have a visible color to a human observer. It may also be possible that the organic aromatic coloring agent is a stabilizer to prevent the oxidation, chain fission, uncontrolled recombination and/or cross-linking reaction that are caused by photo-oxidation of the synthetic or non-synthetic polar polymer material. The synthetic or non-synthetic polar polymer material may become weathered by the direct or indirect impact of heat and ultraviolet light. This effect may amongst others be hindered by hindered amine light stabilizers (HALS).

[0106] Inprinting is also not limited to coloring agents that are visible or invisible to the human eye. Other organic molecules that correspond to the description of coloring agents, such as fragrances, may also be included.

[0107] Furthermore, the solubility of the organic aromatic coloring agent in water may be low. According to an another embodiment the organic aromatic coloring agent free of a sulfonic acid group may have a solubility in water at 23 °C of about ≤ 0.1 g/l and > 0 g/l, preferably about ≤ 0.05 g/l and > 0 g/l, more preferably about ≤ 0.005 g/l and > 0 g/l.

[0108] According to an another embodiment the organic aromatic coloring agent may comprise a sulfonic acid group may have a solubility in water at 23 °C of about ≥ 10 g/l, preferably a solubility in water at 90 °C of about ≥ 20 g/l.

[0109] The organic aromatic coloring agent may comprise at least 2 to 6 aromatic or heteroaromatic six-membered rings, or at least 3 to 5 aromatic or heteroaromatic six-membered rings and at least 1 to 4 five-membered rings. Furthermore, the aromatic coloring agent may have at least 2 to 6 aromatic or heteroaromatic six-membered rings and/or the organic aromatic coloring agent may comprises at least on heteroatom selected from N, O, S, Br.

[0110] Preferably the organic aromatic coloring agent is selected from the group comprising the following dyes having the chemical formulas A1 to A14 according to table 1:

Table 1

Chemical formula A1
Chemical formula A2
Chemical formula A3
Chemical formula A4
Chemical formula A5
Chemical formula A6
Chemical formula A7
Chemical formula A8
Chemical formula A9
Chemical formula A10
Chemical formula A11
Chemical formula A12
Chemical formula A13
Chemical formula A14

[0111] Regarding the chemical formula A7, the methoxy group -[OCH₃] may be an alternative for the hydroxyl group -[OH] on the aromatic moiety, that is not part of the anthraquinone ring system.

[0112] Further the organic aromatic coloring agent may be selected from the group comprising Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacat, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 2,2'-Thiobis(4-tert-octylphenolato)-n-butylamine nickel(II), N-(2-Ethoxyphenyl)-N'-(4-ethylphenyl)-ethlyene diamide. The organic aromatic coloring agent may include UV-absorbers form the company European Additives GmbH and the light stabilizers from the company MPI Chemie B.V.

[0113] Preferably the organic aromatic coloring agent is a dye and selected from the group comprising the coloring agents known under the trademark BEMACRON S/SE/E from CHT Germany GmbH, or from Dystar Pte Ltd. Preferably the organic aromatic coloring agent is selected from the group comprising BEMACRON Yellow S-6GF, BEMACRON Yellow S-4g, BEMACRON Yellow Brown S-2RF1, BEMACRON Orange S-g, BEMACRON Scarlet S-gFl, BEMACRON Scarlet S-BWF1, BEMACRON Rubine S-2GFL, BEMACRON Violet S-3R1, BEMACRON Violet S-B1F, BEMACRON Blue S-Bgl, BEMACRON Blue S-BB, BEMACRON Turquoise S-gF, BEMACRON Navy S-2gl, BEMACRON Navy S-31, BEMACRON Black S-31, BEMACRON Black S-T, BEMACRON Yellow SE-Rdl, BEMACRON Yellow SE-1F, BEMACRON Orange SE-Rdl, BEMACRON Red SE-4g, BEMACRON Pink SE-RE1, BEMACRON Red SE-3B, BEMACRON Red SE-Rdl, BEMACRON Blue SE-1F, BEMACRON Blue SE-Rdl, BEMACRON Navy SE-R1X, BEMACRON Black SE-R1X, BEMACRON Black SE-Rd2R, BEMACRON Yellow E-3gl, BEMACRON Red E-FB1, BEMACRON Blue E-FB1, and BEMACRON Black E-R.

[0114] More preferably the organic aromatic coloring agent is a dye and selected from the group comprising BEMACRON Black E-R, BEMACRON Yellow S-6GF, BEMACRON Rubine S-2GFL, BEMACRON Blue RS, BEMACRON Blue E-FBL 150, BEMACRON Red E-FBL, BEMACRON Blue S-BGL, BEMACRON Yellow E-3gl, BEMACRON Lumin. Yellow SEL-8G, and BEMACRON Lumin. Red SEL-G.

[0115] Furthermore the dye may be selected from the group of acid dyes comprising Bemacid Blau E-TL, Bemacid Rot E-TL or Bemacid Gelb E-TL, Bemacid Blue N-TF, Bemacid Red N-TF, Bemacid Yellow N-TF, Bemacid Leuchtgelb E-B, Bemacid Gelb E-4G, Bemacid Gelb E-T3R, Bemacid Gelb E-5R, Bemacid Leuchtrot E-B, Bemacid Rot E-KRL, Bemacid Rot E-T2B, Bemacid Rot E-3BS, Bemacid Blau E-2R, Bamacid Blau E-T4R, Bemacid Blau E-G, Bemacid Blau E-3GC, Bemacid Gelb N-2G, Bemacid Orange N-BG, Bemacid Rubin N-5B, Bemacid Bordeaux N-BL, Bemacid Blau N-5GL, Bemacid Marine N-5R, Bemacid Schwarz N-TMF,
or the group of metal complex dyes Bemaplex BEMAPLEX Gelb M-T, BEMAPLEX Rot M-T and BEMAPLEX Marine M-T.

[0116] Furthermore, the dye may be selected from the group comprising polymethine dyes. Preferably, the polymethine dyes from the companies BUFA GmbH & Co. KG, BUFA Chemikalien GmbH & Co. KG, BUFA Composite Systems GmbH & Co. KG, and/or BUFA Reinigunssysteme GmbH & Co. KG may be used.

[0117] Preferably the aromatic coloring agent may not comprise a phthalocyanine.

Agent

[0118] The agent may be liquid at 23 °C, preferably the agent is a composition that is liquid at 23 °C, wherein the liquid agent or liquid agent composition is a true solvent, colloid solution, emulsion, dispersion or suspension.

[0119] The agent may be selected from the group comprising organic solvents, water, dispersing agent, solubilizer, carrier agent, viscosity increasing agent, also named viscosifier, thickeners, surface tension modifier, also named surfactants, drying retarder, buffer, humactants, biocides, and/or defoamer/anti foaming additives.

[0120] The agent may be selected from the group comprising a C1 to C15 alcohol, C2 to C20 organic acid, C3 to C6 ketone, C3 to C5 aldehyde, C1 to C6 alkyl, C3 to C6 ester, alkylene glycol alkyl ether, glycol alkyl ether, glycol and glycol oligomers (e.g. PEG 200), glycol ether, ethanol, glycerol, acetone, formic acid, acetic acid, dimethylformamide, dimethylsulfoxide, acetyltributylcitrate, carboxymethylcellulose (CMC), fluorocarbons, fluorine derivates, silicones, hydrocarbons, alkylphosphates, buffers (such as acetic acid/Na-acetat) water or a mixture thereof, preferably the agent is selected from the group comprising glycol and glycol oligomers, ethanol, propanol, isopropanol, amyl alcohol (pentanol isomers), glycerol, acetone, methylethylketone, acetyltributylcitrate, tributylphosphate (defoamer), n-butyl acid ester, diethylenglycol-n-butyl-ether, water or mixture thereof.

[0121] According to a further preferred embodiment the agent may be selected from:

• n-butylacetat; or
• a mixture of glycerol, propanol and water; or
• a mixture of ethanol, amyl alcolhol, carboxymethylcellulose (CMC), tributylphosphate and water to 100%; or
• ethanol, dimethylformamid, tributylphosphate and water; or
• n-butylacetate, diethylenglycol-mono-n-butylether, tributylphosphate and water, or
• acetyltributylcitrat, diethylenglycol-mono-n-butylether, tributylphosphate and water.

[0122] According to a further preferred embodiment the agent may be selected from carboxylic acid ester, such as acetyltributylcitrat (ATBC) as a solvent, organic but not water-miscible solvents (the miscible are the solubilizers), additives, viscosifier, surface tension agents, humectants and/or buffers.

[0123] Most of the agent are liquid at 23 °C, only in the buffers are mixtures of acid / salt, here the salt may be not liquid, but dissolved.

Dispersing agent

[0124] The dispersing agent may be selected from the group comprising at least one:

• anionic tenside, preferably selected from polyphosphates, polyacrylates, aromatic sulfonates, esters with ethoxylate groups, esters with sulfonate groups, fatty acid-based polymers with an anionic group, salts of polycarboxylic acids, ethoxylates, thiourea dioxide;
• cationic tenside, preferably selected from quaternary ammonium compounds, fatty acid-polymers with a cationic group per molecule;
• non-ionic tenside, preferably selected from aromatic esters and hydrocarbons, aromatic and non-aromatic carboxylic acid esters, ethyl acrylate, fatty acid esters, ethoxylated fatty acid, poly oxyethylated compounds derived from sorbitol and oleic acid, polymers that are fatty acid-based with a non-ionic group per molecule, acrylate-copolymers, acrylate/styrene copolymers, fatty acid derivatives, polyalkoxylate;
• polyurethane (PUR) polymers and/or polyacrylate polymers, preferably linear or branched polyurethane (PUR) polymers and/or polyacrylate polymers, more preferred the polyurethane (PUR) polymer and/or polyacrylate polymer having a MW of 5000 to 30000 g/mol.

[0125] The polyacrylate polymers may be preferably selected from the Efka^® 4000 series from BASF SE.

[0126] Non-ionic tenside, in particular polysorbates, may increase the solubilty and/or solved concentration of the coloring agents as used according to the present invention, which are selected from organic aromatic coloring agents having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C, in the coloring composition solution. Therefore it can be preferred that the coloring composition solution comprises at least one polysorbate, preferably in an amount of ≥ 0.1 wt.-% to ≤ 5 wt.-% based on the total amount of the coloring composition solution.

[0127] Polysorbates are oily liquids derived from ethoxylated sorbitan, a derivative of sorbitol, esterified with fatty acids. Polysorbates, such as ethoxylated sorbitan ester, which can be used are described herein.

[0128] The dispersing agent may contain tertiary nitrogen compounds.

[0129] A dispersing agent that can be suitable used may be a substance that holds two or more immiscible liquids or solids in suspension, e.g., water and the organic aromatic coloring agent. Dispersing agents which may be used include ionic dispersing agent, non-ionic dispersing agent, or mixtures thereof. Typical ionic dispersing agents are anionic dispersing agents, including ammonium salts or alkali salts of carboxylic, sulfamic or phosphoric acids, for example, sodium lauryl sulfate, ammonium lauryl sulfate, lignosulfonic acid salts, ethylene diamine tetra acetic acid (EDTA) sodium salts and acid salts of amines such as laurylamine hydrochloride or poly(oxy-1,2 ethanediylphenyl)alpha-sulfo-omega-hydroxy ether with phenol 1-(methylphenyl)ethyl derivative ammonium salts; or amphoteric, that is, compounds bearing both anionic and cationic groups, for example, lauryl sulfobetaine; dihydroxy ethylalkyl betaine; amido betaine based on coconut acids; disodium N-lauryl amino propionate; or the sodium salts of dicarboxylic acid coconut derivatives. Typical non-ionic dispersing agents include but not limited to ethoxylated or propoxylated alkyl or aryl phenolic compounds, such as, octylphenoxypolyethyleneoxyethanol or poly(oxy-1,2-ethanediyl)alpha-phenyl-omega-hydroxy, styrenated. An another dispersing agent may be a mixture of C₁₄-C₁₈ and C₁₆-C₁₈ ethoxylated unsaturated fatty acids and poly(oxy-1,2-ethanediyl)alpha-sulfo-omega-hydroxy ether with phenol 1-(methylphenyl)ethyl derivative ammonium salts and poly(oxy-1,2-ethanediyl), alpha-phenyl-omega-hydroxy, styrenated.

Nonionic Dispersing Agents

[0130] Exemplary nonionic dispersing agents, also named nonionic tenside that can be used in the coloring composition solution are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters preferably containing 1 to 4 carbon atoms in the alkyl chain, more particularly the fatty acid methyl esters.

[0131] The nonionic low alkoxylated alcohol dispersing agents can be used to reduce surface tension, wet the soil particulate to allow penetration of the use solution, separation of the soil.

[0132] The alkoxylated alcohol dispersing agents mentioned above includes end caped alkoxylated alcohol dispersing agents.

[0133] Exemplary nonionic low alkoxylated alcohol dispersing agents that can be used are alkoxylated alcohols containing 1 to 4 ethylene oxide groups (1-4EO), 1 to 4 butylene oxide groups (1-4BO), 1 to 4 propylene oxide groups (1-4PO), end caped alkoxylated alcohol dispersing agents thereof or mixtures thereof.

[0134] Advantageously low alkoxylated alcohols useful according to the invention are particularly primary and/or branched alcohols, preferably containing 8 to 18 carbon atoms, and containing 1 to 4 ethylene oxide groups (1-4EO), 1 to 4 butylene oxide groups (1-4BO), 1 to 4 propylene oxide groups (1-4PO), end caped alkoxylated alcohol dispersing agents thereof or may contain a mixture. The alcohol radical may be linear, branched, or may contain a mixture.

[0135] Exemplary nonionic higher alkoxylated alcohol dispersing agents suitable for use in the coloring composition solution are alkoxylated alcohols containing 5 to 40 ethylene oxide groups (5-40EO), butylene oxide groups (5-40BO), propylene oxide groups (5-40PO), preferably 6 to 30 ethylene oxide groups (6-30EO), butylene oxide groups (6-30BO), propylene oxide groups (6-30PO), further preferred 7 to 20 ethylene oxide groups (7-20EO), butylene oxide groups (7-20BO), propylene oxide groups (7-20PO), more preferred 8 to 10 ethylene oxide groups (8-10EO), butylene oxide groups (8-10BO), propylene oxide groups (8-10PO), and most preferred 8 ethylene oxide groups (8EO), butylene oxide groups (8BO), propylene oxide groups (8PO) groups, end caped alkoxylated alcohol dispersing agents thereof, or mixtures thereof.

[0136] Advantageously higher alkoxylated alcohols useful in the composition of the invention are particularly linear and/or branched alcohols, preferably containing 8 to 18 carbon atoms, and 5 to 40 ethylene oxide groups (5-40EO), butylene oxide groups (5-40BO), propylene oxide groups (5-40PO), preferably 6 to 30 ethylene oxide groups (6-30EO), butylene oxide groups (6-30BO), propylene oxide groups (6-30PO), further preferred 7 to 20 ethylene oxide groups (7-20EO), butylene oxide groups (7-20BO), propylene oxide groups (7-20PO), more preferred 8 to 10 ethylene oxide groups (8-10EO), butylene oxide groups (8-10BO), propylene oxide groups (8-10PO), and most preferred 8 ethylene oxide groups (8EO), butylene oxide groups (8BO), propylene oxide groups (8PO), end caped alkoxylated alcohol dispersing agents thereof, or may contain a mixture. The alcohol radical may be linear, branched, or may contain a mixture.

[0137] Particularly preferred are higher alkoxylated alcohols, preferably alcohol ethoxylates with linear or branched radicals of alcohols with 12 to 18 carbon atoms, e. g. from coco-, palm-, tallow- or oleyl alcohol, containing 8 to 18 carbon atoms, and 5 to 40 ethylene oxide groups (5-40EO), butylene oxide groups (5-40BO), propylene oxide groups (5-40PO), preferably 6 to 30 ethylene oxide groups (6-30EO), butylene oxide groups (6-30BO), propylene oxide groups (6-30PO), further preferred 7 to 20 ethylene oxide groups (7-20EO), butylene oxide groups (7-20BO), propylene oxide groups (7-20PO), more preferred 8 to 10 ethylene oxide groups (8-10EO), butylene oxide groups (8-10BO), propylene oxide groups (8-10PO), and most preferred 8 ethylene oxide groups (8EO), butylene oxide groups (8BO), propylene oxide groups (8PO), end caped alkoxylated alcohol dispersing agents thereof, or may contain a mixture. However, most preferred is isotridecyl alcohol in the composition of the invention with 6EO to 14EO, 6PO to 14PO, 6BO to 14BO, preferably 7EO to 10EO, 7PO to 10PO, 7BO to 10BO, and most preferred 8EO, 8PO, 8BO, or may contain a mixture.

[0138] According to the present invention higher alkoxylated alcohols can be used with 5EO, 6EO, 7EO, 8EO, 9EO, 10EO, 11EO, 12EO, 13EO, 14EO, 15EO, 16EO, 17EO, 18EO, 19EO, 20EO, 21EO, 22EO, 23EO, 24EO or 25EO, 5PO, 6PO, 7PO, 8PO, 9PO, 10PO, 11PO, 12PO, 13PO, 14PO, 15PO, 16PO,17PO, 18PO, 19PO, 20PO, 21PO, 22PO, 23PO, 24PO or 25PO, 5BO, 6BO, 7BO, 8BO, 9BO, 10BO, 11BO, 12BO, 13BO, 14BO, 15BO, 16BO,17BO, 18BO, 19BO, 20BO, 21BO, 22BO, 23BO, 24BO or 25BO, end caped alkoxylated alcohol dispersing agents thereof, or may contain a mixture.

[0139] Exemplary higher alkoxylated alcohols with 5EO to 40EO, preferably 6EO or 30EO, further preferred 7EO to 20EO, more preferred 8EO to 10EO and most preferred 8EO; 5PO to 40PO, preferably 6PO or 30PO, further preferred 7PO to 20PO, more preferred 8PO to 10PO and most preferred 8PO; 5BO to 40BO, preferably 6BO or 30BO, further preferred 7BO to 20BO, more preferred 8BO to 10BO and most preferred 8BO include C₁₂-C₁₄-alcohols; C₉-C₁₁-alcohols, C₁₃-C₁₅- alcohols, C₁₂-C₁₈-alcohols, end caped alkoxylated alcohol dispersing agents thereof, and mixtures thereof, as well as mixtures of C₁₂-C₁₄-alcohols and C₁₂-C₁₈ -alcohols, end caped alkoxylated alcohol dispersing agents thereof, and most preferred is a C₁₃-alcohol.

[0140] In addition to these nonionic dispersing agents, fatty alcohols containing more than 12 EO, 12 PO, 12 BO may also be used. Examples of such fatty alcohols are tallow fatty alcohol containing 14 EO, 25 EO, 30 EO or 40 EO, 14 PO, 25 PO, 30 PO or 40 PO, 14 BO, 25 BO, 30 BO or 40 BO and end caped alkoxylated alcohol dispersing agents thereof.

[0141] The degrees of 5EO to 40EO, 5PO to 40PO, 5BO to 40BO preferably 6EO or 30EO, 6PO or 30PO, 6BO or 30BO,further preferred 7EO to 20EO, 7PO to 20PO, 7BO to 20BO,more preferred 8EO to 10 EO, 8PO to 10 PO, 8BO to 10 BO and most preferred 8EO, 8PO, 8BO alkoxylation mentioned are statistical mean values, which for a special product, may be either a whole number or a fractional number. However, more preferred, the degrees of 5EO to 40EO, 5PO to 40PO, 5BO to 40BO preferably 6EO or 30EO, 6PO or 30PO, 6BO or 30BO further preferred 7EO to 20EO, 7PO to 20PO, 7BO to 20BO, more preferred 8EO to 10 EO, 8PO to 10 PO, 8BO to 10 BO and most preferred 8EO, 8PO, 8BO alkoxylation mentioned may be either a whole number or a fractional number. Most preferred, the degrees of 5EO to 40EO, 5PO to 40PO, 5BO to 40BO, preferably 6EO or 30EO, 6PO or 30PO, 6BO or 30BO, further preferred 7EO to 20EO, 7PO to 20PO, 7BO to 20BO, more preferred 8EO to 10 EO, 8PO to 10PO, 8BO to 10BO and most preferred 8EO, 8PO, 8BO. The alkoxylation grade mentioned may be a whole number.

[0142] Preferred higher alkoxylated alcohols have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0143] Further dispersing agents include alkoxylated long chain fatty acid amides where the fatty acid has 8-20 carbon atoms and the amide group is alkoxylated with 1-20 ethylene oxide, propylene oxide and/or butylene oxide units.

[0144] A further class of nonionic dispersing agents, which can be used in the aqueous dispersed coloring composition solution, is that of the alkyl polyglycosides (APG). Suitable alkyl polyglycosides satisfy the general Formula RO(G)z where R is a linear or branched, particularly 2-methyl-branched, saturated or unsaturated aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms and G stands for a glycose unit containing 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization z is a number between 1.0 and 4.0 and preferably between 1.1 and 1.4.

[0145] Silicone containing nonionic dispersing agents, such as the ABIL B8852 or Silwet 7602, can also be used. An exemplary silicone-containing dispersing agent is silicone polybutane.

[0146] Examples of amine oxide dispersing agents include: dimethyldodecylamine oxide, dimethyltetradecylamine oxide; ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, lauryl dimethyl amine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, bis- (2-hydroxyethyl)-3-dodecoxy-1- hydroxypropyl amine oxide, (2-hydroxypropyl) methyltetradecylamine oxide, dimethyloleyamine oxide, dimethyl- (2-hydroxydodecyl) amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.

[0147] Additional nitrogen-containing dispersing agents include ethoxylated primary alkyl amines where the alkyl group has 10-20 carbon atoms and the amine is ethoxylated with 2-20 ethylene oxide units.

[0148] Additionally, non-ionic dispersing agents derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine are also useful. For example, there are compounds containing from 40% to 80% of polyoxyethylene by weight and having a molecular weight from 5,000 to 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product from ethylene diamine and excess propylene oxide wherein the base has a molecular weight on order of 2,500-3, 000.

[0149] Suitable nonionic dispersing agents include the polyoxyethylene-polyoxypropylene condensates, which are sold by BASF under the trade name 'Pluronic', polyoxyethylene condensates of aliphatic alcohols/ethylene oxide condensates having from 1 to 30 moles of ethylene oxide per mole of coconut alcohol; ethoxylated long chain alcohols sold by Shell Chemical Co. under the trade name 'Neodol', polyoxyethylene condensates of sorbitan fatty acids, alkanolamides, such as the monoalkoanolamides, dialkanolamides and the ethoxylated alkanolamides, for example coconut monoethanolamide, lauric isopropanolamide and lauric diethanolamide; and amine oxides for example dodecyldimethylamine oxide.

[0150] Further exemplary non-ionic dispersing agents include alkylphenol alkoxylates, and amine oxides such as alkyl dimethylamine oxide or bis (2- hydroxyethyl) alkylamine oxide.

[0151] The additional nonionic dispersing agents can be provided in the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, in an amount of ≥ 0 wt.-% to ≤ 40 wt.-%, preferably ≥ 0.1 wt.-% to ≤ 35 wt.-%, further preferred ≥ 0.5 wt.-% to ≤ 32 wt.-%, and more preferred 1.0 wt.-% to 30 wt.-%, based on the weight of all components of the total composition.

[0152] It should be understood that the addition of a nonionic dispersing agent to the coloring composition solution can be omitted.

Anionic Dispersing Agents

[0153] Exemplary anionic dispersing agents, also named anionic tensides that can be used include organic carboxylates, organic sulfonates, organic sulfates, organic phosphates and the like, particularly linear alkylaryl sulfonates, such as alkylarylcarboxylates, alkylarylsulfonates, alkylarylphosphates, and the like. These classes of anionic dispersing agents are known within as linear alkyl benzyl sulfonates (LABS), alpha olefin sulfonates (AOS), alkyl sulfates, and secondary alkane sulfonates.

[0154] The anionic dispersing agents can be provided in the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, in an amount of ≥ 0 wt.-% to ≤ 40 wt.-%, preferably ≥ 0.1 wt.-% to ≤ 35 wt.-%, further preferred ≥ 0.5 wt.-% to ≤ 32 wt.-%, and more preferred 1.0 wt.-% to 30 wt.-%, based on the weight of all components of the total composition.

[0155] It should be understood that the addition of an anionic dispersing agent to the coloring composition solution can be omitted.

Cationic Dispersing Agents

[0156] In a preferred embodiment of the coloring composition solution comprises a cationic dispersing agent, also named cationic tenside.

[0157] Suitable cationic dispersing agents include quaternary ammonium compounds having the formula of RR'R'' R'''N⁺X^-, where R, R', R" and R''' are each a C₁-C₂₄ alkyl, aryl or arylalkyl group that can optionally contain one or more P, O, S or N heteroatoms, and X is F, Cl, Br, I or an alkyl sulfate. Additional preferred cationic dispersing agents include ethoxylated and/or propoxylated alkyl amines, diamines, or triamines.

[0158] Each of R, R', R" and R''' can independently include, individually or in combination, substituents including 6 to 24 carbon atoms, preferably 14 to 24 carbon atoms, and more preferably, 16 to 24 carbon atoms.

[0159] Each of R, R', R" and R''' can independently be linear, cyclic, branched, saturated, or unsaturated, and can include heteroatoms such as oxygen, phosphorous, sulfur, or nitrogen. Any two of R, R', R" and R''' can form a cyclic group. Any one of three of R, R', R" and R''' can independently can be hydrogen. X is preferably a counter ion and preferably a non-fluoride counter ion. Exemplary counter ions include chloride, bromide, methosulfate, ethosulfate, sulfate, and phosphate.

[0160] In an embodiment, the quaternary ammonium compound includes alkyloxylated quaternary ammonium salts (or amines), preferably ethyloxylated and/or propoxylated quaternary ammonium salts (or amines). Preferably, the alkyl group contains between about 6 and about 22 carbon atoms and can be saturated and/or unsaturated. The degree of alkoxylation is preferably between about 2 and about 20, and/or the degree of propoxylation is preferably between about 0 and about 30.
In an embodiment, the quaternary ammonium compound includes an alkyl group with about 6 to about 22 carbon atoms and a degree of alkoxylation between about 2 and about 20.

[0161] The cationic dispersing agents can be provided in the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, in an amount of ≥ 0 wt.-% to ≤ 40 wt.-%, preferably ≥ 0.1 wt.-% to ≤ 35 wt.-%, further preferred ≥ 0.5 wt.-% to ≤ 32 wt.-%, and more preferred 1.0 wt.-% to 30 wt.-%, based on the weight of all components of the total composition.

[0162] It should be understood that the addition of a cationic dispersing agent to the coloring composition solution can be omitted.

Amphoteric Dispersing Agents

[0163] The coloring composition solution is preferably free of amphoteric dispersing agents.

[0164] Examples of suitable amphoteric dispersing agents include capryloamphopropionate, disodium lauryl B-iminodipropionate, and cocoamphocarboxypropionate, and disodium octylimino dipropionate.

[0165] The amphoteric dispersing agents can be provided in the composition in an amount of ≥ 0 wt.-% to ≤ 40 wt.-%, preferably ≥ 0.1 wt.-% to ≤ 35 wt.-%, further preferred ≥ 0.5 wt.-% to ≤ 32 wt.-%, and more preferred 1.0 wt.-% to 30 wt.-%, based on the weight of all components of the total composition.

[0166] It should be understood that the addition of an amphoteric dispersing agent to the coloring composition solution can be omitted.

Solubilizer

[0167] The solubilizer is selected different to the dispersing agent and may be used in addition to the dispersing agent. The solubilizer is at least partially soluble at 23° C and may be selected from the group comprising a C₁ to C₆ alcohol, C₂ to C₂₀ organic acid, C₃ to C₆ ketone, C₃ to C₅ aldehyde, C₁ to C₆ alkyl, C₃ to C₆ ester, alkylene glycol alkyl ether, glycol alkyl ether,; preferably glycol and glycol oligomers, ethanol, acetone, formic or acetic acid, dimethylformamide or dimethylsulfoxide.

[0168] Furthermore, the solubilizer may be a compound according to the following formula R'-[(O(CH₂)_m)_n-]OH, wherein R' is an ethyl, propyl or butyl, m is 2, 3 or 4, and n is 1, 2 or 3, with the proviso that where R' is butyl m is 2 or 4. The solubilizer may be selected from the group consisting of ethylene glycol butyl ether, diethylene glycol ethylether, diethylene glycol butylether, propylene glycol propylether, dipropylene glycol propyl ether and tripropylene glycol propylether.

[0169] Furthermore, the solubilizer may be a compound according to the following formula H-[(O(CH₂)_m)_n-]OH, where m is 2, 3 or 4 and n is 1, 2, or 3. The solubilizer may be selected from the group consisting of diethylene glycol, triethylene glycol and 1,4 butanediol. Preferably the solubilizer forms a homogenous solution with water.

Carrier agent

[0170] The carrier agent is selected different to the dispersing agent and the solubilizer and may be used in addition to the dispersing agent.

[0171] With respect to result of the coloring process it may be advantages when the coloring composition solution further comprises a carrier agent. According to an another embodiment the coloring composition solution may comprise in addition a carrier agent, wherein the carrier agent is preferably selected from the group comprising aromatic esters such as benzoic acid or phthalic acid esters, polyphenylether, phenoles, aromatic alcohols, aromatic ketones, aryl halides, such as halogenized benzene, halogenzide toluene; N-alkylphthalimide, methylnaphthaline, diphenyle, diphenylethere, naphtholether, and oxybiphenyle. Carriers may also be of natural origin such as coumarin or vanillin. Preferably the carrier agent does not form a homogenous solution with water. The carrier agent may decrease the time that is used for coloring and/or enhance the penetration capacity of the organic aromatic coloring agent.

Additives

[0172] According to one embodiment at least one additive can be added to the solution. Suitable additives that can be used are viscosity increasing agent (viscosifier, thickeners), surface tension modifier (surfactants), drying retarder, buffer, humactants, biocides, and/or defoamers or antifoaming additives.

Viscosifer

[0173] According to one embodiment the viscosity of the solution can be adjusted to a desired viscosity value by adding a viscosity increasing agent. Suitable viscosity ranges of the solution may be in the range of about ≥ 0.5 Pa•s to about ≤ 1,000,000 Pa·s, preferably in the range of about ≥ 0.75 Pa·s to about ≤ 500,000 Pa·s, and more preferred in the range of about ≥ 1 Pa·s to about ≤ 100,000 Pa·s.

[0174] Viscosifiers that can be suitable used are selected from the group comprising glycerol, glycols (PEG200) and/or carboxymethylcellulose (CMC).

[0175] The viscosity is measured with a Brookfield LVDVII+, 500 ml of solution sample in a 600 ml beaker, spindle 3 at 20rpm, 25°C, and measurement taken after 30s.

[0176] Substances for adjusting the viscosity that can be used are known viscosity increasing agent such as glycerol, glycols (PEG200), carboxymethylcellulose (CMC), silicone, polyvinyl alcohols, acrylate based compounds, methacrylate based compounds and there like.

Surface tension and Surface Energy

[0177] Plastics/polymers generally have a low surface energy and are difficult to wet. In order to achieve a good wetting of the surface of the plastic (large contact angle), the surface tension of the coloring composition solution also referred to "solution" should not deviate too much from the surface tension of the plastic (surface energy and surface tension are both measured in dynes/cm) and should be somewhat lower than the surface energy. Accordingly, the surface tension of the solution is matched to the surface energy of the plastic surface.

[0178] Suitable surface tensions of the coloring composition solution also referred to "solution" may be in the range of about ≥ 20 dynes/cm to ≤ 60 dynes/cm, preferably ≥ 25 dynes/cm to ≤ 50 dynes/cm, further preferred ≥ 30 dynes/cm to ≤ 45 dynes/cm, and more preferred ≥ 35 dynes/cm to ≤ 45 dynes/cm.

[0179] The surface energy of plastic surfaces is measured with dyne pencils of the company Dynelevel: The surfaces are coated with inks of known surface tension. If no perfect wetting of the surface can be observed and if the ink is drawn together into drops, the surface tension of the ink is higher than the surface energy of the plastic surface. The test is repeated with dyne pens of decreasing surface tension. In the case of the dyne pen, where the ink no longer contracts into drops, the surface tension and surface energy are identical.

[0180] The surface tension of the coloring composition solution also referred to "solution" is determined by the ring method according to Du Noüy using the Force Tensiometer - K100 from Krüss: The force acting on a ring and related to the wetted length is measured, which is generated when the ring is moved from one phase to the other by the tension of the extracted liquid lamella.

[0181] In standard printing processes, in which the ink is bonded to the plastic surface by a binder, a similar surface energy and tension results in good adhesion of the ink to the plastic surface and to avoid air entrapment, crater formation, poor flow and leveling, pinholes and crawling. With InPrinting, the adjustment of the surface tension serves to adjust the drop size and the contact angle of the coloring composition on the plastic surface and thus good absorption/adsorption of the dyes on the plastic surface and rapid migration into the surface.

[0182] For example fluorochemicals, silicones such as polydimethysiloxane (PDMS), modified PDMS with polyethers such as Ethyleneoxide or Propylenoxide or phenyl groups for high temperature applications or hydrocarbons such as xylene, mineral spirits or mineral oils may be used to adjust the surface tension and/or contact angle of the coloring composition solution on the substrate area to be colorized.

Surfactants

[0183] In order to improve the wettability of plastic surfaces, they are often treated with corona, plasma or flame to increase surface energy. Surfactants are also added to the coloring composition solution to improve wettability of plastic surfaces with liquids.

[0184] Surfactants come from the same substance classes as surface tension modifiers. For example fluorocarbons and hydrocarbons may be used to adjust the surface energy and/or contact angle of the substrate area to be colorized.

Drying retarder

[0185] Drying retarders prevent the coloring composition solution from drying too quickly. On the one hand, this prevents the nozzles in the inkjet print head from clogging up, on the other hand it maintains the high mobility of the dye molecules so that a faster migration into the plastic takes place.

[0186] Substances for adjusting the drying speed that can be used are high-boiling organic solvents such as alcohols, esters or glycol and its oligomers and derivates such as mono- or diether or solvents such as dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO).

Buffer

[0187] Buffers keep the pH value of a coloring composition solution constant and avoid undesirable reactions such as the precipitation of ingredients from the coloring composition solution that are only soluble in a certain pH range. Furthermore, mechanisms often run at different speeds with different pH values. Here the buffers keep the pH value and thus the reaction or migration rate at a certain constant level.

[0188] Substances for stabilizing the pH value that can be used are acetic acid buffer (acetic acid / Na-acetat), carbonate buffer (carbonic acid/hydrogen carbonates), HEPES-buffer (4-(2-Hydroxyethyl)-1-piperazinethanesulfonic acid), carbonic acid silicate buffer and/or phosphate-buffer acc. to Sorenson.

Humactants

[0189] Humectants (moisturizers) are mainly used to control or limit the evaporation of the inks. Substances to be used as humectants are glycols and alcohols that act as hygroscopic agents to remove moisture from the air during printing or in the idle position of printer, thus preventing clogging of print heads.

Biocides (Antifoulings)

[0190] Aqueous coloring composition solutions tend to germ formation during long service lives at slightly elevated temperatures. On the one hand this leads to unpleasant odours, on the other hand it has a negative influence on the print quality, e.g. through the formation of suspended particles.

[0191] Substances to be used as biocides are copper and copper compounds, for example dicopper oxide, copper pyrithione, copper thiocyanate), zinc oxide (not officially defined as a biocide). Other common biocides are zinc pyrithione, zineb, isothiazolinone, dichlofluanid and tolylfluanid as well as tralopyril and medetomidine, preferably in an amount of an addition 0.05 wt.-% to 1 wt.-%.

Defoamer/Antifoaming Additives

[0192] Air bubbles or foam lead to insufficient wetting of the plastic surface, so that color differences occur at these points due to poorer color migration into the plastic. Defoamers prevent the formation and accumulation of air bubbles/scahum on the surface to be colored.

[0193] Substances to be used as antifoaming agents/defoamers are often based on mineral oils (hydrocarbons). Typical active ingredients of alternative products are silicones, phosphoric acid esters (especially. tributylphosphates), fatty acid compounds, high molecular alcohols, fluorine derivatives, and mixtures of these components. (addition 0.05 - 5%).

Coloring composition

[0194] A coloring composition also named coloring composition solution may comprise at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C and is dissolved in a solvent. The solvent may be selected beside water from alcohols, esters, ketones and aldehydes, DMF, DMSO, chlorinated solvents such as methylene chloride, or a solvent mixture of at least two solvents differs in its boiling point.

[0195] According to a further preferred embodiment, wherein the coloring composition comprises a non-soluble / miscible cosolvent, for example N-butyl acetate or ATBC, which is added to the water, in which the at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol dissolves molecularly. Drops of the coloring composition, which for example finely distributed by means of ultrasound, may be used to color inprinting a heated area of the synthetic or non-synthetic polar-polymer material. These drops of the coloring composition may be comprise highly concentrated organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol. The concentration of the dye in the drops, based on the total weight of the drop, is ≥ 0.1 wt.-% to ≤ 15 wt.-%, preferably ≥ 1 wt.-% to ≤ 14% wt.-%, further preferred ≥ 2 wt.-% to ≤ 12% wt.-%. The addition of an emulsifier such as phosphoglycerides may be useful for improving the storage stability of the coloring composition.

[0196] According to a further preferred embodiment, wherein the coloring composition exposed to the heated area of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized has a temperature higher than the glass-transition temperature Tg of the synthetic or non-synthetic polar-component of the synthetic or non-synthetic polar-polymer material to be colored; and/or the coloring composition exposing the synthetic or non-synthetic polar-polymer material has a temperature lower than the heat deflection temperature of the synthetic or non-synthetic polar-polymer material to be colored.

[0197] According to a further preferred embodiment, wherein the coloring composition exposed to the heated area of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized has a temperature that is at least 30° C, preferably at least 40° C, and ≥ 0° C ± 5° C to ≤ 30° C above the temperature of the heated area of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized; or wherein the coloring composition exposed to the heated area of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized has a temperature that is at least 40° C and ≥ 0° C to ≤ 20° C below or above the temperature of the heated area of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized; or wherein the coloring composition exposed to the heated area of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized has a temperature that is at least 40° C and ≥ 0° C to ≤ 10° C below or above the temperature of the heated area of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized.

[0198] According to a further preferred embodiment, wherein the step of:

• exposing the heated outer surface of, or
• of exposing the partial heated outer surface of, or
• of exposing the heated outer surface, wherein areas not to be colored by inprinting are covered, of,

the synthetic or non-synthetic polar-polymer material that is to be colored by inprinting to the coloring composition comprises:

• dipping at least the outer surface or the heated outer surface, wherein areas that should not be colorized are covered, or dipping at least the heated intended pattern area of the outer surface to be colored, of the heated area of the synthetic or non-synthetic polar-polymer material into the coloring composition to be colorized; and/or
• flow coating at least the outer surface that corresponds to the intended pattern of the heated area of the synthetic or non-synthetic polar-polymer material with the coloring composition solution; and/or- digitally printed via inkjet printing or inkjet transfer printing at least the outer surface that corresponds to the intended pattern of the heated area of the synthetic or non-synthetic polar-polymer material with the coloring composition solution; and/or
• analogue printing via screen, gravure, offset, flexo or pad printing the outer surface of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material with the coloring composition solution; and/or
• spray coating at least the outer surface that corresponds to the intended pattern area of the synthetic or non-synthetic polar-polymer material with the coloring composition solution; and/or
• pen coating at least the outer surface that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material with the coloring composition solution; and/or
• direct or indirect coating at least the outer surface that corresponds to the intended pattern area of the synthetic or non-synthetic polar-polymer material with the coloring composition solution; and/or combinations thereof.

[0199] According to a further preferred embodiment, wherein the heated area that corresponds to the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colored by inprinting, which is exposed to the coloring composition solution, has a temperature about ≥ 40° C and lower than the heat deflection temperature of the synthetic or non-synthetic polar-polymer material.

[0200] According to a further preferred embodiment, wherein the outer surface of the synthetic or non-synthetic polar-polymer material that is not supposed to be colorized by the coloring composition solution has a temperature ≤ 40° C.

[0201] According to a further preferred embodiment, wherein the synthetic or non-synthetic polar-polymer material is formed in a molding process, a compression molding process, an extruding process, a thermoforming process and/or a blowing process.

[0202] According to a further preferred embodiment, wherein the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material that is to be colorized, is colorized by the coloring composition by means of a 2D-printing process.

[0203] With print-to-object/print-to-shape, either the object to be printed or the print head is guided in such a way that the distance between the two remains as constant as possible in order to produce a flawless print image. For products with an exposed position and planar surface to be pattern colorized/printed, such as containers, the products to be colorized by a pattern can be moved on a conveyor belt passing the print head(s) at a certain speed. Using complex 3D components, the component or the print head must be moved in order to reach all surfaces to be printed by the pattern and to print with constant quality.

[0204] According to a further preferred embodiment, wherein the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material that is to be colorized is colorized by the coloring composition by means of a printing process in which the print head is guided in all 3 dimensions around the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material kept at a constant distance to be printed, e.g. a 5-axis robot.

[0205] According to a further preferred embodiment, wherein the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material that is to be colorized, is colorized by the coloring composition by means of a printing process in which the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material is guided in all 3 dimensions around the print head kept at a constant distance to be printed e.g. a 5-axis robot.

[0206] According to a further preferred embodiment, wherein the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material for coloring is exposed to the coloring composition for about > 0 seconds to about ≤ 600 seconds, preferably about ≥ 0.01 seconds to about ≤ 300 seconds, in addition preferred about ≥ 0.1 seconds to about ≤ 100 seconds, and also preferred about ≥ 0.3 seconds to about ≤ 5 seconds, or about ≥ 0.5 seconds to about ≤ 1 second.

[0207] According to a further preferred embodiment, wherein the coloring composition comprises:

• about ≥ 0.1 wt.-% to about ≤ 25 wt.-% at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol;
• about ≤ 99.9 wt.-% to about ≥ 75 wt.-% of the agent.

[0208] According to a further preferred embodiment, wherein the coloring composition comprises:

• about ≥ 0.1 wt.-% to about ≤ 25 wt.-% at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol; and
• about ≤ 99.9 wt.-% to about ≥ 75 wt.-% of the agent;
• about ≥ 0 wt.-% to about ≤ 20 wt.-% of at least one dispersing agent for dispersing the organic aromatic coloring agent in the aqueous coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, and
• ≥ 0 wt.-% water and preferably water is added to 100 wt.-%.

[0209] According to a further preferred embodiment, wherein the coloring composition comprises:

• about ≥ 0.1 wt.-% to about ≤ 25 wt.-% , preferably about ≥ 0.5 wt.-% to about ≤ 15 wt.-%, of at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol;
• about ≤ 99.9 wt.-% to about ≥ 55 wt.-% of the agent,
• about ≥ 0.01 wt. -% to about ≤ 20 wt.-% of dispersing agent, preferably one dispersing agent, for dispersing the organic aromatic coloring agent in the aqueous coloring composition solution or non-aqueous solution, wherein the non-aqueous solution can be instead of a dispersion a homeogenius solution,
• about ≥ 0 wt.-% to about ≤ 10 wt.-% of least one buffer,
• about ≥ 0.05 wt.-% to about ≤ 10 wt.-% of at least one carrier agent, and
• ≥ 0 wt.-% water and preferably water added to 100 wt.-%.

[0210] According to a further preferred embodiment, wherein the coloring composition solution has a pH in the range of about ≥ 2.5 and about ≤ 12, preferably a pH in the range of about ≥ 3.0 and about ≤ 10; in addition preferred a pH in the range of about ≥ 3.2 and about ≤ 7 and also preferred a pH in the range of about ≥ 4 and about ≤ 5.

[0211] According to a further preferred embodiment, wherein the synthetic or non-synthetic polar-polymer material comprises at least two layers, wherein at least a first layer is of a polar-polymer material, that comprises about ≥ 0.5 wt.-%, preferably about ≥ 5 wt.-%, more preferably ≥ 10 wt.-%, of polar components, such as synthetic or non-synthetic polar polymer, synthetic or non-synthetic polar oligomer and/or polar additive, and is colorable by the coloring composition, where else the second layer comprising less than about 5 wt.-%, preferably about < 3 wt.-%, further preferred about < 2 wt.-% and in addition preferred about < 0.5 wt.-% or about ≥ 0 to < 0.1 wt.-% of a polar component and about ≥ 90 wt.-%, preferably about ≥ 95 wt.-% to about ≤ 100 wt.-% of at least one non-polar component, such as non-polar polymer and/or non-polar oligomer, cannot be colorized by the coloring composition.

[0212] Another object is directed to colored synthetic or non-synthetic polar-polymer material, wherein the synthetic or non-synthetic polar-polymer material, preferably the outer surface of the synthetic or non-synthetic polar-polymer material, is reversibly colored by inprinting according to a method of the present invention.

[0213] According to a further preferred embodiment, wherein the colored synthetic or non-synthetic polar-polymer, preferably the outer surface of the synthetic or non-synthetic polar-polymer material, material exhibits a roughness or a structure.

[0214] According to a further preferred embodiment, wherein the surface of the colored synthetic or non-synthetic polar-polymer material, preferably the outer surface of the synthetic or non-synthetic polar-polymer material, is mirror smooth.

[0215] According to a further preferred embodiment, wherein the colored synthetic or non-synthetic polar-polymer material comprises at least one synthetic or non-synthetic polar-component layer and at least one non-polar-component layer, wherein at least one layer or outer surface of the synthetic or non-synthetic polar-component layer is reversibly colored by an inprinting process according to the present invention, wherein the non-polar-component layer is not colorable by the inprinting process according to the present invention.

[0216] According to a further preferred embodiment, wherein the colored synthetic or non-synthetic polar-polymer material according to claim 37 or 38, wherein at least a layer thickness of about ≥ 0.1 µm, preferably of about ≥ 1 µm to about ≤ 1000 µm, of the colored synthetic or non-synthetic polar-polymer material is homogenous colored.

[0217] According to a further preferred embodiment, wherein the colored synthetic or non-synthetic polar-polymer material comprises a concentration of the organic aromatic coloring agent in at least one colored layer of the synthetic or non-synthetic polar-polymer material, colored by a the inprinting process according to the present invention, is ≥ 0.00001 wt.-% to about ≤ 5 wt.-%, wherein the colored layer has a thickness of about ≥ 0.1 µm, based on the total weight of said colored layer.

[0218] Another object of the present invention is directed to an article comprising at least one colored synthetic or non-synthetic polar-polymer material colored by an inprinting process according to the present invention.

[0219] According to a further preferred embodiment, wherein the article is selected from the group comprising a sheet, a foil, a container, a part, a bottle, a non-woven fabric, and preferably the article is selected from the group comprising computer face-plates, keyboards, bezels and cellular phones, color coded packaging and containers of all types, including ones for industrial components, residential and commercial lighting fixtures and components thereof, such as sheets, used in building and in construction, tableware, including plates, cups and eating utensils, small appliances and their components, optical and sun-wear lenses, decorative films including such films that are intended for use in film insert molding, performs, floor panel, wall panel or crucible.

Temperature

[0220] It may be preferred that the temperature of the coloring composition solution is adjusted according to specific properties of the synthetic or non-synthetic polar-polymer material. For example the temperature of the coloring composition solution exposed to the outer surface of the synthetic or non-synthetic polar-polymer material may be adjusted such that the temperature of the coloring composition solution is higher or same than the glass-transition temperature T_g of the synthetic or non-synthetic polar-component of the synthetic or non-synthetic polar-polymer material to be colored; and/or the coloring composition solution exposing the synthetic or non-synthetic polar-polymer material may have a temperature lower than the heat deflection temperature of the synthetic or non-synthetic polar-polymer material to be colored. This may have the advantages that distortion or deforming of the synthetic or non-synthetic polar-polymer material may be avoided.

[0221] The heat deflection temperature also called heat distortion temperature may be the temperature at which synthetic or non-synthetic polar-polymer material deforms under a specified load. It may be determined by the following test procedure outlined in ASTM D648. The test specimen is loaded in three-point bending in the edgewise direction. The outer fiber stress used for testing is either 0.455 MPa or 1.82 MPa, and the temperature is increased at 2 °C/min until the specimen deflects 0.25 mm.

Selective color inprinting

[0222] The method according to the present invention allows reversible coloring of defined surface areas of a synthetic or non-synthetic polar-polymer material that are heated by a heat source, whereby the color extends into the synthetic or non-synthetic polar-polymer material at the heat treated surface, wherein the color is encapsulated in and under the outer surface due to cooling of the heated colorized surface of the synthetic or non-synthetic polar-polymer material.

[0223] The selectively colorized defined surface areas of a synthetic or non-synthetic polar-polymer material can be decolorized by heat treatment of the colorized defined surface areas and the colorizing agent can be for example washed out. The decolorizing takes place at an elevated temperature in contact with a polar solvent at temperatures of ≥ 80 °C, ≥ 100 °C or ≥ 140 °C depending on the softening point of the colorized synthetic or non-synthetic polar-polymer material. The decolorizing process allows the removal of ≥ 90 wt.-%, preferably ≥ 99 wt.-% of the colorizing agent. With other words "reversible" means that the encapsulated colorizing agent can be decapsulated by a heat treatment step in in contact with a polar solvent. That allows that the selective colorized defined surface areas of a synthetic or non-synthetic polar-polymer material can be decolorized and the decolorized synthetic or non-synthetic polar-polymer material can be reused. That allows for example multiple colorizing cycles of the synthetic or non-synthetic polar-polymer material.

[0224] Defined colorizing means that a color pattern, such has pictures, information text or any other color design can be inprinted , wherein the area of the synthetic or non-synthetic polar-polymer material that is inprinted by the colorizing agent is heat treated or subjected to a heat source.

[0225] The method for reversible color inprinting a pattern into a synthetic or non-synthetic polar-polymer material can be used to colorize synthetic or non-synthetic polar-polymer material.

[0226] In the context of the present invention the term "polar-component" with respect to synthetic or non-synthetic polar-polymer material defines a polymer material or polymer layer that comprises at least about ≥ 5 wt.-% of heteroatoms, wherein the weight % is calculated based on the weights of the synthetic or non-synthetic polar-polymer material or layer that is colorized by the method described herein.

[0227] A polymer material that comprises < 5 wt.-% of heteroatoms, wherein the weight % is calculated based on the weights of the synthetic or non-synthetic polymer material cannot or not sufficient colored by the method of the present invention. For example a polymer material comprising PE or PP-polymer, which is a non-polar polymer, cannot be colored by the method of the present invention. However a polymer material comprising PE or PP-polymer and in addition at least one synthetic or non-synthetic polar-polymer, at least one synthetic or non-synthetic polar-oligomer, and/or at least one polar-additive can be colored by the method of the present invention.

[0228] In the context of the present invention the term "synthetic or non-synthetic polar-polymer material" defines a polymer material that comprises at least about ≥ 0.5 wt.-% of the synthetic or non-synthetic polar-component, preferably about ≥ 5 wt.-% of the synthetic or non-synthetic polar-component, and further preferred about ≥ 10 wt.-% of the synthetic or non-synthetic polar-component, in addition preferred about ≥ 15 wt.-% of the synthetic or non-synthetic polar-component, also preferred about ≥ 20 wt.-% of the synthetic or non-synthetic polar-component, or about ≥ 30 wt.-% and about ≤ 100 wt.-% of the synthetic or non-synthetic polar-component, wherein the weight % is calculated based on the total weight of the synthetic or non-synthetic polar-polymer material that is colored by the method of the present invention.

[0229] In order to increase the flawless of the color inprinting pattern and outlines of colored pattern areas of the synthetic or non-synthetic polar-polymer material it can be preferred that the coloring composition solution exposed to the area of the synthetic or non-synthetic polar-polymer material to be colored has an outer surface temperature below 60 °C, below 50 °C, below 40 °C and most preferred below 30 °C.

[0230] As already mentioned, during the coloring process the area of the heated outer surface of the synthetic or non-synthetic polar-polymer material is exposed to the aqueous dispersed coloring composition solution or non-aqueous dispersed coloring composition solution.

[0231] According to preferred embodiment the step of exposing the heated outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized by forming a pattern with the coloring composition solution may comprises:

• dipping at least the heated outer surface or the heated outer surface, wherein areas that should not be colorized are covered, or dipping at least the heated intended pattern area of the outer surface to be colored, of the synthetic or non-synthetic polar-polymer material into the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution; and/or
• flow coating at least the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended pattern with the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution.

[0232] The specific way how the heated outer surface of the synthetic or non-synthetic polar-polymer material is exposed to the coloring composition solution may be dependent on the article made of the synthetic or non-synthetic polar-polymer material. For example if the article has the form of a bottle, the article may be dipped into the coloring composition solution in such a fashion that the inner surface of the bottle may not be exposed to the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution. However, for other forms of the article made of the synthetic or non-synthetic polar-polymer material it may be advantageous to flow coat the outer surface of the synthetic or non-synthetic polar-polymer material with the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution.

[0233] In order to achieve a homogenous coloring result and according to an another embodiment the step of exposing at least the heated outer surface of the synthetic or non-synthetic polar-polymer material to the coloring composition solution may comprise

• stirring the coloring composition solution while the heated outer surface of the synthetic or non-synthetic polar-polymer material is exposed to the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, and/or
• applying ultrasound to the coloring composition solution while the heated outer surface of the synthetic or non-synthetic polar-polymer material is exposed to the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution.

[0234] These method steps may increase and/or homogenize the migration of the organic aromatic coloring agent into the heated synthetic or non-synthetic polar-polymer material.

[0235] A color pattern can be obtained by heat treatment of the outer surface or of defined areas of the outer surface of the synthetic or non-synthetic polar-polymer material and contacting at least the heated surface of the heated synthetic or non-synthetic polar-polymer material that correspond to the intended pattern with the coloring composition solution. The organic aromatic coloring agent of the coloring composition solution than migrates into the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material. Cooling down of the colored areas of the synthetic or non-synthetic polar-polymer material leads to an encapsulation of the organic aromatic coloring agent.

[0236] Furthermore, the heated area that corresponds to the intended pattern or areas of the synthetic or non-synthetic polar-polymer material, which is exposed to the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, may have a temperature in the range of about ≥ 40° C to about ≤ 150° C, preferably the heated area that corresponds to the intended pattern or areas of the synthetic or non-synthetic polar-polymer material, which is exposed to the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, may have a temperature about ≥ 40° C and lower than the heat deflection temperature of the synthetic or non-synthetic polar-polymer material. It may be preferably that the heated area that corresponds to the intended pattern or areas of the synthetic or non-synthetic polar-polymer material may have a temperature that corresponds to the temperature of the coloring composition solution +/- 30%.

[0237] Therefore the temperature difference between the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material and the coloring composition solution may not be higher than +/- 30%. This may reduce unwanted effects in the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material caused by a fast increase or decrease of the temperature.

[0238] Furthermore it may be preferable that the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material may have a temperature lower than the heat deflection temperature of the synthetic or non-synthetic polar-polymer material. Preferably the heated area that corresponds to the intended pattern or areas of the synthetic or non-synthetic polar-polymer material does not deflect and/or deform when exposed to the conditions of the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution.

[0239] It may be advantageous that the surface of the synthetic or non-synthetic polar-polymer material that should not be colored may be partially cooled while being exposed to the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution. For example if the synthetic or non-synthetic polar-polymer material is a film, the film may be imprinted with the coloring composition solution in such a fashion that the reverse side of the film may be cooled, while the heated area that corresponds to the intended pattern of the front side of the film to be inprinted is exposed to the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution.

[0240] It may be advantageous to expose the synthetic or non-synthetic polar-polymer material to the coloring composition solution right after the synthetic or non-synthetic polar-polymer material is formed in a manufacturing process. According to the above and to another preferred embodiment the synthetic or non-synthetic polar-polymer material may be formed in a molding process, a compression molding process, an extruding process, a thermoforming process, a blowing process and/or a 3D-printing process, thereafter at least the heated area that corresponds to the intended pattern is exposed to the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution.

[0241] Actually the so called "3D-printing process" is a 2D printing process, wherein the surface of a 3D component or article is printed. The print head is moved in all spatial directions to achieve an all-round printing. Thus the 3D printing process is the printing of a surface of a 3-dimensional structure, not the printing as such.

[0242] Accoring to one embodiment at least the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material that is to be colorized is colorized by the coloring composition by means of a 3D-printing process, wherein the print head is guided around at least the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material kept at a constant distance to be printed, preferably by means of a 5-axis robot.

[0243] The synthetic or non-synthetic polar-polymer material may be further formed in a compression molding, an injection molding, a rotational molding, an extrusion, an injection and/or extrusion blow molding, and/or casting process. The method of forming the synthetic or non-synthetic polar-polymer material may not be critical to the method of reversibly and selectively coloring the synthetic or non-synthetic polar-polymer material. Furthermore it may be possible that the synthetic or non-synthetic polar-polymer material may be formed in another manufacturing process including all other manufacturing processes not explicitly listed here for the manufacturing of plastic parts.

Time

[0244] According to an another embodiment at least the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, may be exposed to the coloring composition solution for about ≥ 1 second to about ≤ 60 minutes, preferably about ≥ 3 seconds to about ≤ 30 minutes, in addition preferred about ≥ 5 seconds to about ≤ 10 minutes, and also preferred about ≥ 10 seconds to about ≤ 1 minute, or about ≥ 15 seconds to about ≤ 30 seconds. However it is preferred that at least the heated area that corresponds to the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material may be exposed to the coloring composition solution for about ≥ 1 second to about < 10 minutes, preferably about ≥ 2 seconds to about ≤ 8 minutes, in addition preferred about ≥ 5 seconds to about ≤ 6 minutes, and also preferred about ≥ 10 seconds to about ≤ 4 minutes, or about ≥ 15 seconds to about ≤ 2 minutes.

[0245] In general the defined heated outer surface for providing the inprinting pattern of a synthetic or non-synthetic polar-polymer material is completely colored at about ≥ 1 second to about < 10 minutes, preferably about ≥ 2 seconds to about ≤ 8 minutes, in addition preferred about ≥ 5 seconds to about ≤ 6 minutes, and also preferred about ≥ 10 seconds to about ≤ 4 minutes, or about ≥ 15 seconds to about ≤ 2 minutes. The colorized surface pattern of the synthetic or non-synthetic polar-polymer material may have a color as the color defined by the organic aromatic coloring agent or coloring agent mixtures used.

[0246] The synthetic or non-synthetic polar-polymer material may be withdrawn at a specific rate from the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, including a rate sufficient to effect a coloring gradient. Therefore, the portion of the synthetic or non-synthetic polar-polymer material that remains in the coloring composition solution longest may contain the most organic aromatic coloring agent per unit volume so that it exhibits the darkest color tint.

[0247] The synthetic or non-synthetic polar-polymer material may be imprinted differently according amount of ink, area coverage, concentration of solution, temperature or other suitable parameters from bottom to top including a rate sufficient to effect a coloring gradient. Therefore, the portion of the synthetic or non-synthetic polar-polymer material that is imprinted with the largest amount of ink, largest area coverage, highest concentration of solution or higher temperature may contain the most organic aromatic coloring agent per unit volume so that it exhibits the darkest color tint.

[0248] The outer surface areas of the synthetic or non-synthetic polar-polymer material that has a temperature below 30° C is not colorized.

Layer thickness to be colorized

[0249] The thickness of the layer that is colored by the inprinting process may be about 1% to about 100% for a single layer, or about 0.1% to about 99% for a multilayer, regardless of the total thickness, or about 0.1 µm to about 1000 µm, or preferably about 1% to about 40%. The thickness of the layer that is completely colored by the inprinting process may be about 1 µm to about 50 µm, more preferably about 5 µm to about 25 µm.

[0250] According to one embodiment the layer thickness of the synthetic or non-synthetic polar-polymer material that is colorized by the inprinting process may be about ≥ 0.1 µm, preferably of about ≥ 1 µm to about ≤ 1000 µm, preferably the colorized area or areas of the synthetic or non-synthetic polar-polymer material is homogenously colored.

[0251] According to one embodiment the layer thickness of the synthetic or non-synthetic polar-polymer material that is colorized by the inprinting process may be about ≥ 0.1 µm, preferably of about ≥ 1 µm to about ≤ 1000 µm, with a coloring grade of 0.1% to ≤ 100%, preferably ≥ 1% to ≤ 90%.

[0252] It is not always the case that a layer of the synthetic or non-synthetic polar-polymer material is completely colored by the inprinting process. For a PET preform, the total thickness of the layer is may be about 3 mm, but the colorizing agent penetrates into the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material may be only about 2 µm to about 20 µm.

[0253] In furniture applications, the layer pattern is 25% colorized of a thickness of 2mm, or the layer is 50% colorized of a thickness of 100µm. The thickness and % of colorization is depending on the article that is colorized by a method according to the invention.

[0254] Even with multilayer parts, with short dyeing times, it may happen that the colorizing agent does not penetrate the entire colorable layer, only the top layer of the part has a colored pattern obtained by the inprinting process, although the thickness of the synthetic or non-synthetic polar-polymer material, also named additivated layer, is significantly larger.

[0255] The layer thickness of the polar-polymer material that is colored by a pattern by the inprinting process may be about ≥ 1 µm to about ≤ 50 µm, preferably about ≥ 2 µm to about ≤ 30 µm, further preferred about ≥ 3 µm to about ≤ 20 µm, also preferred about ≥ 4 µm to about ≤ 15 µm, in addition preferred about ≥ 5 µm to about ≤ 12 µm and furthermore preferred about ≥ 6 µm to about ≤ 10 µm. The pattern of the colorized layer of the synthetic or non-synthetic polar-polymer material has a color as determined by the organic aromatic coloring agent or coloring agent mixtures as used.

[0256] According to an another embodiment the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, preferably at least one outer surface of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, may be exposed to the coloring composition solution for about ≥ 1 second to about ≤ 60 minutes, preferably about ≥ 3 seconds to about ≤ 30 minutes, in addition preferred about ≥ 5 seconds to about ≤ 10 minutes, and also preferred about ≥ 10 seconds to about ≤ 1 minute, or about ≥ 15 seconds to about ≤ 30 seconds; wherein the layer thickness of the polar-polymer material that is colored by the process according to the invention is about ≥ 1 µm to about ≤ 50 µm, preferably about ≥ 2 µm to about ≤ 30 µm, further preferred about ≥ 3 µm to about ≤ 20 µm, also preferred about ≥ 4 µm to about ≤ 15 µm, in addition preferred about ≥ 5 µm to about ≤ 12 µm and furthermore preferred about ≥ 6 µm to about ≤ 10 µm. The colorized layer of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material may have a color as determined by the organic aromatic coloring agent or coloring agent mixtures used for coloring.

[0257] However it is preferred that the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, preferably at least one outer surface of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, may be exposed to the coloring composition solution for about ≥ 1 second to about < 10 minutes, preferably about ≥ 2 seconds to about ≤ 8 minutes, in addition preferred about ≥ 5 seconds to about ≤ 6 minutes, and also preferred about ≥ 10 seconds to about ≤ 4 minutes, or about ≥ 15 seconds to about ≤ 2 minutes; wherein the layer thickness of the polar-polymer material that is colored by the process according to the invention is about ≥ 1 µm to about ≤ 50 µm, preferably about ≥ 2 µm to about ≤ 30 µm, further preferred about ≥ 3 µm to about ≤ 20 µm, also preferred about ≥ 4 µm to about ≤ 15 µm, in addition preferred about ≥ 5 µm to about ≤ 12 µm and furthermore preferred about ≥ 6 µm to about ≤ 10 µm. The colorized layer of the heated area that corresponds to the intended pattern or areas of the synthetic or non-synthetic polar-polymer material may have a color as determined by the organic aromatic coloring agent or organic aromatic coloring agent mixtures used for coloring.

pH

[0258] The result of the coloring process with aqueous dispersed coloring composition solutions may be influenced by the pH of the aqueous dispersed coloring composition solution. Preferably the coloring composition solution may have a pH in the acidic range. According to an another embodiment the coloring composition solution has a pH in the range of about ≥ 3.2 and about ≤ 6.5, preferably a pH in the range of about ≥ 3.4 and about ≤ 6; in addition preferred a pH in the range of about ≥ 3.5 and about ≤ 5.5 and also preferred a pH in the range of about ≥ 4 and about ≤ 5. It may be possible to reduce the pH of the coloring composition solution by adding acetic acid to the aqueous dispersed coloring composition solution.

Surprising effect

[0259] It is surprising that the colorizing speed of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material can be significantly increased by a pH < 7. The colorizing speed of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material seems to be highest at a pH range of the coloring composition solution of about ≥ 2.5 and about < 6, in particular at a pH range of about ≥ 3.5 and about < 5.

[0260] For example at a pH range of about ≥ 2.5 and about ≤ 6 of the aqueous dispersed coloring composition solution, the colorizing time for colorizing a layer thickness of the polar-polymer material that is colored by the process according to the invention can be of about ≥ 1 µm to about ≤ 50 µm, preferably about ≥ 2 µm to about ≤ 30 µm, further preferred about ≥ 3 µm to about ≤ 20 µm, also preferred about ≥ 4 µm to about ≤ 15 µm, in addition preferred about ≥ 5 µm to about ≤ 12 µm and furthermore preferred about ≥ 6 µm to about ≤ 10 µm, is < 10 minutes, preferably about ≥ 2 seconds to about ≤ 8 minutes, in addition preferred about ≥ 5 seconds to about ≤ 6 minutes, and also preferred about ≥ 10 seconds to about ≤ 4 minutes, or about ≥ 15 seconds to about ≤ 2 minutes.

[0261] In other words, the coloring process is rather fast. By changing the duration of the exposure the migration depth of the migration of the organic aromatic coloring agent into the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material and/or the concentration of the organic aromatic coloring agent in the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material may be varied. Therefore, the color appearance of the colored pattern of the synthetic or non-synthetic polar-polymer material may also vary according to the duration of exposure. For example the color of a colored synthetic or non-synthetic polar-polymer material that has been exposed to the coloring composition solution for < 10 minutes may be more intense than the color of a colored synthetic or non-synthetic polar-polymer material that has been exposed to the coloring composition solution for ≤ 5 minutes.

Embodiments

[0262] In another preferred embodiment the coloring composition solution may comprise:

• about ≥ 0.1 wt.-% to about ≤ 15 wt.-% at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol;
• about ≥ 0.01 wt.-% to about ≤ 40 wt.-% one dispersing agent for dispersing the organic aromatic coloring agent in the aqueous solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution,
• about ≥ 0 wt.-% to about ≤ 50 wt.-% of least one solubilizer, and
• water added to 100 wt.-%.

[0263] In another preferred embodiment the coloring composition solution may comprise:

• about ≥ 0.1 wt.-% to about ≤ 15 wt.-% at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol or ≥ 250 g/mol to about ≤ 550 g/mol;
• about ≥ 0.01 wt.-% to about ≤ 40 wt.-% one dispersing agent for dispersing the organic aromatic coloring agent in the aqueous solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution,
• about ≥ 0 wt.-% to about ≤ 50 wt.-% of least one solubilizer,
• about ≥ 0.05 wt.-% to about ≤ 5 wt.-% of at least one carrier agent, and
• water added to 100 wt.-%.

Multiple layer

[0264] The polar-polymer material can comprise at least one or more layers. For example the polar-polymer material can comprises a multi-layer. The layers may be differently composed. One layer of the polymer material may have a content of polar components and non-polar polymers, wherein the content of the polar components are less than about 5 wt.-%, preferably about < 3 wt.-%, further preferred about < 2 wt.-% and in addition preferred about < 0.5 wt.-% or about < 0.1 wt.-% and about ≥ 90 wt.-%, preferably about ≥ 95 wt.-%, more preferably about ≥ 99.5 wt.-% of non-polar components, such as non-polar polymer and/or non-polar oligomer cannot be colorized by the method according to the present invention.

[0265] The advantage is that a two layer polar-polymer material, such as a bottle, wherein the outer surface directed outwards is of a polar-polymer material comprises about ≥ 0.5 wt.-%, preferably about ≥ 5 wt.-%, more preferably ≥ 10 wt.-%, of polar components, such as synthetic or non-synthetic polar polymer, synthetic or non-synthetic polar oligomer and/or polar additive, can be colored by the method according to the invention, where else the inner layer facing to the inside of the bottle, which is a layer comprising less than about 5 wt.-%, preferably about < 3 wt.-%, further preferred about < 2 wt.-% and in addition preferred about < 1 wt.-%, and more preferably < 0.5 wt.-%, or about ≥ 0 to < 0.1 wt.-% of a polar component and about ≥ 90 wt.-%, preferably about ≥ 95 wt.-%, more preferably about ≥ 99.5 wt.-% to about < 100 wt.-% of non-polar components, such as non-polar polymer and/or non-polar oligomer, cannot be colorized by the method according to the present invention.

[0266] Therefore it is possible to color for example a multilayer package, wherein only the outer layer is colored by a pattern. Thus the inner layer that is supposed to be in contact to the filling of the package may be free of the organic aromatic coloring agent.

[0267] According to an embodiment a synthetic or non-synthetic polar-polymer material may comprises at least two layers, wherein at least a first layer is of a polar-polymer material, that comprises about ≥ 0.5 wt.-%, further ≥ 5 wt.-%, preferably ≥ 10 wt.-%, of polar components, such as synthetic or non-synthetic polar polymer, synthetic or non-synthetic polar oligomer and/or polar additive, and is colorable to design a pattern, where else the second layer comprising less than about 5 wt.-%, preferably about < 3 wt.-%, further preferred about < 2 wt.-% and in addition preferred about < 1 wt.-%, more preferably less than 0.5 wt.-% or about ≥ 0 to < 0.1 wt.-% of a polar component and about ≥ 90 wt.-%, preferably about ≥ 95 wt.-% to about ≤ 100 wt.-% of at least one non-polar component, such as non-polar polymer and/or non-polar oligomer, cannot be colorized.

[0268] This is very useful for containers where the inner surface comes into contact with foodstuffs, such as beverages, fruits or there like, because the inner non-polar surface of that container is not colored by the method according to the invention so that the foodstuff cannot be contaminated by the coloring agent of the pattern of the outer polar surface layer and thus functions rather as a barrier layer.

Article that can be colorized

[0269] According to an another embodiment the article showing a pattern provided by the inprinting process described herein may be selected from the group comprising a sheet, a foil, a tube, a container, a part, a bottle, a non-woven fabric, and preferably the article may be selected from the group comprising computer face-plates, keyboards, bezels and cellular phones, color coded packaging and containers of all types, including ones for industrial components, residential and commercial lighting fixtures and components therefor, such as sheets, used in building and in construction, tableware, including plates, cups and eating utensils, small appliances and their components, optical and sun-wear lenses, as well as decorative films including such films that are intended for use in film insert molding.

Pattern

[0270] Any kind of pattern can be designed by the inprinting process. Patterns that can be designed by the inprinting process comprises product information, bar-codes, text, pictures, decors, symbols, hazard symbols, scales, lines, grids, (conductive) tracks, passepartouts advertising messages, numbers, prices, serial numbers, number plates, negatives and much more.

Further advantages

[0271] The present invention further relates to the colored synthetic or non-synthetic polar-polymer material, wherein the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, preferably the outer surface of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, is colored by the above described method. This is not only an easy way for coloring a synthetic or non-synthetic polar-polymer material by a specific pattern but allows also for decoloring of the colored synthetic or non-synthetic polar-polymer material.

[0272] According to another preferred embodiment the colored synthetic or non-synthetic polar-polymer material may comprise at least one synthetic or non-synthetic polar-component layer and at least one non-polar-component layer, wherein at least one layer or outer surface of the synthetic or non-synthetic polar-component layer is colored by the above described method, wherein the non-polar-component layer is not colorable by the above described method. In other words the colored synthetic or non-synthetic polar-polymer material may have a layered structure, comprising the synthetic or non-synthetic polar-component layer and the non-polar-component layer. Only the synthetic or non-synthetic polar-component layer may be colorable with the above described method but not the non-polar-component layer. Therefore, by adjusting the polarity of the different layers it may be possible to selectively color the desired layers while the other layers remain colorless.

[0273] The dosage of the polar polymer, oligomer or additive in the synthetic or non-synthetic non-polar polymer also determines the coloring by means of inprinting. Therefore, different degrees/levels of coloring can be achieved with identical inprinting times and temperatures due to the different dosage of the polar polymer, oligomer or additive in the synthetic or non-synthetic non-polar polymer in one object or different layers of the object. The higher the dosage of the polar polymer, oligomer or additive in the synthetic or non-synthetic non-polar polymer the higher the coloring level.

[0274] As described above the coloring process is based on migration of the organic aromatic coloring agent into the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material. By exposing the outer surface of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material with the aqueous dispersed coloring composition solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution, the outer layer of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material gets colored. According to the above a colored synthetic or non-synthetic polar-polymer material may be provided, wherein at least a layer thickness of about ≥ 0.1 µm of an outer layer of the colored synthetic or non-synthetic polar-polymer material is homogenously colored. Homogeneous coloration of the outer layer of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material may be achieved by having the same amount of the organic aromatic coloring agent per area of the outer surface of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material. The organic aromatic coloring agent may be essentially homogenously distributed in the colored part or layer of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, meaning that that for the eye of a human being the colored outer surface or the colored part or the colored layer of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material appear uniformly colored without color variations. The outer surface may be homogenously colored by migration of the organic aromatic coloring agent into the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material up to certain migration depth. At the same time, a fine, uniform and homogeneous distribution of the polar component in the polymer material is the basic prerequisite for homogeneous coloring of the polymer material. A migration depth further into the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material may only further increase the opacity, darkness, and/or color depth of the color but not the homogeneity of the colored surface. The colored surface may be homogenously colored when no significant color fluctuations may be visible by the human eye. For a homogenously colored surface the color differences, given in ΔF*_ab, according to the International Commission on Illumination (CIE), over the outer surface of the colored synthetic or non-synthetic polar-polymer material may be about ≤ 2.

[0275] According to an another embodiment the concentration of the organic aromatic coloring agent in at least one colored layer pattern of the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, colored by the above described method, wherein the colored layer pattern has a thickness of about ≥ 0.1 µm, may be 0.00001 wt.-% to about ≤ 5 wt.-%, based on the total weight of said colored layer.

[0276] With regard to further advantages and technical features of the colored synthetic or non-synthetic polar-polymer material it is referred to the method for reversible coloring the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, the article comprising at least one colored synthetic or non-synthetic polar-polymer material, the examples and the further description.

[0277] The present invention further relates to an article comprising at least one colored synthetic or non-synthetic polar-polymer material by a pattern as described above and colored by the method as described above. By using the above described method for reversibly and selectively coloring an article with a pattern the advantages is that the article can be decolored, with other words the coloring process is reversible and for the colored polymer materials that have been colored with the inprinting technology described here.

[0278] With regard to further advantages and technical features of the article it is referred to the method for reversibly coloring the heated area that corresponds to the intended pattern of the synthetic or non-synthetic polar-polymer material, the colored synthetic or non-synthetic polar-polymer material, examples and the further description.

[0279] To summarize the above, the present invention solves an important object how to design a coloring process to ease recycling processes by avoiding foreign materials and with that being environmentally friendly.

[0280] Other example embodiments will be described in the following with reference to the examples. It has to be noted that the examples are only provided for illustration of the general concept by examples not defining the scope of protection of the invention. The examples are not drawn to scale. Features shall not be considered to be essential for the present invention because they are depicted in the examples.

DETAILED DESCRIPTION OF THE EXAMPLES

[0281] The invention will be described in the following with reference to exemplary coloring composition solutions of examples 1 to 10.

Example 1

[0282] 7g of Disperse Blue 56 (Disperse Blue 56 has a solubility in double distilled water of about 14 mg/l) is dissolved in 93g dimethylformamid to result in a 7 wt.% color composition. The color composition is filtered by a 400µm filter to give a transparent solution.

Example 2

[0283] 1g of BEMACRON Blue E-FBL 150 is dispersed in a mixture of 66 wt.% of destilled water, 30 wt.% of ethanol (analytical grade), 3,9 wt.% of glycerol and 0.1 wt% Mergal K 14 (Troy, USA; biocice)). The color composition is filtered by a 400µm filter to give a translucent solution.

Example 3

[0284] 15g of BEMACRON Blue E-FBL 150 is dispersed in a mixture of 800g water, 180g iso-propanol and 20g diethylene glycol (DEG). The dispersion is buffered with addition of acetic acid/Na-acetate to pH 4,5. 2g Breviol DCR (Pulcra Chemical, a.o. benzylbenzoate) as carrier and 2g BYK-333 as surface tension modifier is added. The coloring composition is heated to 80°C and filtered by a 400µm filter. The color composition is a translucent solution

Example 4

[0285] 5g BEMACRON Rot E-FBL and 5,0g o-Vanillin are dissolved in 12mL of n-butyl acetate and made to 100 ml with distilled water containing 0.1 wt.% Mergal K 14 (Troy, USA, biocide). The emulsification is facilitated by mechanical stirring with a propeller shaker, followed by ultrasound (2 w/ml, 1 min). The emulsion is warmed to 50°C and filtered by a 400µm filter to give a translucent solution

Example 5

[0286] 5g BEMACRON Yellow E-3GL and 5,0g o-Vanillin are dissolved at 60°C in 12mL of acetyl tri-n-butyl citrate (ATBC), 2,5 g soya lecithin (phosphoglyceride) is added and made to 100 ml with distilled water containing 0.1 wt.% Mergal K 14 (Troy, USA, biocide). The emulsification is facilitated by mechanical stirring with a propeller shaker, followed by ultrasound (2 w/ml, 1 min). The emulsion is warmed to 50°C and filtered by a 400µm filter to give a translucent solution.

Example 6

[0287] 5,01 g of Disperse Yellow 54 (Disperse Yellow 54 has a solubility in double distilled water of about 14 mg/1), 2,76 g dispersing agent (Shanghai Jiuyu Chemical Co. Ltd., TD-1109), 5,01 g diethylene glycol (Alfa Aesar Co. Ltd.) and 32,08 g deionized water were accurately weighed and added into an agate mortar with 50 g of 0.4-0.6 mm diameter zirconia beads. Grinding was performed using a planetary ball mill (NETZSCH Group, Germany) at 800 rpm for 3 h. After removing the beads additional 32,08 g deionized water, 22,5 g ethylene glycol (Sinopharm Chemical BeijingReagent Co.), 0.25g polyvinylalkohol (Macklin Biochemical Co., 1788 low viscosity), 0.5 g organosilicon defoamer (Shnaghai BBI Co. Ltd.) and 0.05 g tetraethanolamin (Macklin Biochemical Co., EOA) are added under stirring at 1.000 rpm and 25°C until a homogeneous dispersion of a a total amount of 100g is obtained. The dispersion of pH 8,2 is warmed to 50°C and filtered by a 400µm filter membrane to give a translucent dispersion.

Example 7

[0288] 5,01 g of Disperse Red 60, 2,76 g dispersing agent (Shanghai Jiuyu Chemical Co. Ltd., TD-1109), 5,01 g diethylene glycol (Alfa Aesar Co. Ltd.) and 32,08 g deionized water were accurately weighed and added into an agate mortar with 50 g of 0.4-0.6 mm diameter zirconia beads. Grinding was performed using a planetary ball mill (NETZSCH Group, Germany) at 800 rpm for 3 h. After removing the beads additional 32,08 g deionized water, 22,5 g ethylene glycol (Sinopharm Chemical BeijingReagent Co.), 0.5 g water solulable polyester (Nichigo-Polyester WR-901), 0.5 g organosilicon defoamer (Shanghai BBI Co. Ltd.) and 0.05 g tetraethanolamin (Macklin Biochemical Co., EOA) are added under stirring at 1.000rpm and 25°C until a homogeneous dispersion of a a total amount of 100g is obtained. The dispersion of pH 8,2 is warmed to 50°C and filtered by a 400µm filter membrane to give a translucent dispersion.

Example 8

[0289] 10g Bemacron Yellow E-3GL are dispersed in 100g of deionized water. 10g ethylene glycol, 20g diethylene glycol butylether, 3g polyvinylalkohol (Macklin Biochemical Co., 1788 low viscosity) and 1g BYK-019 (defoamer) are added and stirred for 15 min. Finally 0.25g BYK-347 (polyether modified siloxane; surface tension modifier) is added. The dispersion is filtered by a 400µm filter membrane to give a translucent dispersion.

Example 9

[0290] 10g Bemacron Blau E-FBL 150 are dispersed in 100g of deionized water. 10g ethylene glycol, 20g diethylene glycol butylether, 7g poly acrylicacid and 1g BYK-019 (defoamer) are added and stirred for 15 min. Finally 0.25g BYK-347 (polyether modified siloxane; surface tension modifier) is added. The dispersion is filtered by a 400µm filter membrane to give a translucent dispersion.

Example 10

[0291] 3g BEMACRON Rot E-FBL are dispersed in 22g of deionized water. 5g ethylene glycol, 10g diethylene glycol, 10g sodium alginate (thickener, 3% gel, Sigma-Aldrich, UK) and 1g BYK-800 (alkoholalkoxylate antifoam) are added and stirred for 15 min. The pH value is adjusted to 4.5 by successively adding acetic acid. The dispersion is filtered by a 400µm filter membrane to give a translucent dispersion.

Preparation of a film

[0292] On a cast film device obtainable from the company Reifenhäuser a multi-layered PP film with a total thickness of 100 µm is produced by coextrusion. The film has a structure according to A-B-A. The layer B has a thickness of 70 µm and consists of a commercial PP obtainable from the company Borealis suitable for the cast film process. Layer B is admixed with about 4 wt.-% of the titanium dioxide masterbatch of Plasgrey PG4166 (Density @ 23°C, CTM E023: 1790 kg/m³; MFI 2.16 kg/190°C, CTM E005 (ISO 1133): 19 g/10 min) obtainable from Cabot Corporation, in order to color the film in a white-opaque manner. The layers A each have a thickness of 15 µm. The layers A are admixed with 8 wt.-% of a 2 : 1 mixture of a random terpolymer of ethylene, acrylic ester and maleic anhydride (acrylate content 17%, MSA content 3%, MFI 5g/10min, 190°C, 2,16kg) and a random terpolymer of ethylene, butyl acrylate and glycidyl methacrylate (acrylate content 23 - 28%, Gly content 8%, MFI 10 - 14g/10min, 190°C, 2,16kg) to the same PP as the layer B. The multilayer film is extruded, cooled and wound up. Depending on customer requirements, the film can be provided in rolls, for example longitudinally cut and cut to length for processing on a printing press or cut into sheets.

Printing the Film with Example

[0293] The film is placed in a digital printing machine from Canon and printed by means of aqueous inkjet printing (printheads from Dimatix, analogue printing press from Fujifilm, printheads Samba). The coloring composition solution is a printing ink that is formulated without binder and contains as color Bemacron Blau E-FBL obtainable from company CHT.

[0294] After being placed in the printing machine, the surface of the film that corresponds to the desired pattern is first heated to about 80 °C for about 5 to about 60 seconds by means of an IR illuminator from Krelus (or Hereaus) to activate the surface area for the migration of the dye. In order to avoid deformation of the film by the effect of temperature, the film backside is held by a plate cooling to about 40 °C. By means of print-on-demand IJ printing - printheads from Samba - the printing ink is preheated to 80 °C and the heated ink is printed or sprayed onto the surface with a print or spray temperature at a temperature in the range of 70 °C to 80 °C onto the heated areas of the film for inprinting the desired pattern.

[0295] Immediately after the ink drop of 1-5 pL (pico litres) per drop has contacted the heat activated surface area of the film, the dye penetrates into the film and migrates. The solvent remains largely on the surface and evaporates at a surface temperature of about 100 °C within ≥ 20 second and ≤ 60 seconds. It can be preferred that the solvent remains on the surface and evaporates at a surface temperature, this is the temperature of the surface to which the dye composition also called ink is applied, of about 100 °C within ≥ 5 second and ≤ 50 seconds and more preferred ≥ 10 second and ≤ 40 seconds and even more preferred ≥ 20 second and ≤ 30 seconds.

[0296] The homogenous penetration depth of the organic aromatic coloring agent of the coloring agent used in Example 1 to 10 into the layer is at least 2 µm.

[0297] Compared to full-surface inking, the applied amounts of dye and liquid are significantly lower by the selective inprinting process. Because the dyes do not migrate to deeper layers, thus producing a good print image.

[0298] The inprinting process is energy saving because the heat source moves immediately before applying the printing ink to the printing area of the heated surface. A sharp printing pattern can be obtained because adjacent areas of the polymer surface that are not heat activated, dyes cannot migrate into the polymer surface. For example a color line broadening is avoided since the dye can only penetrate into the heat activated areas.

[0299] Another way to apply patterns, fonts, lines or there like is to partially mask the surface of the polymer material. Surface areas of the film which are not supposed to be colored are covered by means of a lacquer or there like which serves as a barrier for the dyes. The surface of the polymer material that is imprinted by a color pattern is heat activated and immersed in a dyebath, the dye penetration takes place only where the heat activated surface is accessible and not covered.

[0300] The order of presented actions or steps is not mandatory; alternative orders are possible. It is to be understood that the described embodiments are examples only, which may be modified and/or supplemented in many ways within the scope of the claims. In particular, any feature described for a particular embodiment can be used by itself or in combination with other features in any other embodiment. Each feature that has been described for an embodiment of a particular category can also be used in an equivalent manner in an embodiment of any other category.

Claims

1. Method for reversible color inprinting a pattern into a synthetic or non-synthetic polar-polymer material comprising the step:

a) exposing an outer surface or a defined area of an outer surface of the synthetic or non-synthetic polar-polymer material to a heat source,

b) subjecting the heated outer surface of the synthetic or non-synthetic polar-polymer material to a coloring composition solution at areas of the heated outer surface of the synthetic or non-synthetic polar-polymer material that corresponds to the intended design of the pattern;

wherein the coloring composition solution comprises:

- at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, wherein the organic aromatic coloring agent is not liquid at 23° C,

- at least one agent that is not an organic aromatic coloring agent;

wherein the outer surface or defined area of the outer surface of the synthetic or non-synthetic polar-polymer material is heated to a temperature in the range of about ≥ 30 °C to about ≤ 150 °C; and wherein the coloring composition solution has a temperature below 30 °C or is heated to a temperature in the range of about ≥ 30 °C to about ≤ 190 °C.

2. The method according to claim 1, wherein the synthetic or non-synthetic polar-polymer material that is colored by inprinting comprises at least one synthetic or non-synthetic polar-component, wherein the synthetic or non-synthetic polar-component comprises

- at least one synthetic or non-synthetic polar-polymer having a Mw about ≥ 1000 g/mol; or

- at least one composition of a non-polar-polymer having a Mw about ≥ 1000 g/mol containing

- at least one synthetic or non-synthetic polar-polymer having a Mw about ≥ 1000 g/mol, and/or

- at least one synthetic or non-synthetic polar-oligomer having a Mw about ≥ 600 g/mol and < 1000 g/mol, and/or

- at least one polar-additive having a Mw about ≥ 70 and < 600 g/mol, wherein the polar-additive is selected different to the organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol or ≥ 250 g/mol to about ≤ 550 g/mol.

3. The method according to claim 2, wherein the synthetic or non-synthetic polar-polymer having a Mw about ≥ 1000 g/mol, the synthetic or non-synthetic polar-oligomer having a Mw about ≥ 600 g/mol and < 1000 g/mol, and the polar-additive having a Mw about ≥ 70 and < 600 g/mol each comprises at least about ≥ 5 wt.-% of heteroatoms, wherein the weight % is calculated based on the individual weights of the synthetic or non-synthetic polar-polymer, the synthetic or non-synthetic polar-oligomer, and the polar-additive.

4. The method according to claim 2 or 3, wherein the synthetic or non-synthetic polar-polymer material that is colored by inprinting comprises at least about ≥ 0.5 wt.-% of the synthetic or non-synthetic polar-component, preferably about ≥ 5 wt.-% of the synthetic or non-synthetic polar-component, and further preferred about ≥ 10 wt.-% of the synthetic or non-synthetic polar-component, in addition preferred about ≥ 15 wt.-% of the synthetic or non-synthetic polar-component, also preferred about ≥ 20 wt.-% of the synthetic or non-synthetic polar-component, or about ≥ 30 wt.-% and about ≤ 100 wt.-% of the synthetic or non-synthetic polar-component, wherein the weight % is calculated based on the total weight of the synthetic or non-synthetic polar-polymer material.

5. The method according to claims 1 to 4, wherein

a) the synthetic or non-synthetic polar-polymer comprises an amorphous phase of at least about ≥ 10 vol.-%, preferably about ≥ 30 vol.-%, more preferably about ≥ 50 vol.-% and about ≤ 100 vol.-%, wherein the volume % is calculated on the total volume of the synthetic or non-synthetic polar-polymer; and/or

b) the synthetic or non-synthetic polar-oligomer comprises an amorphous phase of at least about ≥ 10 vol.-%, preferably about ≥ 30 vol.-%, more preferably about ≥ 50 vol.-% and about ≤ 100 vol.-%, wherein the volume % is calculated on the total volume of the synthetic or non-synthetic polar-oligomer.

6. The method according to any of claims 1 to 5, wherein

a) the synthetic or non-synthetic polar-polymer has, above the glass-transition temperature Tg, a free volume, in the range of about ≥ 1 vol.-% to 25 %, preferably about ≥ 2 % to about ≤ 20 %, further preferred about ≥ 2.2 % to about ≤ 15 %, based on the total volume of the synthetic or non-synthetic polar-polymer material; and/or

b) the synthetic or non-synthetic polar-oligomer has, above the glass-transition temperature Tg, a free volume in the range of about ≥ 1 % to 25 %, preferably about ≥ 2 % to about ≤ 20 %, further preferred about ≥ 2.2 % to about ≤ 15 %, based on the total volume of the synthetic or non-synthetic polar-oligomer material.

7. The method according to any of claims 1 to 6, wherein the glass-transition temperature Tg of the synthetic or non-synthetic polar-polymer is in the range of about ≥ -75°C to about ≤ 160°C, preferably about ≥ -50°C to about ≤ 120°C, further preferred about ≥ 0°C to about ≤ 115°C.

8. The method according to any of claims 1 to 7, wherein

a) the synthetic or non-synthetic polar-polymer is selected from the group comprising synthetic or non-synthetic polar-homopolymers, synthetic or non-synthetic polar-copolymers, and/or synthetic or non-synthetic polar-terpolymers; and/or

b) the synthetic or non-synthetic polar-oligomer is selected from the group comprising synthetic or non-synthetic polar-homo oligomers, synthetic or non-synthetic polar-cooligomers, and/or synthetic or non-synthetic polar-teroligomers; and/or

c) the synthetic or non-synthetic polar-polymer is selected from a water-swellable crosslinked polymer matrix, wherein the matrix comprises a water-soluble polymer and a polymer latex in a weight ratio of 1:1 to 10:1, preferred from 1 : 1 to 5 : 1 and more preferred from 1 : 1 to 3 : 1 which are crosslinked.

9. The method according to any of claims 1 to 8, wherein the synthetic or non-synthetic polar-polymer or mixture thereof is a synthetic or non-synthetic polar-homo polymers, synthetic or non-synthetic polar-copolymers, and/or synthetic or non-synthetic polar-terpolymers, further preferred the synthetic or non-synthetic polar-polymer or mixture thereof is selected from the group:

- polyacrylate with methyl (polymethylacrylate), ethyl (polyethylacrylate), propyl (polypropylacrylate), or butyl (polybutylacrylate),

- polymethacrylate with methyl (polymethylmathacrylate), ethyl (polyethylmethacrylate), propyl (polypropylmethacrylate), or butyl (polybutylmethacrylate),

- copolymers of acrylic and methacrylic esters including, among others, tert. - Butyl (meth)acrylate, pentyl(meth)acrylate and 2-ethylhexyl(meth)acrylate; (Meth)acrylates derived from unsaturated alcohols, preferably oleyl(meth)acrylate, 2-propynyl(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate;

- aryl(meth)acrylate polymers, preferably benzyl(meth)acrylate polymers or phenyl(meth)acrylate polymers, the aryl radicals each being unsubstituted or up to four times substituted;

- cycloalkyl(meth)acrylates polymers, preferably 3-vinylcyclohexyl(meth)acrylate polymers, bornyl (meth)acrylate polymers;

- hydroxylalkyl (meth)acrylates polymers, preferably 3- hydroxypropyl (meth)acrylate polymers, 3,4- dihydroxybutyl(meth)acrylate polymers, 2-hydroxyethyl(meth)acrylate polymers, 2-hydroxypropyl(meth)acrylate polymers;

- glycol di(meth)acrylates polymers, preferably 1,4-butanediol (meth)acrylate polymers;

- (meth)acrylates of ether alcohols polymers, preferably tetrahydrofurfuryl (meth)acrylate polymers, vinyloxyethoxyethyl(meth)acrylate polymers;

- polymers of amides and nitriles of the (meth)acrylic acid, preferably N-(3-dimethylaminopropyl)(meth)acrylamide polymers, N-(diethylphosphono)(meth)acrylamide polymers, 1 -methacryloylamido-2-methyl-2-propanol polymers;

- polymers of sulfur-containing methacrylates, preferably ethylsulfinylethyl(meth)acrylate, 4-thiocyanatobutyl(meth)acrylate polymers, ethylsulfonylethyl(meth)acrylate polymers, thiocyanatomethyl(meth)acrylate polymers, methylsulfinylmethyl(meth)acrylate polymers, bis((meth)acryloyloxyethyl)sulfide polymers;

- polyhydric (meth)acrylates, preferably trimethyloylpropanetri(meth)acrylate polymers;

- acrylonitrile polymers;

- vinyl ester polymers, preferably vinyl acetate polymers;

- styrene polymers, substituted styrenes polymers with an alkyl substituent in the side chain, preferably α-methylstyrene and α -ethylstyrene, substituted styrenes polymers with an alkyl substituent on the ring, preferably vinyl toluene, and p-methylstyrene, halogenated styrene polymers, preferably monochlorostyrene polymers, dichlorostyrene polymers, tribromostyrene polymers and tetrabromostyrene polymers;

- heterocyclic vinyl polymers, preferably 2-vinylpyridine polymers, 3-vinylpyridine polymers, 2-methyl-5-vinylpyridine polymers, 3-ethyl-4-vinylpyridine polymers, 2,3-dimethyl-5-vinylpyridine polymers, vinylpyrimidine polymers, vinylpiperidine polymers, 9-vinylcarbazole polymers, 3-vinylcarbazole polymers, 4-vinylcarbazole polymers, 1-vinylimidazole polymers, 2-methyl-1-vinylimidazole polymers, N-vinylpyrrolidone polymers, 2-vinylpyrrolidone polymers, N-vinylpyrrolidine polymers, 3-vinylpyrrolidine polymers, N-vinylcaprolactam polymers, N-vinylbutyrolactam polymers, vinyl oxolane polymers, vinyl furan polymers, vinyl thiophene polymers, vinylthiolane polymers, vinylthiazoles and hydrogenated vinylthiazoles polymers, vinyloxazoles and hydrogenated vinyloxazoles;

- polymers of vinyl and isoprenyl ethers;

- maleic acid polymers, preferably maleic anhydride polymers, methyl maleic anhydride polymers, maleimide polymers, methyl maleimide; and

- dienes polymers, preferably divinylbenzene polymers;

- copolymers of ethylene and propylene with acrylic esters, preferably polyethylen-block-co-polymethylmethacrylate, polypropylen-block-co-polymethylmethacrylat;

- aliphatic and/or aromatic polyesters, preferably, hydroxyl-functional dendritic polyesters, polycaprolactone, polyethylenterephthalate (PET), polytrimethylenterephthalate (PTT), polybutylenterephthalate (PBT), glycolized polyglycolterephthaltate (G-PET), amorphous polyethylenterephthalate (A-PET), polyethylenfuranoate (PEF), polyethylennaphthylate (PEN), polyesters of terephthalic acid, polyspiro-diol-terephthalate, polypentaspiroglycol-terephthalate (PSG), polycyclohexylenedimethylene-terephthalate, polyester based copolymer including a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4-(hydroxymethyl)cyclohexylmethyl-4'-(hydroxymethyl)cyclohexane carboxylate, polyester based copolymer including a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4,4-(oxybis(methylene)bis) cyclohexane methanol;

- polycarbonate (PC), 2,2-Bis-(4-hydroxyphenyl)-propan (Bisphenol A) polycarbonate, 2,2-Bis-(4-hydroxyphenyl)-butan (Bisphenol B) polycarbonate, 1,1-Bis(4-hydroxyphenyl)cyclohexan (Bisphenol C) polycarbonate, 2,2'-Methylendiphenol (Bisphenol F) polycarbonate, 2,2-Bis(3,5-dibrom-4-hydroxyphenyl)propan (Tetrabrombisphenol A) polycarbonate und 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propan (Tetramethylbisphenol A) polycarbonate, bisphenol S polycarbonate, dihydroxydiphenylsulfid polycarbonate, tetramethylbisphenol A polycarbonate, 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) polycarbonate, 1,1,1-Tris(4-hydroxyphenyl)-ethane (THPE) polycarbonate;

- aliphatic polyamide (PA), preferably PA 6 based on polycaprolactam, PA 6.6 based on 6,6-hexamethylendiamin and adipic acid, PA 6.66 based on caprolactam, co-poymer of hexamethylendiamin and adipic acid, PA 66.610 based on hexamethylendiamin, copolymer of adipic acid and sebaic acid, PA 4.6, PA10, PA 12 and PA copolymers;

- polyurethane (PU),

- polar-copolymere, maleic anhydride-olefin copolymer;

- polyalkylenoxide, polyalkylene block copolymer, propylenoxide-ethylenoxide copolymer, (m)ethylene acrylate-maleic anhydride copolymer;

- polar-terpolymere, preferably reactive terpolymers of ethylene, acrylic ester and maleic anhydride, or ethylene, methacrylic ester and maleic anhydride, or ethylene, acrylic esters and glycidyl methacrylate, or ethylene, methacrylic esters and glycidyl methacrylate, or ethylene, (meth)acrylic esters and methyl (methyl(meth)acrylate), ethyl (ethy(meth)-acrylate), propyl (propyl(meth)acrylate), or butyl (butyl(meth)acrylate), polyamide, polyester-polyamides, or butyl (butyl(meth)acrylate), polyether-polyamide copolymers;

- polar polymer blends, preferably polycarbonate/polyethylenterephthalate blends (PC/PET blends), polycarbonate/polybutyleneterephthalate blends (PC/PBT blends), blends of polycyclohexylene dimethylene terephthalate copolymer, blends of poly(butylene-adipate-terephthalate);

- polyacrylnitril and polyacrylnitril-copolymers, preferably poly acrylonitrile butadiene styrene (ABS), poly styrene-acrylonitrile;

- polystyrene and polystyrene copolymers, preferably styrene/butadiene co-polymer (SBR), poly styrene-isoprene-styrene (SIS), poly(glycidyl methacrylate) grafted sulfonamide based polystyrene resin with tertiary amine;

- ethylene-vinyl acetate;

- polyether, preferably polyethyleneglycol, polyethyleneglycol with at least one fatty acid coupled to the polyethyleneglycol, terminating functional groups such NH₂-terminated polyethers;

- functionalized polyacrylamide polymers, copolymers and terpolymers, preferably poly(2-acrylamido-2-aminopropionicacid) (polyAMPA), poly(2-acrylamido-2-amino propane sulfonic acid), poly(N-isopropylacylamide (polyPNIPAM); poly (amidoamine-co-acrylic acid) copolymer, poly(N,N-dimethylacrylamide-co-sodium acrylate), poly(acrylamide-co-sodium acrylate)/poly(ethylene glycol) semi-IPN, poly(acrylamide-co-sodium 4-styrenesulfonate), poly(acrylamide-co-sodium 4-styrenesulfonate)/poly(ethylene glycol) semi-IPN, poly(acrylamide-co-sodium methacrylate), poly(acrylamide-co-sodium methacrylate)/poly(ethylene glycol) semi-IPN, and/or poly(N-isopropylacrylamide-co-acrylic acid) andpoly(acrylamide-co-acrylic acid;

- poly(ether sulfones)/poly(ethyleneimine) (PES/PEI);

- polyvinylpyrrolidone, preferably poly(N-vinyl-2-pyrrolidone), poly(N-vinyl-2-pyrrolidone-co-acrylonitrile) treated with hydroxylamine-hydrochloride

- polyvinyl alcohol;

- poly(1-naphthylamine)-camphorsulphonic acid.

10. The method according to any of claims 1 to 9, wherein the synthetic or non-synthetic polar-oligomer or mixture thereof is selected from the group comprising:

- oligoacrylate with methyl (oligomethylacrylate), ethyl (oligoethylacrylate), propyl (oligopropylacrylate), or butyl (oligobutylacrylate),

- oligomethacrylate with methyl (oligomethylmathacrylate), ethyl (oligoethylmethacrylate), propyl (oligopropylmethacrylate), or butyl (oligobutylmethacrylate),

- cooligomers of acrylic and methacrylic esters including, among others, tert. - Butyl (meth)acrylate, pentyl(meth)acrylate and 2-ethylhexyl(meth)acrylate; (Meth)acrylates derived from unsaturated alcohols, preferably oleyl(meth)acrylate, 2-propynyl(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate;

- aryl(meth)acrylates oligomers, preferably benzyl(meth)acrylate oligomers or phenyl(meth)acrylate oligomers, the aryl radicals each being unsubstituted or up to four times substituted;

- cycloalkyl(meth)acrylates oligomers, preferably 3-vinylcyclohexyl(meth)acrylate oligomers, bornyl (meth)acrylate oligomers;

- hydroxylalkyl (meth)acrylates oligomers, preferably 3- hydroxypropyl (meth)acrylate oligomers, 3,4- dihydroxybutyl(meth)acrylate oligomers, 2-hydroxyethyl(meth)acrylate oligomers, 2-hydroxypropyl(meth)acrylate oligomers;

- glycol di(meth)acrylates oligomers, preferably 1,4-butanediol (meth)acrylate oligomers;

- (meth)acrylates of ether alcohols oligomers, preferably tetrahydrofurfuryl (meth)acrylate oligomers, vinyloxyethoxyethyl(meth)acrylate oligomers;

- oligomers of amides and nitriles of the (meth)acrylic acid, preferably N-(3-dimethylaminopropyl)(meth)acrylamide oligomers, N-(diethylphosphono)(meth)acrylamide oligomers, 1-methacryloylamido-2-methyl-2-propanol oligomers;

- oligomers of sulfur-containing methacrylates, preferably ethylsulfinylethyl( meth)acrylate, 4-thiocyanatobutyl(meth)acrylate oligomers, ethylsulfonylethyl(meth)acrylate oligomers, thiocyanatomethyl(meth)acrylate oligomers, methylsulfinylmethyl(meth)acrylate oligomers, bis((meth)acryloyloxyethyl)sulfide oligomers;

- oligohydric (meth)acrylates, preferably trimethyloylpropanetri(meth)acrylate oligomers;

- acrylonitrile oligomers;

- vinyl ester oligomers, preferably vinyl acetate oligomers;

- styrene oligomers, substituted styrenes oligomers with an alkyl substituent in the side chain, preferably α-methylstyrene and α -ethylstyrene, substituted styrenes oligomers with an alkyl substituent on the ring, preferably vinyl toluene, and p-methylstyrene, halogenated styrene oligomers, preferably monochlorostyrene oligomers, dichlorostyrene oligomers, tribromostyrene oligomers and tetrabromostyrene oligomers;

- heterocyclic vinyl oligomers, preferably 2-vinylpyridine oligomers, 3-vinylpyridine oligomers, 2-methyl-5-vinylpyridine oligomers, 3-ethyl-4-vinylpyridine oligomers, 2,3-dimethyl-5-vinylpyridine oligomers, vinylpyrimidine oligomers, vinylpiperidine oligomers, 9-vinylcarbazole oligomers, 3-vinylcarbazole oligomers, 4-vinylcarbazole oligomers, 1-vinylimidazole oligomers, 2-methyl-1-vinylimidazole oligomers, N-vinylpyrrolidone oligomers, 2-vinylpyrrolidone oligomers, N-vinylpyrrolidine oligomers, 3-vinylpyrrolidine oligomers, N-vinylcaprolactam oligomers, N-vinylbutyrolactam oligomers, vinyl oxolane oligomers, vinyl furan oligomers, vinyl thiophene oligomers, vinylthiolane oligomers, vinylthiazoles and hydrogenated vinylthiazoles oligomers, vinyloxazoles and hydrogenated vinyloxazoles;

- oligomers of vinyl and isoprenyl ethers;

- maleic acid oligomers, preferably maleic anhydride oligomers, methyl maleic anhydride oligomers, maleimide oligomers, methyl maleimide; and

- dienes oligomers, preferably divinylbenzene oligomers;

- cooligomers of ethylene and propylene with acrylic esters, preferably oligoethylen-block-co-oligomethylmethacrylate, oligopropylen-block-co-oligomethylmethacrylat;

- aliphatic and/or aromatic oligoesters, preferabl, hydroxyl-functional dendritic oligoesters, preferably oligocaprolactone, oligoethylenterephthalate (PET), oligotrimethylenterephthalate (PTT), oligobutylenterephthalate (PBT), glycolized oligoglycolterephthaltate (G-PET), amorphes oligoethylenterephthalate (A-PET), oligoethylenfuranoate (PEF), oligoethylennaphthylate, oligoesters of terephthalic acid, oligospiro-diol-terephthalate, oligopentaspiroglycol-terephthalate (PSG), polycyclohexylenedimethylene-terephthalate, oligoester based cooligomer including a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4-(hydroxymethyl)cyclohexylmethyl-4' -(hydroxymethyl)cyclohexane carboxylate, oligester based cooligomer including a dicarboxylic acid-derived residue including a residue derived from an aromatic dicarboxylic acid and a diol-derived residue including a residue derived from 4,4-(oxybis(methylene)bis) cyclohexane methanol;

- oligocarbonate (PC), 2,2-Bis-(4-hydroxyphenyl)-propan (Bisphenol A) oligocarbonate, 2,2-Bis-(4-hydroxyphenyl)-butan (Bisphenol B) oligocarbonate, 1,1-Bis(4-hydroxyphenyl)cyclohexan (Bisphenol C) oligocarbonate, 2,2'-Methylendiphenol (Bisphenol F) oligocarbonate, 2,2-Bis(3,5-dibrom-4-hydroxyphenyl)propan (Tetrabrombisphenol A) oligocarbonate und 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propan (Tetramethylbisphenol A) oligocarbonate, bisphenol S oligocarbonate, dihydroxydiphenylsulfid oligocarbonate, tetramethylbisphenol A oligocarbonate, 1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) oligocarbonate, 1,1,1-Tris(4-hydroxyphenyl)-ethane (THPE) oligocarbonate;

- aliphatic oligoamide (PA), preferably PA 6 based on oligocaprolactam, PA 6.6 based on 6,6-hexamethylendiamin and adipic acid, PA 6.66 based on caprolactam, co-poymer of hexamethylendiamin and adipic acid, PA 66.610 based on hexamethylendiamin, cooligomer of adipic acid and sebaic acid, PA 4.6, PA10, PA 12 and PA cooligomers;

- oligourethane (PU),

- polar-cooligomere, maleic anhydride-olefin cooligomer;

- oligoalkylenoxide, oligoalkylene block cooligomer, propylenoxide-ethylenoxide cooligomer, (m)ethylene acrylate-maleic anhydride cooligomer;

- polar-teroligomere, preferably reactive teroligomers of ethylene, acrylic ester and maleic anhydride, or ethylene, methacrylic ester and maleic anhydride, or ethylene, acrylic esters and glycidyl methacrylate, or ethylene, methacrylic esters and glycidyl methacrylate, or ethylene, (meth)acrylic esters and methyl (methyl(meth)acrylate), ethyl (ethy(meth)-acrylate), propyl (propyl(meth)acrylate), or butyl (butyl(meth)acrylate), oligoamide, oligoester-oligoamides, or butyl (butyl(meth)acrylate), oligoether-oligoamide cooligomers;

- polar oligomer blends, preferably oligocarbonate/oligoethylenterephthalate blends (PC/PET blends), oligocarbonate/oligobutyleneterephthalate blends (PC/PBT blends), blends of oligocyclohexylene dimethylene terephthalate cooligomer, blends of oligo(butylene-adipate-terephthalate);

- oligoacrylnitril and oligoacrylnitril-cooligomers, preferably oligo acrylonitrile butadiene styrene (ABS), oligo styrene-acrylonitrile;

- oligostyrene and oligostyrene cooligomers, preferably styrene/butadiene co-oligomer (SBR), oligo styrene-isoprene-styrene (SIS), oligo(glycidyl methacrylate) grafted sulfonamide based oligostyrene resin with tertiary amine;

- ethylene-vinyl acetate;

- oligoether, preferably oligoethyleneglycol, oligoethyleneglycol with at least one fatty acid coupled to the oligoethyleneglycol, oligoether with terminating functional groups, preferbyl NH₂-terminated oligoethers,

- functionalized oligoacrylamide oligomers, cooligomers and teroligomers, preferably oligo(2-acrylamido-2-aminopropionicacid) (oligoAMPA), oligo(2-acrylamido-2-amino propane sulfonic acid), oligo(N-isopropylacylamide (oligoPNIPAM); oligo (amidoamine-co-acrylic acid) co-oligomer, oligo(N,N-dimethylacrylamide-co-sodium acrylate), oligo(acrylamide-co-sodium acrylate)/oligo(ethylene glycol) semi-IPN, oligo(acrylamide-co-sodium 4-styrenesulfonate), oligo(acrylamide-co-sodium 4-styrenesulfonate)/oligo(ethylene glycol) semi-IPN, oligo(acrylamide-co-sodium methacrylate), oligo(acrylamide-co-sodium methacrylate)/oligo(ethylene glycol) semi-IPN, and/or oligo(N-isopropylacrylamide-co-acrylic acid) andoligo(acrylamide-co-acrylic acid;

- oligo(ether sulfones)/oligo(ethyleneimine) (PES/PEI);

- oligovinylpyrrolidone, preferably oligo(N-vinyl-2-pyrrolidone), oligo(N-vinyl-2-pyrrolidone-co-acrylonitrile) treated with hydroxylamine-hydrochloride

- oligovinyl alcohol;

- oligo(1-naphthylamine) camphorsulphonic acid.

11. The method according to any of the preceding claims 1 to 10, wherein, wherein the polar-additive having a Mw about ≥ 70 and < 600 g/mol is selected from the group comprising aliphatic acids CH₃-[CH₂]_n-COOH acids (n about ≥ 3), amino acids, carboxylic acid amide, hydroxyl acids, fatty acids, aliphatic or aliphatic/aromatic aldehydes and ketones, esters, pentaerithritol, pentaerithrtiol ester preferably carboxylic acid ester, benzoic acid esters comprising benzylbenzoate or phenylbenzoate, phenylether, alcohols and polyvalent alcohols and their esters, preferably glycerine and glycerine esters, amines, wherein the polar-additive is selected different to the organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol; and preferably the polar-additive having a Mw about ≥ 100 and < 600 g/mol is containing a heteroatom selected from N, O, S, P and/or halogene.

12. The method according to any of the preceding claims 1 to 11, wherein the non-polar-polymer is selected from the group of polyalkylene polymers, polyalkylene copolymers, polyakylene block copolymers; the non-polar-polymer is preferably selected from of polymeric aliphatic or aromatic hydrocarbons, preferably polyalkylene polymers, polyalkylene co- and terpolymer with random or block-structure; and more preferred from polyethylen (PE), polypropylene (PP), polybutene (PB), polystyrene, polyisobutylene, polybutadiene, polyisoprene.

13. The method according to any of the preceding claims 1 to 12, wherein the organic aromatic coloring agent has a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol, preferably the organic aromatic coloring agent has a molecular weight Mw in the range of about ≥ 270 g/mol to about ≤ 450 g/mol, and more preferably the organic aromatic coloring agent has a molecular weight Mw in the range of about ≥ 285 g/mol to about ≤ 400 g/mol.

14. The method according to any of the preceding claims 1 to 13, wherein

- the organic aromatic coloring agent in form of a powder has an average particle diameter of about ≥ 50 nm to about ≤ 0.5 µm, preferably an average particle diameter of about ≥ 500 nm to about ≤ 2 µm; or

- the organic aromatic coloring agent in form of a powder has a particle size D₁₀ of about ≥ 300 nm and about ≤ 0.75 µm, preferaply the organic aromatic coloring agent has a particle size D₅₀ of about ≥ 450 nm and about ≤ 1.5 µm, and further preferred the organic aromatic coloring agent has a particle size D₁₀₀ of about ≥ 1 µm and about ≤ 3 µm.

15. The method according to any of the preceding claims 1 to 14 wherein the organic aromatic coloring agent free of a sulfonic acid group have a solubility in water at 23 °C of about ≤ 0.1 g/l and > 0 g/l, preferably about ≤ 0.05 g/l and > 0 g/l, more preferably about ≤ 0.005 g/l and > 0 g/l; and the organic aromatic coloring agent comprising a sulfonic acid group have a solubility in water at 23 °C of about ≥ 10 g/l, preferably a solubility in water at 90 °C of about ≥ 20 g/l.

16. The method according to any of the preceding claims 1 to 15, wherein the organic aromatic coloring agent comprises at least 2 to 6 aromatic or heteroaromatic six-membered rings, at least 3 to 5 aromatic or heteroaromatic six-membered rings and at least 1 to 4 five-membered aromatic or heteroaromatic rings, or having at least 2 to 6 aromatic or heteroaromatic six-membered rings; and/or wherein the organic aromatic coloring agent comprises at least on heteroatom selected from N, O, S, halogens.

17. The method according to any of the preceding claims 1 to 16, wherein the agent is liquid at 23 °C, preferably the agent is a composition that is liquid at 23 °C, wherein the liquid agent or liquid agent composition is a true solvent, colloid solution, emulsion, dispersion or suspension.

18. The method according to any of the preceding claims 1 to 17, wherein the agent is selected from the group comprising a C₁ to C₁₅ alcohol, C₂ to C₂₀ organic acid, C₃ to C₆ ketone, C₃ to C₅ aldehyde, C₁ to C₆ alkyl, C₃ to C₆ ester, alkylene glycol alkyl ether, glycol alkyl ether, glycol and glycol oligomers (e.g. PEG 200), glycol ether, ethanol, glycerol, acetone, formic acid, acetic acid, dimethylformamide, dimethylsulfoxide, acetyltributylcitrate, carboxymethylcellulose (CMC), fluorocarbons, fluorine derivates, silicones, hydrocarbons, alkylphosphates, buffers (such as acetic acid/Na-acetat) water or a mixture thereof, preferably the agent is selected from the group comprising glycol and glycol oligomers, ethanol, propanol, isopropanol, amyl alcohol (pentanol isomers), glycerol, acetone, methylethylketone, acetyltributylcitrate, tributylphosphate (defoamer), n-butyl acid ester, diethylenglycol-n-butyl-ether, water or mixture thereof.

19. The method according to any of the preceding claims 1 to 18, wherein the agent is selected from:

- n-butylacetat; or

- a mixture of glycerol, propanol and water; or

- a mixture of ethanol, amyl alcolhol, carboxymethylcellulose (CMC), tributylphosphate and water to 100%; or

- ethanol, dimethylformamid, tributylphosphate and water; or

- n-butylacetate, diethylenglycol-mono-n-butylether, tributylphosphate and water, or

- acetyltributylcitrat, diethylenglycol-mono-n-butylether, tributylphosphate and water.

20. The method according to any of the preceding claims 1 to 19, wherein the coloring composition comprises in addition a dispersing agent, wherein the dispersing agent is preferably selected from the group comprising at least one:

- anionic tenside, preferably selected from polyphosphates, polyacrylates, aromatic sulfonates, esters with ethoxylate groups, esters with sulfonate groups, fatty acid-based polymers with an anionic group, salts of polycarboxylic acids, ethoxylates, thiourea dioxide;

- cationic tenside, preferably selected from quaternary ammonium compounds, fatty acid-polymers with a cationic group per molecule;

- non-ionic tenside, preferably selected from aromatic esters and hydrocarbons, aromatic and non-aromatic carboxylic acid esters, ethyl acrylate, fatty acid esters, ethoxylated fatty acid, poly oxyethylated compounds derived from sorbitol and oleic acid, polymers that are fatty acid-based with a non-ionic group per molecule, acrylate-copolymers, acrylate/styrene copolymers, fatty acid derivatives, polyalkoxylate;

- polyurethane (PUR) polymers and/or polyacrylate polymers, preferably linear or branched polyurethane (PUR) polymers and/or polyacrylate polymers, more preferred the polyurethane (PUR) polymer and/or polyacrylate polymer have a MW of 5000 to 30000 g/mol.

21. The method according to any of the preceding claims 1 to 20, wherein the coloring composition comprises in addition a carrier agent, wherein the carrier agent is preferably selected from the group comprising aromatic esters such as benzoic acid or phthalic acid esters, polyphenylether, phenoles, aromatic alcohols, aromatic ketones, aryl halides, such as halogenized benzene, halogenized toluene; N-alkylphthalimide, methylnaphthaline, diphenyle, diphenylethere, naphtholether, oxybiphenyle, o-vanilline, coumarin and/or mitxtures thereof.

22. The method according to any of the claims 1 to 21, wherein the coloring composition exposed to at least the heated area of the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized has a temperature higher than the glass-transition temperature Tg of the synthetic or non-synthetic polar-component of the synthetic or non-synthetic polar-polymer material to be colored; and/or the coloring composition exposing the synthetic or non-synthetic polar-polymer material has a temperature lower than the heat deflection temperature of the synthetic or non-synthetic polar-polymer material to be colored.

23. The method according to any of the claims 1 to 22, wherein the coloring composition exposed to at least the heated area of the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized has a temperature that is at least 30° C, preferably at least 40° C, and ≥ 0° C ± 5° C to ≤ 30° C above the temperature of at least the heated area of the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized; or wherein the coloring composition exposed to at least the heated area of the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized has a temperature that is at least 40° C and ≥ 0° C to ≤ 20° C below or above the temperature of at least the heated area of the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized; or wherein the coloring composition exposed to at least the heated area of the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized has a temperature that is at least 40° C and ≥ 0° C to ≤ 10° C below or above the temperature of at least the heated area of the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized.

24. The method according to any of the previous claims 1 to 23, wherein the step of exposing the heated outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized to the coloring composition comprises:

- dipping at least the outer surface or the heated outer surface, wherein areas that should not be colorized are covered, or dipping at least the heated intended pattern area of the outer surface to be colored, of the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material to be colorized into the coloring composition; and/or

- flow coating at least the outer surface of the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material to be colorized with the coloring composition; and/or- digitally printed via inkjet printing at least the outer surface of the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material to be colorized with the coloring composition; and/or

- analogue printing via screen, gravure, offset, or flexo printing at least the outer surface of the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material to be colorized with the coloring composition; and/or

- spray coating at least the outer surface of the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material to be colorized with the coloring composition; and/or

- pen coating at least the outer surface of the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material to be colorized with the coloring composition; and/or

- direct or indirect coating at least the outer surface of the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material to be colorized with the coloring composition; and/or
combinations thereof.

25. The method according to any of the previous claims 1 to 24, wherein at least the heated area of the intended pattern of the outer surface of the synthetic or non-synthetic polar-polymer material that is to be colorized, which is exposed to the coloring composition has a temperature about ≥ 40° C and lower than the heat deflection temperature of the synthetic or non-synthetic polar-polymer material.

26. The method according to any of the previous claims 1 to 25, wherein the outer surface of the synthetic or non-synthetic polar-polymer material that is not supposed to be colorized by the coloring composition has a temperature ≤ 40° C.

27. The method according to any of the preceding claims 1 to 26, wherein the synthetic or non-synthetic polar-polymer material is formed in a molding process, a compression molding process, an extruding process, a thermoforming process and/or a blowing process.

28. The method according to any of the preceding claims 1 to 27, wherein at least the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material that is to be colorized is colorized by the coloring composition by means of a 2D-printing process.

29. The method according to any of the preceding claims 1 to 28, wherein at least the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material that is to be colorized is colorized by the coloring composition by means of a 3D-printing process, wherein the print head is guided around at least the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material kept at a constant distance to be printed, preferably by means of a 5-axis robot.

30. The method according to any of the preceding claims 1 to 29 wherein at least the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material that is to be colorized is colorized by the coloring composition by means of a 3D-printing process in which at least the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material is guided around the print head kept at a constant distance to be printed e.g. a 5-axis robot.

31. The method according to any of the preceding claims 1 to 30, wherein at least the heated area of the intended pattern of the synthetic or non-synthetic polar-polymer material for coloring is exposed to the coloring composition for about > 0 second to about ≤ 600 seconds, preferably about ≥ 0.01 seconds to about ≤ 300 seconds, in addition preferred about ≥ 0.1 seconds to about ≤ 100 seconds, and also preferred about ≥ 0.3 seconds to about ≤ 5 seconds, or about ≥ 0.5 seconds to about ≤ 1 second.

32. The method according to any of the preceding claims 1 to 31, wherein the coloring composition comprises:

- about ≥ 0.1 wt.-% to about ≤ 25 wt.-% at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol;

- about ≤ 99.9 wt.-% to about ≥ 75 wt.-% of the agent.

33. The method according to any of the preceding claims 1 to 32, wherein the coloring composition comprises:

- about ≥ 0.1 wt.-% to about ≤ 25 wt.-% at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol; and

- about ≤ 99.9 wt.-% to about ≥ 75 wt.-% of the agent;

- about ≥ 0 wt.-% to about ≤ 20 wt.-% of at least one dispersing agent for dispersing the organic aromatic coloring agent in the aqueous solution or non-aqueous solution, and

- ≥ 0 wt.-% water and preferably water is added to 100 wt.-%.

34. The method according to any of the preceding claims 1 to 33, wherein the coloring composition comprises:

- about ≥ 0.1 wt.-% to about ≤ 25 wt.-% , preferably about ≥ 0.5 wt.-% to about ≤ 15 wt.-%, of at least one organic aromatic coloring agent having a molecular weight Mw in the range of about ≥ 250 g/mol to about ≤ 750 g/mol;

- about ≤ 99.9 wt.-% to about ≥ 55 wt.-% of the agent,

- about ≥ 0.01 wt. -% to about ≤ 20 wt.-% of dispersing agent for dispersing the organic aromatic coloring agent in the aqueous solution or non-aqueous solution, wherein the non-aqueous solution is optional a homeogenius solution,

- about ≥ 0 wt.-% to about ≤ 10 wt.-% of least one buffer,

- about ≥ 0.05 wt.-% to about ≤ 10 wt.-% of at least one carrier agent, and

- ≥ 0 wt.-% water and preferably water added to 100 wt.-%.

35. The method according to any of the preceding claims 1 to 34, wherein the coloring composition has a pH in the range of about ≥ 2.5 and about ≤ 12, preferably a pH in the range of about ≥ 3.0 and about ≤ 10; in addition preferred a pH in the range of about ≥ 3.2 and about ≤ 7 and also preferred a pH in the range of about ≥ 4 and about ≤ 5.

36. The method according to any of the preceding claims 1 to 35, wherein the synthetic or non-synthetic polar-polymer material comprises at least two layers, wherein at least a first layer is of a polar-polymer material, that comprises about ≥ 0.5 wt.-%, preferably about ≥ 5 wt.-%, more preferably ≥ 10 wt.-%, of polar components, such as synthetic or non-synthetic polar polymer, synthetic or non-synthetic polar oligomer and/or polar additive, and is colorizable by the coloring composition, where else the second layer comprising less than about 5 wt.-%, preferably about < 3 wt.-%, further preferred about < 2 wt.-% and in addition preferred about < 0.5 wt.-% or about ≥ 0 to < 0.1 wt.-% of a polar component and about ≥ 90 wt.-%, preferably about ≥ 95 wt.-% to about ≤ 100 wt.-% of at least one non-polar component, such as non-polar polymer and/or non-polar oligomer, cannot be colorized by the coloring composition.

37. A colored synthetic or non-synthetic polar-polymer material, wherein the synthetic or non-synthetic polar-polymer material, preferably the outer surface of the synthetic or non-synthetic polar-polymer material, is reversible colored by a method according to any of claims 1 to 36.

38. A colored synthetic or non-synthetic polar-polymer material according to claim 37 comprising at least one synthetic or non-synthetic polar-component layer and at least one non-polar-component layer, wherein at least one layer or outer surface of the synthetic or non-synthetic polar-component layer is reversible colored by a method according to any of claims 1 to 35, wherein the non-polar-component layer is not colorable by the method according to claims 1 to 36.

39. A colored synthetic or non-synthetic polar-polymer material according to claim 37 or 38, wherein at least a layer thickness of about ≥ 0.1 µm, preferably of about ≥ 1 µm to about ≤ 1000 µm, of the colored synthetic or non-synthetic polar-polymer material is homogenous colored.

40. A colored synthetic or non-synthetic polar-polymer material according to any of claims 37 to 39, wherein the concentration of the organic aromatic coloring agent in at least one colored layer of the synthetic or non-synthetic polar-polymer material, colored by a method according to any of claims 1 to 32, is 0.00001 wt.-% to about ≤ 5 wt.-%, wherein the colored layer has a thickness of about ≥ 0.1 µm, based on the total weight of said colored layer.

41. Article comprising at least one colored synthetic or non-synthetic polar-polymer material according to claims 37 to 40 colored by a method according to claims 1 to 36.

42. Article according to claim 41, wherein the article is selected from the group comprising a sheet, a foil, a container, a part, a bottle, a non-woven fabric, and preferably the article is selected from the group comprising computer face-plates, keyboards, bezels and cellular phones, color coded packaging and containers of all types, including ones for industrial components, residential and commercial lighting fixtures and components thereof, such as sheets, used in building and in construction, tableware, including plates, cups and eating utensils, small appliances and their components, optical and sun-wear lenses, decorative films including such films that are intended for use in film insert molding, performs, floor panel, wall panel or crucible.