(19)
(11)EP 2 288 506 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
20.12.2017 Bulletin 2017/51

(21)Application number: 08772201.3

(22)Date of filing:  27.06.2008
(51)Int. Cl.: 
B41M 5/52  (2006.01)
C09D 11/322  (2014.01)
B41M 5/00  (2006.01)
(86)International application number:
PCT/US2008/068662
(87)International publication number:
WO 2009/157952 (30.12.2009 Gazette  2009/53)

(54)

SURFACE TREATMENT COMPOSITION, INKJET PRINTABLE ARTICLE AND METHOD OF MAKING THE SAME

OBERFLÄCHENBEHANDLUNGSZUSAMMENSETZUNG, TINTENSTRAHLBEDRUCKBARER ARTIKEL UND HERSTELLUNGSVERFAHREN DAFÜR

COMPOSITION DE TRAITEMENT DE SURFACE, ARTICLE POUVANT ÊTRE IMPRIMÉ PAR JET D'ENCRE ET PROCÉDÉ DE RÉALISATION CORRESPONDANT


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

(43)Date of publication of application:
02.03.2011 Bulletin 2011/09

(73)Proprietor: Hewlett-Packard Development Company, L.P.
Houston, TX 77070 (US)

(72)Inventor:
  • ZHOU, Xiaoqi
    San Diego, CA 92127-1899 (US)

(74)Representative: Rees, Simon John Lewis 
Haseltine Lake LLP Redcliff Quay 120 Redcliff Street
Bristol BS1 6HU
Bristol BS1 6HU (GB)


(56)References cited: : 
EP-A1- 0 827 842
WO-A1-2007/044228
US-A1- 2005 107 254
US-B2- 6 880 928
WO-A1-96/35841
WO-A2-03/104336
US-B2- 6 761 942
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    BACKGROUND



    [0001] The present disclosure relates generally to printing media used with the latest digital printing technology, e.g. thermal inkjet printers, especially ones using pigmented inks. Such high quality, low cost printing equipment does not always work at an optimum level with traditional printing papers. Furthermore, issues relating to cost, image quality, environmental impact and mechanical ease of use (e.g. minimal paper jams) all must be addressed with these products. Pigmented inks make the resolution of such problems more complex because of the differences with the way pigment particles react with media in comparison with dye molecules in dye based inks. Image qualities such as ink bleed, black optical density and color saturation are greatly dependent upon the diffusion and/or interaction of pigmented ink with printing papers. Another problem that occurs is "image strike through," when images printed on one side come through to the other side of the paper. An additional problem is extended ink dry time which refers to the time it takes for the ink to dry such that it will not smear or transfer to other surfaces.

    [0002] It has been found that divalent salt, such as calcium chloride, as an additive in the surface sizing layer added during the media making process, can react with the pigments in the ink. By this means, the pigment colorant can be made to stay on the outermost layer of the media. This increases the optical density of the image on the media and reduces the dry time. However, to achieve such effects, the divalent salt needs to be used at a concentration greater than from about 6 to about 12 kg salt per ton (T) of paper. Such a high loading of chloride-containing compounds may promote drastic corrosion of the paper milling equipment used to produce the print media, and may significantly reduce the life span of the salt-contacting parts of the paper manufacturing equipment, such as, e.g., sizing rolls.

    [0003] Another drawback commonly associated with the use of calcium chloride salt arises from its exothermic dissolution in water. A significant amount of heat is produced when large batches of calcium chloride salt solution is prepared, as is customary in commercial paper manufacturing processes. Solution temperatures can easily reach from about 90°C to about 100°C or more. The chloride-containing vapors from such a heated solution may, in some instances, cause potential environmental issues for workers involved with the mixing process. Further, the di-valent salts like calcium chloride or magnesium chloride are very moisture-absorbent. The use of this type of salt can easily change the stiffness of the paper due to absorption of water into the paper. This inevitably causes some issues related to the runnability of the media in the print. These issues can cause, for example, paper jamming and/or multi-picking of the sheets from a paper tray.

    [0004] WO 03/104336 describes a coating composition comprising a blend of at least two dye fixatives, at least one of which is a cationic polymer, and at least one of the other dye fixatives is a polyvalent metal salt, to form a water-insoluble complex.

    [0005] US 6761942 describes an ink jet recording sheet comprising a non-water absorptive support having thereon an ink absorptive layer comprising polyvinyl alcohol, a cationic polymer, and a compound containing zirconium or aluminum atom other than zirconium oxide and aluminum oxide.

    BRIEF DESCRIPTION OF THE DRAWING



    [0006] Features and advantages of embodiments of the present disclosure will become apparent by reference to the following detailed description and drawing, in which:

    Figure 1 is a graph showing color gamut vs. weight percentage of salt in the composition.


    DETAILED DESCRIPTION



    [0007] The present invention provides: a surface treatment composition as set out in claim 1 or claim 2; a method of making a surface-treated inkjet media as set out in claim 8; a system of inkjet printing as set out in claim 10; and an inkjet printable paper as set out in claim 11.

    [0008] The inkjet printing media of the present application includes a base stock and a surface treatment composition. The surface treatment composition can be applied on either one or both sides of the base stock. Non-limiting examples of base stocks include cellulose paper, polymeric film and cellulose paper laminate which are coated by polymeric materials on one or both sides of the base stock. The basis weight of the base stock ranges from about 35 gsm to about 250 gsm.

    [0009] The substrate used to make inkjet printing media can include cellulose fibers. The type of fiber is not critical, and any such fiber known for use in papermaking can be used. For example, the substrate can be made from pulp fibers derived from hardwood trees, softwood trees, or a combination of hardwood and softwood trees prepared for use in papermaking fiber furnished by any known suitable digestion, refining, and bleaching operations as are, for example, known in mechanical, thermomechanical, chemical and semichemical, etc., pulping and other well-known pulping processes. The term "hardwood pulps" refers to fibrous pulp derived from the woody substance of deciduous trees (angiosperms) such as birch, oak, beech, maple, and eucalyptus. The term "softwood pulps" refers to fibrous pulps derived from the woody substance of coniferous trees (gymnosperms) such as varieties of fir, spruce, and pine, as for example loblolly pine, slash pine, Colorado spruce, balsam fir and Douglas fir. In certain embodiments, at least a portion of the pulp fibers may be provided from non-woody herbaceous plants including, but not limited to, kenaf, hemp, jute, flax, sisal, or abaca. Either bleached or unbleached pulp fiber may be utilized in the process of this disclosure. Recycled pulp fibers are also suitable for use. In an embodiment, the cellulosic fibers in the paper include from about 30% to about 100% by weight hardwood fibers, and from about 0% to about 70% by weight softwood fibers.

    [0010] Additionally, a number of fillers may be included in the above-mentioned pulps during formation of the substrate. According to one exemplary embodiment, the fillers that may be incorporated into the pulp to control physical properties of the final substrate include, but are in no way limited to, ground calcium carbonate, precipitated calcium carbonate, titanium dioxide, kaolin clay, silicates, and combinations thereof. As incorporated in the present example system and method, the amount of fillers may vary widely. However, according to one embodiment, the fillers (if used) represent from approximately 0% to approximately 40% by weight of the dry fibers; and according to another embodiment, the filler represents from approximately 10% to approximately 20% by weight of the dry fibers.

    [0011] The capability and speed of the base stock to absorb aqueous solvent is an important aspect of the inkjet printing media of the present application. Excessive absorption will bring the colorant into the bulk area of the base, generally resulting in low black and color optical density and low color gamut. This will create a "washed out" image. Poor absorption, on the other hand, creates a situation in which the ink bleeds and smears readily. Furthermore, poor absorption also necessitates an increase in dry time.

    [0012] Aqueous solvent absorption in base stock is primarily controlled by the sizing processing on the base stock. This includes both the process of internal sizing and surface sizing. During the process of internal sizing, chemicals are added to the papermaking furnish and retained on the fiber by appropriate means in the wet end of the papermaking system before the pulp suspension is converted to a paper web or substrate. By this means, resistance to wetting and penetration by liquids is controllable.

    [0013] The internal sizing agents for use in this application encompass all those commonly used at the wet end of a paper machine. For example, internal sizing agents include but are not limited to: starch; carboxymethylcellulose (CMC); polyvinyl alcohol; methyl cellulose; alginates; waxes; wax emulsions; alkylketene dimer (AKD); alkyl succinic anhydride (ASA); alkenyl ketene dimer emulsion (AKD); emulsions of ASA or AKD with cationic starch; ASA incorporating alum; and combinations of such sizing agents. The internal sizing agents are generally used at concentration levels normal for the art of papermaking. For example, a concentration of internal sizing agents from about 0.01 weight% to about 0.5 weight% based on the weight of the dry paper sheet would be considered normal, but an optimum amount is decided according to absorption requirements as described below.

    [0014] The degree of internal sizing can be characterized in terms of how much the paper stock absorbs the aqueous solvents, and how quickly the aqueous solvent penetrates through the paper stock. The Cobb test is used for measurement of liquid absorption, where one surface of the paper sample is exposed under a given
    hydrostatic head to water under a specified time, i.e., 60 seconds with the circular area of the sample being 100 cm2. After a fixed time of 60 seconds, the water is decanted, and excess water is blotted off. The water absorbed in terms of gram per square meter (gsm) is used to evaluate absorption capability. To obtain optimum printing results in the instant disclosure, the internal sizing agents should be applied in an amount that yields a Cobb value in the range from about 20 to about 50 gsm. An even better result can be achieved in the range from about 25 gsm to about 40 gsm. The penetration property of the paper sample is determined by the Hercules Size Test (HST) method, where a green dyed (Naphtol Green B) formic acid solution is used to determine the time spent to reach the 80% of remitted monochromatic light. To achieve the optimum printing quality, the value of the HST test should be controlled from about 25 seconds to about 400 seconds.

    [0015] In the surface sizing process, a surface sizing composition is applied to the surface of the paper web. Specifically in this disclosure, a surface treatment composition can be the surface sizing composition applied to the surface of the paper web. By such a fiber surface modification process, not only the integrity of the fabric web structure is improved, but also the absorbency, repellency and spreading of the aqueous liquid can be controlled at a desired level so that ink absorption and penetration are optimized to produce a better image. Further in the instant disclosure, the media surface is modified to become more "adaptable" to the pigmented inkjet inks. Described herein is a surface treatment composition including at least one surface sizing agent as well as at least one high valence metallic salt such as a trivalent salt as colorant fixer. The surface sizing agents can include starches and/or starch derivatives; carboxymethylcellulose (CMC); methyl cellulose; alginates; waxes; wax emulsions; alkylketene dimer (AKD); alkyl succinic anhydride (ASA); alkenyl ketene dimer emulsion (AKD); emulsions of ASA or AKD with cationic starch; ASA incorporating alum; water-soluble and/or water-dispersible polymeric materials; and combinations thereof.

    [0016] Such water-soluble and/or water-dispersible polymeric materials can include polyvinyl alcohol; gelatin; cellulose derivatives; acrylamide polymers; acrylic polymers or copolymers; vinyl acetate latex; polyesters; vinylidene chloride latex; styrene-butadiene; acrylonitrile-butadiene copolymers; styrene acrylic polymers and copolymers; and combinations thereof. Examples of starches include corn starch, tapioca starch, wheat starch, rice starch, sago starch and potato starch. These starch species can be unmodified starch, enzyme modified starch, thermal and thermal-chemical modified starch and chemically modified starch. In one embodiment, the chemically modified starch is used, which includes, but is not limited to, converted starches such as acid fluidity starches; oxidized starches and pyrodextrins; derivatized starches such as hydroxyalkylated starches; cyanoethylated starch; cationic starch ethers; anionic starches; starch esters; starch grafts; and hydrophobic starches. Non-limitative examples of other suitable surface sizing agents also include styrene-based emulsion polymers, AKD, and/or combinations thereof.

    [0017] The surface treatment composition includes at least one ink fixative made of high valence metallic salt ("high valence" being defined as greater than the valence of a divalent salt), such as trivalent salts. The pigmented ink for inkjet printing is usually an aqueous suspension system, where the pigmented colorants are dispersed into the aqueous vehicle to form a stable ink suspension. When pigmented ink drops are ejected on the surface of the media of the instant disclosure, the salts are firstly able to "crash-out" the pigmented ink suspension ("crash-out" being defined as precipitating or causing the precipitation of pigments or dyes out of dispersion or solution in an ink) so that the colorants, for example like color pigments, can quickly separate from the ink vehicle and stay on the outmost surface of the media, while the aqueous ink vehicle can be readily absorbed into the paper base stock and evaporated gradually. Secondly, these salts need to be able to chemically, physically, and/or electrostatically bind the pigmented colorant materials at or near the outer surface of the printing media. By this means, a high degree of water-fastness, smear-fastness, and overall image stability is obtained. Another function of the fixatives is to reduce the ink dry time. One embodiment of the high valence salt is the water-soluble or water-dispersible trivalent aluminum salts. The term "water-soluble or water-dispersible aluminum salts" encompasses all salts of aluminum which are sufficiently water-soluble or water-dispersible to function effectively in the surface treatment composition. In an embodiment, these salts have at least some ionic character. Examples of such ionic salts include aluminum acetate, aluminum bromate, aluminum bromide and the hexa- and pentadecyl hydrates thereof, aluminum ammonium sulfate, aluminum sodium sulfate, aluminum chlorate, aluminum citrate, aluminum chloride and the hexahydrate thereof, aluminum fluoride, aluminum iodide and the hexahydrate thereof, aluminum lactate, aluminum nitrate, aluminum stearate, aluminum sulfate, aluminum tartrate, aluminum triformate, aluminum formoacetate and the hydrate thereof. Of the above-listed salts, the following are particularly effective: aluminum chloride, aluminum bromide, aluminum fluoride, aluminum iodide, aluminum nitrate, aluminum sulfate, aluminum citrate, and aluminum lactate. Of these, aluminum chloride, aluminum sulfate, aluminum fluoride and aluminum citrate are even more effective than the others.

    [0018] The salts that can be used in accordance with the present disclosure also include complex poly-salts with high valence such as polyaluminum chloride, polyaluminum hydroxychloride; polyaluminol ACH; polyaluminum chlorohydrate; aluminum chlorhydroxide; aluminum chloride hydroxide oxide, basic; polyaluminum chlorohydrol, or aluminum chlorohydroxide. These polyaluminum chloride or polyaluminum hydroxychloride salts are made by partially reacting aluminum chloride (ACH) with a base. The relative amount of OH compared to the amount of Al can determine the basicity of a particular product. As a non-limiting example, the high valence ionic composition that can be formed from polyaluminum hydroxychloride are [Al6(OH)15]3+, [Al12 (OH)24AlO4(H2O)12]7+, [Al8(OH)20]4+, [Al21(OH)60]3+, and [Al13(OH)34]5+. One of the notable characteristics of the poly-salts is solubility in water. The ionic composition formed has a basic (as opposed to acidic) nature, and it is stable with cationically-charged high valence centers.

    [0019] In an embodiment, high valence salts of the instant application are added to water to form an aqueous solution/suspension. The aqueous solution/suspension of the salt is added to the surface sizing agent solution, e.g. starch solution. In some instances, the surface sizing agent contains both starch and a synthetic sizing agent. For example, the pick-up amount of starch is from about 0.5 to about 3 grams per square meter (gsm) per paper side, and the amount of synthetic surface sizing agent is in the range of from 0 to about 6kg/T of base paper stock.

    [0020] To achieve the optimum effect in improving the inkjet image quality, an "effective" amount of salts is needed in the surface treatment composition. The effective amount of the salt ranges from about 10% to about 50% by dry weight in the surface treatment composition, and preferably, in the range of from about 15% to about 25% by dry weight in the surface treatment composition. If the salt usage is lower than the minimum amount of about 10% by dry weight in the surface treatment composition, a low image quality print-out will appear.

    [0021] The surface treatment composition can be applied on base paper stock by a surface size press process such as a puddle-size press and a film-size press, or other similar press types. The puddle-size press can be configured with any of horizontal, vertical and inclined rollers. The film-size press can include a metering system, such as gate-roll metering, blade metering, Meyer rod metering, or slot metering. For some embodiments, a film-size press with short-dwell blade metering can be used as an application head to apply the coating solution. A calendaring process can optionally be used after drying the surface treatment composition to improve the surface smoothness and gloss.

    [0022] In order to test the image attributes conferred on a media surface treated with the surface treatment composition of the instant disclosure, various methods and approaches may be used. Of the image attributes in a print-out, the black ink optical density (KOD), color gamut and printed line raggedness were found to be the most important attributes to characterize the image quality.

    [0023] Black optical density (KOD) is the measurement of the change in reflectance OD=log10(Ii/Ir), where Ii and Ir are incident and reflected light intensities, respectively. The higher the KOD value, the darker the black colored image obtained.

    [0024] Color gamut refers to the subset of colors which can be accurately represented in a given circumstance, such as within a given color space like CIE 1976 (L*, a*, b*) color space. The bigger the color gamut volume, the more vivid in color is the resulting colored image.

    [0025] Line raggedness refers to the average of the leading edge and trailing edge raggedness of a printed line, and it measures the appearance of geometric distortion of an edge from its ideal position. A high line raggedness value indicates greater geometric distortion of an edge, and the image will reveal some defects like feathering and bleeding.

    [0026] To further illustrate embodiment(s) of the present disclosure, examples are given herein. It is to be understood that these examples are provided for illustrative purposes and are not to be construed as limiting the scope of the disclosed embodiment(s).

    EXAMPLES


    Example 1: Preparation of paper base stock and surface treatment composition



    [0027] Paper substrates were made on a paper machine from a fiber furnish consisting of 30% softwood and 50% hardwood fibers and 12% precipitated calcium carbonate with alkenyl succinic anhydride (ASA) internal size. The basis weight of the substrate paper was about 75 gsm.

    [0028] Surface sizing composition was prepared in the laboratory using a 208 litre (55 gallon) jacked processing vessel made of stainless steel (A&B Processing System Corp., Stratford, WI). A Lighthin® mixer (Lighthin Ltd., Rochester NY) mixer with a 5:1 gear ratio and a speed of 1500 rpm was used to mix the formulation. The starches and their derivatives which were used as the surface sizing agent were first pre-cooked at 95°C for 2 hours and cooled to room temperature. An amount of pre-cooked starch was added to the mixing container. This was followed by adding into the mixture the water, and then the other additives such as fluorescent whitening agents (FWA) and pH buffer. The tri-valent salt, aluminum sulfate octadecahydrate, was pre-dissolved and filtered, and then mixed with starch. An effective mixing speed can be achieved with a range between about 500 rpm and about 1000 rpm.

    [0029] Surface treated ink-jet printing media was prepared by applying the resulting surface sizing composition by hand drawdown using a Meyer rod, or a laboratory coater. By controlling the formulation solids, rod size, nip pressure, and machine running speed, an effective pickup weight of the surface treatment composition was achieved. Effective pickup weight conditions can be achieved in a range from about 0.5 gsm to about 5.0 gsm per side. The treated sheets were dried by a hand-held drier for about 5 to 10 minutes. Effective drying conditions can be achieved with a handheld drier or in a drying oven, either of which applies heat at a temperature ranging from about 80°C to about 120°C.

    Example 2: Black optical density comparison of inkjet printing media containing different salts



    [0030] The black optical density of the print media samples prepared as described in Example 1 were tested in order to compare the image quality with other commercial media containing different types of salts.

    [0031] The samples were printed using a PhotoSmart Pro B9180 printer with pigmented black and color inks, manufactured by Hewlett-Packard Co. The black optical density was measured using an X-Rite densitometer to measure the reflectance of the area filled. The results were listed in Table 1.
    Table 1
    SAMPLEBlack optical densityColor gamutLine raggedness (micrometer)
    Example 2* 1.39    
    Example 3*   177800  
    Example 4*     8.70
    Commercial paper with CaCl2 1.41 176200 12.40
    * Salt amount is 16.7% by dry weight of surface treatment composition

    Example 3: Color gamut comparison of inkjet printing media containing different salts



    [0032] The color gamut of the print media samples prepared as described in Example 1 were tested to compare the image quality with other commercial media containing different types of salts.

    [0033] The samples were printed using a PhotoSmart Pro B9180 printer with pigmented black and color inks, manufactured by Hewlett-Packard Co. The color gamut measurements were carried out on squares of primary color (cyan, magenta, and yellow) and secondary colors (red, green, and blue) plus white (un-imaged sheets) and black colors. L*a*b* values of these squares were first measured and thereafter were used to calculate the 8-point color gamut, where the higher value of color gamut indicates that the prints showed richer or more saturated colors. The results were listed in Table 1.

    Example 4: Line raggedness comparison of inkjet printing media containing different salts



    [0034] The line raggedness of the print media samples prepared as described in Example 1 were tested in order to compare the image quality with other commercial media containing different type of salts. In this evaluation, media samples were imaged as black line or black lines on a yellow background with a PhotoSmart Pro B9180 printer with pigmented black and color inks, manufactured by Hewlett-Packard Co. The samples were then allowed to air dry. The edge acuity of the black-to-yellow bleed was measured with a QEA Personal Image Analysis System (Quality Engineering Associates, Burlington, MA). Smaller values were indicative of better edge quality of the printed image. The results were listed in Table 1.

    Example 5: Influence of tri-valent salt amount on image quality



    [0035] The aluminum sulfate octadecahydrate was used as the ink fixative in the surface treatment composition as described in Example 1. When aluminum sulfate octadecahydrate increased, the image quality, as represented by color gamut, was increased, but a significant improvement only happened when the weight percentage of salt was over 10 weight% in the surface treatment composition.

    [0036] Various color gamut results from this Example 5 for samples of colored inks having various weight percent concentrations of aluminum sulfate octadecahydrate salts in the surface treatment composition were graphed in Figure 1. As can be seen in Figure 1, samples which had higher salt concentration from around 15 weight% up to around 25 weight% also had higher color gamut.

    Example 6: Print Quality (PQ) improvement by high valence salt



    [0037] The paper substrates used in this experiment were made on a paper machine from a fiber furnish consisting of 30% softwood and 50% hardwood fibers and 12% precipitated calcium carbonate with alkenyl succinic anhydride (ASA) internal size. The basis weight of the substrate paper was about 75 gsm.

    [0038] The surface sizing composition was prepared in the laboratory using a 208 litre (55 gallon) jacked processing vessel made by stainless steel (A&B Processing System Corp., Stratford, WI). A Lighthin® mixer (Lighthin Ltd., Rochester NY) mixer with a 95:1 gear ratio and a speed of 1500 rpm was used to mix the formulation. When the starches or their derivatives were used as the surface sizing agent, they were first pre-cooked at 95°C for 2 hours and cooled to room temperature. An amount of pre-cooked starch was added to the mixing container, then the water was added, and then the other additives such as fluorescent whitening agents (FWA) and pH buffer were added. Basic polyaluminum chlorohydrate salts were pre-dissolved and filtered to generate a high valence ionic solution of [Al8(OH)20]4+. These were then mixed with starch mixture in a weight percentage of 14.8%. Effective mixing conditions can be achieved under these conditions in a range between about 500 rpm and about 1000 rpm.

    [0039] Surface treated ink-jet printing media was prepared by applying the resulting surface sizing composition either by hand drawdown using a Meyer rod. By controlling the formulation solids, rod size, nip pressure, and machine running speed, an effective pickup weight of surface treatment composition was achieved. Effective pick up weight can be achieved in a range between 500 rpm and 1000 rpm. The treated sheets were dried for 20 minutes. Effective drying conditions can be achieved with either a handheld drier or a drying oven, either of which applies a temperature ranging between 80°C and 120°C.

    [0040] The samples were printed using a PhotoSmart Pro B9180 printer with pigmented black and color inks, manufactured by Hewlett-Packard Co. The black optical density, color gamut and line raggedness were measured using the method described in Examples 2-4. The results are listed in Table 2.
    Table 2
    FixativeWt % in surface treatment compositionColor gamutKODLine raggedness (micrometer)
    Commercial paper with CaCl2 N/A 176200 1.41 12.40
    Commercial paper with NaCl N/A 105300 0.86 20.70
    CaCl2 16.7% 181200 1.39 10.50
    Basic polyaluminum chlorohydrate salt 14.8% 172400 1.37 8.75


    [0041] While several embodiments have been described in detail, it will be apparent to those skilled in the art that the disclosed embodiments may be modified. Therefore, the foregoing description is to be considered exemplary rather than limiting.


    Claims

    1. A surface treatment composition for inkjet media, comprising:

    at least one surface sizing agent selected from the group consisting of starch, starch derivatives and combinations thereof; and

    aluminium sulfate octadecahydrate as an ink fixative;

    wherein the ink fixative is present in the surface treatment composition from 10 weight% to 50 weight% of the surface treatment composition.


     
    2. A surface treatment composition for inkjet media, consisting essentially of:

    at least one surface sizing agent selected from the group consisting of starch, starch derivatives and combinations thereof;

    an ink fixative selected from the group consisting of at least one high valence metallic salt, at least one high valence complex poly-salt, and combinations thereof; and

    water,

    wherein the ink fixative is present in the surface treatment composition from 10% to 50% by dry weight of the surface treatment composition;

    and wherein the at least one high valence metallic salt and the at least one high valence complex poly-salt have a valence greater than divalent.


     
    3. The surface treatment composition of claim 1 or claim 2 wherein the ink fixative is present in the surface treatment composition from 15 weight% to 25 weight%.
     
    4. The surface treatment composition of claim 2 wherein the ink fixative is a high valence aluminum salt, optionally wherein the high valence aluminum salt is selected from the group consisting of aluminum acetate, aluminum bromate, aluminum bromide, aluminum bromide hexahydrate, aluminum bromide pentadecyl hydrate, aluminum ammonium sulfate, aluminum sodium sulfate, aluminum chlorate, aluminum citrate, aluminum chloride, aluminum hexahydrate, aluminum fluoride, aluminum iodide, aluminum iodide hexahydrate, aluminum lactate, aluminum nitrate, aluminum stearate, aluminum sulfate, aluminium sulfate octadecahydrate, aluminum tartrate, aluminum triformate, aluminum formoacetate, and aluminum formoacetate hydrate.
     
    5. The surface treatment composition of claim 4 wherein the high valence aluminum salt is a water-soluble or water-dispersible aluminum salt.
     
    6. The surface treatment composition of claim 2 wherein the ink fixative is a high valence, complex polysalt selected from the group consisting of polyaluminum chloride; polyaluminum hydroxychloride; polyaluminol aluminum cholorohydrate; polyaluminum chlorohydrate; aluminum chlorhydroxide; aluminum chloride hydroxide oxide, basic; polyaluminum chlorohydrol; aluminum chlorohydroxide; and combinations thereof.
     
    7. The surface treatment composition of claim 1 or claim 2 wherein the at least one surface sizing agent includes starch derivatives selected from the group consisting of potato derivatives, corn derivatives, tapioca derivatives, cationic starch, anionic starch, oxidized starch, starch esters, starch ethers, starch acetates, starch phosphates, and combinations thereof.
     
    8. A method of making surface-treated inkjet media, the method comprising:

    providing a base stock treated with internal sizing agents;

    applying a surface treatment composition of any of claims 1 to 7 to the base stock.


     
    9. The method according to claim 8 wherein the internal sizing agents are selected from the group consisting of carboxymethylcellulose; polyvinyl alcohol; methyl cellulose; alginates; waxes; wax emulsions; alkylketene dimmer; alkyl succinic anhydride; alkenyl ketene dimmer emulsion; emulsions of alkyl succinic anhydride with cationic starch; emulsions of alkenyl ketene dimmer emulsion with cationic starch; alkyl succinic anhydride incorporating alum; water-soluble polymeric materials; water-dispersible polymeric materials; and combinations thereof;
    and wherein the base stock treated with the internal sizing agents has a Cobb value in a range from 20 gsm to 50 gsm.
     
    10. A system of inkjet printing with surface treated inkjet media with the surface treatment composition as claimed in any one of claims 1 through 7, the system comprising:

    an inkjet printer;

    pigment based ink;

    an inkjet media treated with the surface treatment composition of any of claims 1 to 7.


     
    11. Inkjet printable paper, comprising a surface coated with a surface treatment composition as claimed in any one of claims 1 through 7;
    wherein the paper includes a base stock treated with internal sizing agents selected from the group consisting of carboxymethylcellulose; polyvinyl alcohol; methyl cellulose; alginates; waxes; wax emulsions; alkylketene dimmer; alkyl succinic anhydride; alkenyl ketene dimer emulsion; emulsions of alkyl succinic anhydride with cationic starch; emulsions of alkenyl ketene dimmer emulsion with cationic starch; alkyl succinic anhydride incorporating alum; water-soluble polymeric materials; water-dispersible polymeric materials; and combinations thereof;
    and wherein the base stock treated with the internal sizing agents has a Cobb value in a range from 20 gsm to 50 gsm.
     
    12. The inkjet printable paper of claim 11 wherein the base stock is selected from the group consisting of cellulose paper, polymeric film, and cellulose paper coated with polymeric materials on one or both sides.
     
    13. The inkjet printable paper of claim 11 wherein the base stock is cellulose paper selected from the group consisting of wood pulp, wood-free pulp, and combinations thereof.
     
    14. The inkjet printable paper of claim 11 wherein the base stock is sized with internal sizing agents, the internal sizing agents being selected from the group consisting of rosin sizes, ketene dimmers, ketene multimers, alkenylsuccinic anhydrides, and combinations thereof.
     


    Ansprüche

    1. Oberflächenbehandlungszusammensetzung für Tintenstrahlmedien, Folgendes umfassend:

    wenigstens ein Oberflächenleimungsmittel, ausgewählt aus der Gruppe bestehend aus Stärke, Stärkederivaten und Kombinationen daraus; und

    Aluminiumsulfatoctadecahydrat als ein Tintenfixiermittel;

    wobei das Tintenfixiermittel in der Oberflächenbehandlungszusammensetzung von 10 Gew.-% bis 50 Gew.-% der Oberflächenbehandlungszusammensetzung vorliegt.


     
    2. Oberflächenbehandlungszusammensetzung für Tintenstrahlmedien, im Wesentlichen bestehend aus:

    wenigstens einem Oberflächenleimungsmittel, ausgewählt aus der Gruppe bestehend aus Stärke, Stärkederivaten und Kombinationen daraus;

    einem Tintenfixiermittel, ausgewählt aus der Gruppe bestehend aus wenigstens einem Metallsalz hoher Wertigkeit, wenigstens einem komplexen Polysalz hoher Wertigkeit und Kombinationen daraus; und Wasser,

    wobei das Tintenfixiermittel in der Oberflächenbehandlungszusammensetzung von 10 Gew.-% bis 50 Gew.-% nach Trockengewicht der Oberflächenbehandlungszusammensetzung vorliegt;

    und wobei das wenigstens eine Metallsalz hoher Wertigkeit und das wenigstens eine komplexe Polysalz hoher Wertigkeit eine höhere Valenz aufweisen als das divalente.


     
    3. Oberflächenbehandlungszusammensetzung nach Anspruch 1 oder 2, wobei das Tintenfixiermittel in der Oberflächenbehandlungszusammensetzung von 15 Gew.-% bis 25 Gew.-% vorliegt.
     
    4. Oberflächenbehandlungszusammensetzung nach Anspruch 2, wobei das Tintenfixiermittel ein Aluminiumsalz hoher Wertigkeit ist, optional wobei das Aluminiumsalz hoher Wertigkeit ausgewählt ist aus der Gruppe bestehend aus Aluminiumacetat, Aluminiumbromat, Aluminiumbromid, Aluminiumbromidhexahydrat, Aluminiumbromidpentadecylhydrat, Aluminiumammoniumsulfat, Aluminiumnatriumsulfat, Aluminiumchlorat, Aluminiumcitrat, Aluminiumchlorid, Aluminiumhexahydrat, Aluminiumfluorid, Aluminiumiodid, Aluminiumiodidhexahydrat, Aluminiumlactat, Aluminiumnitrat, Aluminiumstearat, Aluminiumsulfat, Aluminiumsulfatoctadecahydrat, Aluminiumtartrat, Aluminiumtriformat, Aluminiumformacetat und Aluminiumformacetathydrat.
     
    5. Oberflächenbehandlungszusammensetzung nach Anspruch 4, wobei das Aluminiumsalz hoher Wertigkeit ein wasserlösliches oder wasserdispergierbares Aluminiumsalz ist.
     
    6. Oberflächenbehandlungszusammensetzung nach Anspruch 2, wobei das Tintenfixiermittel ein komplexes Polysalz hoher Wertigkeit ist, ausgewählt aus der Gruppe bestehend aus Polyaluminiumchlorid; Polyaluminiumhydroxychlorid; Polyaluminolaluminiumcholorhydrat; Polyaluminiumchlorhydrat; Aluminiumchlorhydroxid; Aluminiumchloridhydroxidoxid, basisch; Polyaluminiumchlorhydrol; Aluminiumchlorhydroxid und Kombinationen daraus.
     
    7. Oberflächenbehandlungszusammensetzung nach Anspruch 1 oder 2, wobei das wenigstens eine Oberflächenleimungsmittel Stärkederivate enthält, ausgewählt aus der Gruppe bestehend aus Kartoffelderivaten, Maisderivaten, Tapiokaderivaten, kationischer Stärke, anionischer Stärke, oxidierter Stärke, Stärkeestern, Stärkeethern, Stärkeacetaten, Stärkephosphaten und Kombinationen daraus.
     
    8. Verfahren zum Herstellen oberflächenbehandelter Tintenstrahlmedien, wobei das Verfahren Folgendes umfasst:

    Bereitstellen eines mit internen Leimungsmitteln behandelten Grundmaterials;

    Auftragen einer Oberflächenbehandlungszusammensetzung nach einem der Ansprüche 1 bis 7 auf das Grundmaterial.


     
    9. Verfahren nach Anspruch 8, wobei die internen Leimungsmittel ausgewählt sind aus der Gruppe bestehend aus Carboxymethylcellulose; Polyvinylalkohol; Methylcellulose; Alginaten; Wachsen; Wachsemulsionen; Alkylketendimer; Alkylbernsteinanhydrid; Alkenylketendimeremulsion; Emulsionen aus Alkylbernsteinanhydrid mit kationischer Stärke, Emulsionen aus Alkenylketendimeremulsion mit kationischer Stärke; Alaun einbindendes Alkylbernsteinanhydrid; wasserlöslichen Polymermaterialien; wasserdispergierbaren Polymermaterialien und Kombinationen daraus;
    und wobei das mit den internen Leimungsmitteln behandelte Grundmaterial einen Cobb-Wert in einem Bereich von 20 g/m2 bis 50 g/m2 aufweist.
     
    10. System zum Tintenstrahldrucken mit oberflächenbehandelten Tintenstrahlmedien mit der Oberflächenbehandlungszusammensetzung nach einem der Ansprüche 1 bis einschließlich 7, wobei das System Folgendes umfasst:

    einen Tintenstrahldrucker;

    Tinte auf Pigmentbasis;

    ein mit der Oberflächenbehandlungszusammensetzung nach einem der Ansprüche 1 bis 7 behandeltes Tintenstrahlmedium.


     
    11. Tintenstrahlbedruckbares Papier, umfassend eine mit einer Oberflächenbehandlungszusammensetzung nach einem der Ansprüche 1 bis einschließlich 7 beschichteten Oberfläche;
    wobei das Papier ein mit internen Leimungsmitteln behandeltes Grundmaterial enthält, die ausgewählt sind aus der Gruppe bestehend aus Carboxymethylcellulose; Polyvinylalkohol; Methylcellulose; Alginaten; Wachsen; Wachsemulsionen; Alkylketendimer; Alkylbernsteinanhydrid; Alkenylketendimeremulsion; Emulsionen aus Alkylbernsteinanhydrid mit kationischer Stärke, Emulsionen aus Alkenylketendimeremulsion mit kationischer Stärke; Alaun einbindendes Alkylbernsteinanhydrid; wasserlöslichen Polymermaterialien; wasserdispergierbaren Polymermaterialien und Kombinationen daraus;
    und wobei das mit den internen Leimungsmitteln behandelte Grundmaterial einen Cobb-Wert in einem Bereich von 20 g/m2 bis 50 g/m2 aufweist.
     
    12. Tintenstrahlbedruckbares Papier nach Anspruch 11, wobei das Grundmaterial ausgewählt ist aus der Gruppe bestehend aus Cellulosepapier, Polymerfolie und Cellulosepapier, beschichtet mit Polymermaterialien auf einer oder beiden Seiten.
     
    13. Tintenstrahlbedruckbares Papier nach Anspruch 11, wobei das Grundmaterial Cellulosepapier ist, ausgewählt aus der Gruppe bestehend aus Holzhalbstoff, holzfreiem Halbstoff und Kombinationen daraus.
     
    14. Tintenstrahlbedruckbares Papier nach Anspruch 11, wobei das Grundmaterial mit internen Leimungsmitteln geleimt ist, wobei die internen Leimungsmittel ausgewählt sind aus der Gruppe bestehend aus Harzleimen, Ketendimeren, Ketenmultimeren, Alkenylbernsteinanhydriden und Kombinationen daraus.
     


    Revendications

    1. Composition de traitement de surface pour un support à jet d'encre, comprenant :

    au moins un agent d'encollage de surface choisi dans le groupe constitué par de l'amidon, des dérivés de l'amidon et des combinaisons de ces derniers ; et

    l'octadécahydrate de sulfate d'aluminium comme fixateur d'encre ;

    dans laquelle le fixateur d'encre est présent dans la composition de traitement de surface de 10 % en poids à 50 % en poids de la composition de traitement de surface.


     
    2. Composition de traitement de surface pour un support à jet d'encre, comprenant essentiellement :

    au moins un agent d'encollage de surface choisi dans le groupe constitué par de l'amidon, des dérivés de l'amidon et des combinaisons de ces derniers ;

    un fixateur d'encre choisi dans le groupe constitué d'au moins un sel métallique à haute valence, au moins un polysel complexe à haute valence, et de combinaisons de ces derniers ; et

    d'eau,

    dans laquelle le fixateur d'encre est présent dans la composition de traitement de surface de 10 % à 50 % en poids sec de la composition de traitement de surface ;

    et dans laquelle ledit sel métallique à haute valence et ledit polysel complexe à haute valence ont une valence supérieure à la valence divalente.


     
    3. Composition de traitement de surface selon la revendication 1 ou la revendication 2, dans laquelle le fixateur d'encre est présent dans la composition de traitement de surface de 15 % en poids à 25 % en poids.
     
    4. Composition de traitement de surface selon la revendication 2, dans laquelle le fixateur d'encre est un sel d'aluminium à haute valence, facultativement dans laquelle le sel d'aluminium est choisi dans le groupe constitué par de l'acétate d'aluminium, du bromate d'aluminium, du bromure d'aluminium, de l'hexahydrate de bromure d'aluminium, de l'hydrate de pentadécyle de bromure d'aluminium, du sulfate d'aluminium ammonium, du sulfate d'aluminium sodium, du chlorate d'aluminium, du citrate d'aluminium, du chlorure d'aluminium, de l'hexahydrate d'aluminium, du fluorure d'aluminium, de l'iodure d'aluminium, de l'hexahydrate d'iodure d'aluminium, du lactate d'aluminium, du nitrate d'aluminium, du stéarate d'aluminium, du sulfate d'aluminium, de l'octadécahydrate de sulfate d'aluminium, du tartrate d'aluminium, du triformate d'aluminium, du formoacétate d'aluminium et de l'hydrate de formoacétate d'aluminium.
     
    5. Composition de traitement de surface selon la revendication 4, dans laquelle le sel d'aluminium à haute valence est un sel d'aluminium hydrosoluble ou hydrodispersable.
     
    6. Composition de traitement de surface selon la revendication 2, dans laquelle le fixateur d'encre est un polysel complexe à haute valence choisi dans le groupe constitué par du chlorure de polyaluminium ; de l'hydroxychlorure de polyaluminium ; ledu chlorhydrate d'aluminium de polyaluminol ; du chlorhydrate de polyaluminium ; du chlorhydroxyde d'aluminium ; de l'oxyde d'hydroxyde de chlorure d'aluminium de base ; du chlorhydrol de polyaluminium ; du chlorhydroxyde d'aluminium ; et des combinaisons de ces derniers.
     
    7. Composition de traitement de surface selon la revendication 1 ou la revendication 2, dans laquelle ledit agent d'encollage de surface comporte des dérivés de l'amidon choisis dans le groupe constitué par des dérivés de pomme de terre, des dérivés de maïs, des dérivés de tapioca, de l'amidon cationique, l'amidon anionique, de l'amidon oxydé, des esters d'amidon, des éthers d'amidon, des acétates d'amidon, des phosphates d'amidon et des combinaisons de ces derniers.
     
    8. Procédé de fabrication d'un support à jet d'encre traité en surface, le procédé comprenant :

    la fourniture d'un stock de base traité avec des agents d'encollage internes ;

    l'application d'une composition de traitement de surface selon l'une quelconque des revendications 1 à 7 au stock de base.


     
    9. Procédé selon la revendication 8 dans lequel les agents d'encollage internes sont choisis dans le groupe constitué par de la carboxyméthylcellulose ; de l'alcool polyvinylique ; de la méthylcellulose ; des alginates ; des cires ; des émulsions de cire ; du dimère d'alkylcétène ; de l'anhydride alkylsuccinique ; l'émulsion de dimère d'alcénylcétène ; des émulsions d'anhydride alkylsuccinique avec de l'amidon cationique ; des émulsions d'émulsion de dimère d'alcénylcétène avec de l'amidon cationique ; de l'anhydride alkylsuccinique incorporant de l'alun ; des matériaux polymères hydrosolubles ; des matériaux polymères hydrodispersables ; et des combinaisons de ces derniers ;
    et dans lequel le stock de base traité avec les agents d'encollage internes a une valeur de Cobb dans une plage de 20 gsm à 50 gsm.
     
    10. Système d'impression à jet d'encre avec un support à jet d'encre traité en surface avec la composition de traitement de surface selon l'une quelconque des revendications 1 à 7, le système comprenant :

    une imprimante à jet d'encre ;

    une encre à base de pigment ;

    un support à jet d'encre traité avec la composition de traitement de surface selon l'une quelconque des revendications 1 à 7.


     
    11. Papier imprimable par jet d'encre, comprenant une surface revêtue d'une composition de traitement de surface selon l'une quelconque des revendications 1 à 7;
    dans lequel le papier comporte un stock de base traité avec des agents d'encollage internes choisis dans le groupe constitué par de la carboxyméthylcellulose ; de l'alcool polyvinylique ; de la méthylcellulose ; des alginates ; des cires ; des émulsions de cire ; du dimère d'alkylcétène ; l'anhydride alkylsuccinique ; de l'émulsion de dimère d'alcénylcétène ; des émulsions d'anhydride alkylsuccinique avec de l'amidon cationique ; des émulsions d'émulsion de dimère d'alcénylcétène avec de l'amidon cationique ; l'anhydride alkylsuccinique incorporant de l'alun ; des matériaux polymères hydrosolubles ; des matériaux polymères hydrodispersables ; et des combinaisons de ces derniers ;
    et dans lequel le stock de base traité avec les agents d'encollage internes a une valeur de Cobb dans une plage de 20 gsm à 50 gsm.
     
    12. Papier imprimable par jet d'encre selon la revendication 11, dans lequel le stock de base est choisi dans le groupe constitué par du papier cellulosique, du film polymère et du papier cellulosique revêtu de matériaux polymères sur un ou sur les deux côtés.
     
    13. Papier imprimable par jet d'encre selon la revendication 11, dans lequel le stock de base est un papier cellulosique choisi dans le groupe constitué par de la pâte de bois, de la pâte sans bois et des combinaisons de ces dernières.
     
    14. Papier imprimable par jet d'encre selon la revendication 11, dans lequel le stock de base est calibré avec des agents d'encollage internes, les agents d'encollage internes étant choisis dans le groupe constitué par des colles de colophane, du dimères de cétène, des multimères de cétène, des anhydrides alcénylsucciniques et des combinaisons de ces derniers.
     




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    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description