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(11) | EP 1 106 377 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
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| (54) |
Ink jet printing method Tintenstrahldruckverfahren Procédé d'impression à jet d'encre |
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| 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). |
[0001] This invention relates to an ink jet printing method. More particularly, this invention relates to an ink jet printing method that uses a recording element containing pigments.
[0002] In a typical ink jet recording or printing system, ink droplets are ejected from a nozzle at high speed towards a recording element or medium to produce an image on the medium. The ink droplets, or recording liquid, generally comprise a recording agent, such as a dye or pigment, and a large amount of solvent. The solvent, or carrier liquid, typically is made up of water, an organic material such as a monohydric alcohol, a polyhydric alcohol or mixtures thereof.
[0003] An ink jet recording element typically comprises a support having on at least one surface thereof an ink-receiving or image-forming layer, and includes those intended for reflection viewing, which have an opaque support, and those intended for viewing by transmitted light, which have a transparent support.
[0004] While a wide variety of different types of image-recording elements for use with ink jet devices have been proposed heretofore, there are many unsolved problems in the art and many deficiencies in the known products which have limited their commercial usefulness.
[0005] It is well known that in order to achieve and maintain photographic-quality images on such an image-recording element, an ink jet recording element must:
- Be readily wetted so there is no puddling, i.e., coalescence of adjacent ink dots, which leads to nonuniform density
- Exhibit no image bleeding
- Exhibit the ability to absorb high concentrations of ink and dry quickly to avoid elements blocking together when stacked against subsequent prints or other surfaces
- Exhibit no discontinuities or defects due to interactions between the support and/or layer(s), such as cracking, repellencies, comb lines and the like
- Not allow unabsorbed dyes to aggregate at the free surface causing dye crystallization, which results in bloom or bronzing effects in the imaged areas
- Have an optimized image fastness to avoid fade from contact with water or radiation by daylight, tungsten light, or fluorescent light
[0006] An ink jet recording element that simultaneously provides an almost instantaneous ink dry time and good image quality is desirable. However, given the wide range of ink compositions and ink volumes that a recording element needs to accommodate, these requirements of ink jet recording media are difficult to achieve simultaneously.
[0007] Ink jet recording elements are known that employ porous or non-porous single layer or multilayer coatings that act as suitable image receiving layers on one or both sides of a porous or non-porous support. Recording elements that use non-porous coatings typically have good image quality but exhibit poor ink dry time. Recording elements that use porous coatings typically have poorer image quality but exhibit superior dry times.
[0008] US-A-5,851,651 relates to an ink jet recording element comprising a paper substrate with a coating comprising inorganic pigments and an anionic, organic co-binder system. The co-binder system consists of polyvinyl alcohol (PVOH) and polyvinylpyrrolidone (PVP) or a copolymer of polyvinylpyrrolidone-vinyl acetate (PVP-VA). However, there is a problem with this element in that less than desirable image quality, as measured by optical density, image bleed, and waterfastness, is obtained.
[0009] JP-A-10 217601, US-A-5 908 723, EP-A-1 013 464 and WO-00 02736 relate to ink jet recording elements using various binders and pigments.
[0010] German Patent DE 19,534,327A1 relates to an ink jet recording element which contains a recording layer comprising an inorganic, cationic pigment and a cationic organic binder. However, this recording layer also has less than desirable image quality, as measured by optical density, image bleed, and waterfastness.
[0011] It is an object of this invention to provide an inkjet printing method that uses a recording element that has a fast ink dry time. It is another object of this invention to provide an ink jet printing method that uses a recording element that has good image quality.
[0012] These and other objects are achieved in accordance with the invention, which comprises an inkjet printing method comprising the steps of:
a) providing an ink jet printer that is responsive to digital data signals;
b) loading the printer with an ink jet recording element comprising a substrate having
thereon an image-receiving layer comprising an inorganic, anionic pigment, an organic,
anionic binder, and an organic, cationic mordant which is a polymer latex dispersion;
said inorganic, anionic pigment being present in an amount of from 50% to 95 weight
% of said image-receiving layer;
said organic, anionic binder being present in an amount of from 5% to 20 weight
% of said image-receiving layer; and the ratio of pigment to binder is from 5:1 to
8:1; and
said organic, cationic mordant being present in an amount of from 1% to 75 weight
% of said image-receiving layer;
c) loading the printer with an ink jet ink composition; and
d) printing on said recording element using said ink jet ink in response to the digital data signals.
[0013] The ink jet recording element produced by the method of the invention provides good gloss, good image quality and fast ink dry times.
[0014] The inorganic, anionic pigment useful in the recording element employed in the process of the invention may be a kaolin clay, a calcined clay, titanium dioxide, talc or a silicate. In a preferred embodiment of the invention, the inorganic, anionic pigment is a kaolin clay sold under the trade name Hydragloss® 92 (J.M.Huber Company). The amount of inorganic, anionic pigment used is in the range from 50% to 95% of the image-receiving layer.
[0015] The organic, anionic binder useful in the recording element employed in the process of the invention may be a styrene acrylic latex, a styrene butadiene latex, a poly(vinyl alcohol) or a poly(vinyl acetate). A commercially-available styrene acrylic latex useful in the invention is Acronal ® S-728 (BASF Corp.). A commercially-available styrene butadiene latex useful in the invention is Styronal ® BN 4606X (BASF Corp.). A commercially-available poly(vinyl alcohol) useful in the invention is Airvol ® 21-205 (Air Products Inc.). A commercially-available poly(vinyl acetate) useful in the invention is Vinac ® 884 (Air Products Inc.).
[0016] The organic, anionic binder is used in an amount of from 5% to 20% of the image-receiving layer. The ratio of pigment to binder is from 5:1 to 8:1.
[0017] The organic, cationic mordant useful in the recording element employed in the process of the invention is a polymer latex dispersion. Examples of mordants useful in the invention are disclosed in US-A-5,474,843. Other useful mordants include cationic urethane dispersions sold under the trade name Witcobond® W-213 and Witcobond ®W-215 (Witco Corporation).
[0018] In a preferred embodiment of the invention, the organic, cationic mordant is:
M1: poly(N-vinyl benzyl-N-benzyl-N,N-dimethyl ammonium chloride-co-styrene-co-divinyl benzene),
M2: poly(N-vinylbenzyl-N,N,N-trimethylammonium chloride-co-ethylene glycol dimethacrylate), or
M3: poly(N-vinylbenzyl-N,N,N-trimethylammonium chloride-co-divinyl benzene).
[0019] The mordant polymer is present in an amount of from 1% to 75% by weight of the image-receiving layer, preferably from 10% to 20%.
[0020] Smaller quantities of up to 10 % of other binders may also be added to the image-receiving layer such as PVP sold as Luviskol ®VA 64W (BASF Corp.) or copolymer PVP-VA sold as Luviquat® PQ11PN (BASF Corp.). In addition to the above major components, other additives such as pH-modifiers like nitric acid, cross-linkers, rheology modifiers, surfactants, UV-absorbers, biocides, lubricants, dyes, optical brighteners etc. may be added as needed.
[0021] The substrate may be porous such as paper or non-porous such as cellulose acetate or polyester films. The surface of the substrate may be treated in order to improve the adhesion of the image-receiving layer to the support. For example, the surface may be corona discharge treated prior to applying the image-receiving layer to the support. Alternatively, an under-coating or subbing layer, such as a layer formed from a halogenated phenol or a partially hydrolyzed vinyl chloride-vinyl acetate copolymer, can be applied to the surface of the support.
[0022] The ink jet coating may be applied to one or both substrate surfaces through conventional pre-metered or post-metered coating methods such as blade, air knife, rod, roll coating, etc. The choice of coating process would be determined from the economics of the operation and in turn, would determine the formulation specifications such as coating solids, coating viscosity, and coating speed. In a preferred embodiment, the coating formulation would have a coating solids of 40-60% and a low shear 10.5 s-1 (100 rpm Brookfield) viscosity of 500-2000 mPa.s (500-2000 centiPoise).
[0023] The image-receiving layer thickness may range from 5 to 60 µm, preferably from 20 to 40 µm. The coating thickness required is determined through the need for the coating to act as a sump for absorption of ink solvent and the need to hold the ink near the coating surface. The coating may be applied in a single layer or in multiple layers so the functionality of each coating layer may be specified; for example, a two-layer structure can be created wherein the base coat functions as a sump for absorption of ink solvent while the top coat holds the ink.
[0024] After coating, the ink jet recording element may be subject to calendering or supercalendering to enhance surface smoothness. In a preferred embodiment, the ink jet recording element is subject to hot, soft-nip calendering at a temperature of 65°C and pressure of 14000 kg/m at a speed of from 0.15 m/s to 0.3 m/s.
[0025] The substrate used in the ink jet recording element employed in the process of the invention may be opaque, translucent, or transparent. There may be used, for example, plain papers, resin-coated papers, various plastics including a polyester resin such as poly(ethylene terephthalate), poly(ethylene naphthalate) and poly(ester diacetate), a polycarbonate resin, a fluorine resin such as poly(tetra-fluoro ethylene), metal foil, various glass materials, and the like. The thickness of the substrate employed in the invention can be from 12 to 500 µm, preferably from 75 to 300 µm.
[0026] Ink jet inks used to image the recording elements employed in the process of the invention are well-known in the art. The ink compositions used in ink jet printing typically are liquid compositions comprising a solvent or carrier liquid, dyes or pigments, humectants, organic solvents, detergents, thickeners, preservatives, and the like. The solvent or carrier liquid can be solely water or can be water mixed with other water-miscible solvents such as polyhydric alcohols. Inks in which organic materials such as polyhydric alcohols are the predominant carrier or solvent liquid may also be used. Particularly useful are mixed solvents of water and polyhydric alcohols. The dyes used in such compositions are typically water-soluble direct or acid type dyes. Such liquid compositions have been described extensively in the prior art including, for example, US-A-4,381,946; US-A-4,239,543 and US-A-4,781,758.
Example 1 (Reference Only)
[0028] Coating formulations were prepared as follows (in dry grams):
| Constituent | Control Coating 1 | Control Coating 2 | Coating 1 |
| Kaolin clay (Hydragloss ® 92) as a dry powder | 100 | 100 | 100 |
| Mordant M3 as a 15% solids dispersion | -- | -- | 30 |
| PVP (Luviskol® 64W) as a 50% solids solution | -- | 10 | -- |
| Styrene acrylic latex (Acronal ®S728) as a 50% solids dispersion | 10 | 10 | 10 |
| Nitric Acid (1N) | -- | -- | 1.0 |
[0029] The above kaolin clay and styrene acrylic latex are both predominantly anionic. The mordant polymer M3 is cationic. The coating formulation thus comprises a mixture of anionic and cationic materials. To achieve a stable formulation, it is necessary to minimize the anionic charge keeping the cationic charge constant. This is achieved by adjusting the pH of the kaolin clay and styrene acrylic latex using nitric acid.
[0030] In addition, in order to achieve a stable formulation, the kaolin clay and styrene acrylic latex are added to the cationic Mordant M3 and then the pH is adjusted.
[0031] Each coating was applied onto a paper base using a wire wound Meyer rod of wire diameter 0.51 µm with a wet laydown thickness of 40 µm to form Control Elements 1 and 2 and Element 1. The base paper used was Nekoosa Solutions Smooth® (Georgia Pacific Co.), Grade 5128 (Carrara White ®, Color 9220), basis weight 150 g/m2. After application, the elements were air-dried. The Element 1 was then subjected to hot, soft-nip calendering at a temperature of 65°C and pressure of 14,000 kg/m at a speed of 0.3 m/s.
[0032] Samples from each of the elements above were printed on a Hewlett Packard Photosmart ® printer with printer settings at "photoglossy paper, best" and subsequently tested for dry time and optical density of the composite black stripe. The inks used were Hewlett Packard Photosmart ® inks.
[0033] Dry time, defined as the time after printing at which no ink retransfer from the printed element to a blotting sheet is observed, was measured using a blotting technique. One sample per element was subjected to the dry time test. A striped target was printed comprising 100% coverage of yellow, cyan, and magenta, 200% coverage for red, green, and blue, and 300% coverage for black in areas of 1 cm by 23 cm. Immediately after printing was finished, the sample was placed on a foam base, a piece of copy paper placed on top of the sample, and a weighted smooth rod was rolled over the paper. The copy sheet was then taken off the sample and studied for retransfer. The results in Table 1 are given as ratings from 1-5, where 1 corresponds to no transfer (fast dry time) to the copy paper, while 5 corresponds to complete transfer (the whole stripe is visible on the copy paper).
[0034] Optical density of the printed recording elements was measured using a X-Rite ® model 820 transmission/reflection densitometer with status A filtration. The black stripe on the target was tested. The results are the average of three measurements.
[0035] The following results were obtained:
| Element | Dry time | Optical Density (Composite Black) |
| Control 1 | 1 | 0.91 |
| Control 2 | 1 | 1.05 |
| Coating 1 | 1 | 1.61 |
[0036] The above results show that element 1 had a higher optical density as compared to the control elements while maintaining a fast dry time.
Example 2 (Reference only)
[0037] Waterfastness, defined as the loss in image optical density after prolonged submersion in water, was measured using a soak test. The ink jet recording elements of Example 1 were soaked in distilled water for five minutes with mild agitation.. The elements were then allowed to dry on a bench-top overnight. The optical density was measured before and after immersion and the % change in density of each color stripe was recorded. The following results were obtained:
| Waterfastness | ||||
| Element | % Change in Cyan Density | % Change in Magenta Density | % Change in Yellow Density | % Change in Black Density |
| Control 1 | -65 | -55 | -68 | -58 |
| Control 2 | -58 | -47 | -62 | -51 |
| Coating 1 | -3 | 2 | 3 | -10 |
a) providing an ink jet printer that is responsive to digital data signals;
b) loading said printer with an ink jet recording element comprising a substrate having
thereon an image-receiving layer comprising an inorganic, anionic pigment, an organic,
anionic binder, an organic, cationic mordant which is a polymer latex dispersion;
said inorganic, anionic pigment being present in an amount of from 50% to 95 weight
% of said image-receiving layer;
said organic, anionic binder being present in an amount of from 5% to 20 weight
% of said image-receiving layer; and the ratio of pigment to binder is from 5:1 to
8:1; and
said organic, cationic mordant being present in an amount of from 1% to 75 weight
% of said image-receiving layer;
c) loading said printer with an ink jet ink composition; and
d) printing on said recording element using said ink jet ink in response to said digital data signals.
a) Bereitstellen eines Tintenstrahldruckers, der auf digitale Datensignale anspricht;
b) Laden des Druckers mit einem Tintenstrahlaufzeichnungselement, das ein Substrat
umfasst, auf dem eine Bildempfangsschicht angeordnet ist, die ein anorganisches, anionisches
Pigment, ein organisches, anionisches Bindemittel und ein organisches, kationisches
Beizmittel, das eine Polymerlatexdispersion ist, umfasst;
wobei das anorganische, anionische Pigment in einer Menge von 50 bis 95 Gew.-% der
Bildempfangsschicht vorhanden ist;
das organische, anionische Bindemittel in einer Menge von 5 bis 20 Gew.-% der Bildempfangsschicht
vorhanden ist, und das Verhältnis von Pigment zu Bindemittel 5:1 bis 8:1 beträgt,
und
das organische, kationische Beizmittel in einer Menge von 1 bis 75 Gew.-% der Bildempfangsschicht
vorhanden ist;
c) Laden des Druckers mit einer Tintenstrahltintenzusammensetzung; und
d) Bedrucken des Aufzeichnungselements mit der Tintenstrahltinte in Abhängigkeit von den digitalen Datensignalen.
a) disposer d'une imprimante à jet d'encre sensible aux signaux numériques ;
b) charger dans ladite imprimante un élément d'enregistrement pour jet d'encre comprenant
un substrat revêtu d'une couche réceptrice d'image comprenant un pigment inorganique
anionique, un liant organique anionique, un mordant cationique organique qui est une
dispersion d'un latex polymère ;
ledit pigment anionique inorganique étant présent en une quantité comprise entre 50
et 95% en poids de ladite couche réceptrice d'image ;
ledit liant anionique organique étant présent en une quantité comprise entre 5 et
20% en poids de ladite couche réceptrice d'image et le rapport du pigment au liant
étant compris entre 5:1 et 8:1 ; et
ledit mordant cationique organique étant présent en une quantité comprise entre 1
et 75% en poids de ladite couche réceptrice d'image ;
c) charger dans ladite imprimante une composition d'encre pour jet d'encre ; et
d) imprimer sur ledit élément d'enregistrement en utilisant ladite encre pour jet d'encre en réponse auxdits signaux numériques.