JP2002301866A - Ink jet recording element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous ink jet recording element, providing an excellent optical density as well as a good quality of image when printing is effected by a dye base ink while having a drying time superior to the other elements. SOLUTION: The ink jet recording element comprises a substrate, on which a porous image receiving layer consisting of (a) particles having the primary grain size of 7-40 nm whose diameter can be agglomerated to the maximum 300 nm and (b) cationic polymer grains, containing at least 20 mol% of cationic mordant portion insoluble to water, is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a porous ink jet recording element and a printing method using the element.

[0002]

BACKGROUND OF THE INVENTION In a typical ink jet recording or printing system, ink droplets are ejected from nozzles at high speed toward a recording element or medium, producing an image on the medium. Ink droplets (or recording liquids) generally comprise a recording agent such as a dye or pigment and a large amount of solvent. The solvent (or carrier liquid) is generally made from water and organic materials (such as monohydric alcohols, polyhydric alcohols or mixtures thereof) and the like.

[0003] Ink jet recording elements generally comprise a support bearing on at least one surface thereof an ink-receiving layer or an image-receiving layer, which is intended to be viewed in reflection (opaque supports). Having) and those intended to be viewed by transmitted light (with transparent support)
Is included.

[0004] An important characteristic of an ink jet recording element is:
It is necessary to dry quickly after printing.
For this reason, porous recording elements have been developed that provide almost instantaneous drying as long as they have sufficient thickness and pore volume to contain the liquid ink efficiently. For example,
Porous recording elements can be produced by cast coating, in which a coating containing particulates is applied to a support and dried in contact with a polished smooth surface.

When a porous recording element is printed with a dye-based ink, the dye molecules penetrate this coating layer.
However, there is a problem with such porous recording elements that the optical density of the printed image is lower than desired. It is believed that this low optical density is due to light scattering caused by dye molecules penetrating too far into the porous layer.

[0006] European Patent Application Publication No. 1,002,660 states that
The present invention relates to a porous inkjet recording element comprising fine particles, a hydrophilic binder and a water-soluble, cationic polymer. However, there is a problem with this element in that the density of the image printed on such an element using a water-soluble cationic polymer is lower than desired.

US Pat. No. 6,089,704 relates to a non-porous ink jet recording element comprising a cationic vinyl latex and a hydrophilic polymer. However, there is a problem with this non-porous recording element that the image printed thereon is very slow to dry.

[0008] US Pat. No. 6,096,469 relates to an ink jet recording element in which medium porous particles are dispersed in an organic binder. In column 8 of the specification, it is disclosed that the organic binder can be a cationic latex polymer having less than 10 mole% of a copolymerizable monomer having "tetraamino or quaternary ammonium functionality". ing. However, for this element, 1
The problem is that the density of the image printed on such an element using a binder having a cationic mordant functionality of less than 0 mol% is lower than desired.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a porous ink jet recording element which prints with dye-based inks, provides excellent optical density, good image quality, and has a drying time which is superior to others. That is. Another object of the present invention is to provide a printing method using the above elements.

[0010]

The above objects are achieved by (a) particles having a primary particle diameter of 7 to 40 nm which can be aggregated up to 300 nm, and (b) at least 20 mol% of a cationic mordant portion. This is achieved according to the present invention which is an ink jet recording element comprising a support having thereon a porous image-receiving layer comprising water-insoluble cationic polymer particles.

The use of the present invention results in a porous ink jet recording element that provides excellent optical density, good image quality, and has a drying time superior to others when printed with dye-based inks.

Another aspect of the present invention is: A) providing an ink jet printer responsive to a digital data signal; B) mounting the above ink jet recording element on the printer; C) applying the ink jet ink composition to the printer. And D) printing on the image receiving layer using the inkjet ink composition in response to the digital signal.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Examples of (a) particles useful in the present invention include alumina, boehmite, clay, calcium carbonate,
Includes titanium dioxide, calcined clay, aluminosilicate, silica, barium sulfate, or polymer beads. These particles may be porous or non-porous. In a preferred embodiment of the invention, the particles are metal oxides, preferably smoke treated. Although many types of inorganic and organic particles are produced by a wide variety of methods for image receiving layers and are commercially available, the porosity of the ink receiving layer is necessary to obtain very fast ink drying. is there. The pores formed between the particles must be large and interconnected enough so that the printing ink passes quickly through this layer and gives the impression of fast drying away from the outer surface. At the same time, the pores formed between the particles must be arranged so that they are small enough not to scatter visible light.

(A) The particles can be in the form of primary or secondary aggregated particles. This aggregate has a diameter of 7 to 4
Consists of smaller primary particles of 0 nm and aggregates up to 300 nm in diameter. The pores in the dry coating of such agglomerates fall within the range required to ensure low optical scattering and still sufficient ink wicking.

(A) Preferred examples of smoke-treated metal oxides that can be used in the present invention as particles include fumed oxides of silica and alumina. Fumed oxides are available in dry form or as a dispersion of the agglomerates described above.

The (b) water-insoluble cationic polymer particles containing at least 20 mol% of a cationic mordant moiety useful in the present invention include latexes, water-dispersible polymers, beads, or organic or inorganic cores and shells. In each case, it can be in the form of core / shell particles which are cationic polymers. Such particles can be the product of addition or condensation polymerization, or a combination of both. They can be linear, branched, over-branched,
It can be grafted, random, block, and can have other polymer microstructures well known in the art. They may also be partially crosslinked. Examples of core / shell particles useful in the present invention are Lawren
No. 09 / 772,097 to Ce, et al. (Title of Invention: Ink Jet Printing Method, filed Jan. 26, 2000, Docket No. 81894HEC). Examples of water-dispersible particles useful in the present invention are described in US Patent Application Ser.
No. 70,128 (Title of Invention: Inkjet printing method,
Filed on January 26, 2000, Docket No. 81815HEC) and Lawre
No. 09 / 770,127 to Ince et al. (Title of Invention: Ink Jet Printing Method, filed Jan. 26, 2000, Docket No. 81817HEC). In a preferred embodiment, the water-insoluble cationic polymer particles have at least 5
Contains 0 mole% cationic mordant portion.

The (b) water-insoluble cationic polymer particles useful in the present invention can be derived from nonionic, anionic, or cationic monomers. In a preferred embodiment, a combination of a nonionic monomer and a cationic monomer is used. Generally, the amount of cationic monomer used in this combination is at least 20 mol%.

The nonionic, anionic or cationic monomer used is an addition-polymerizable monomer such as acrylate ester, methacrylate ester, vinylimidazole, vinylpyridine derived from styrene, α-alkylstyrene, alcohol or phenol. ,
Vinylpyrrolidinone, acrylamide, methacrylamide, linear and branched acids derived vinyl esters (eg, vinyl acetate), vinyl ethers (eg, vinyl methyl ether), vinyl nitriles, vinyl ketones, halogen-containing monomers (eg, vinyl chloride) ) And olefins (eg, butadiene).

The nonionic, anionic or cationic monomers used may be condensation-polymerizable monomers such as the neutral or cationic derivatives used to prepare polyesters, polyethers, polycarbonates, polyureas and polyurethanes. Can be included.

The (b) water-insoluble cationic polymer particles useful in the present invention can be prepared using conventional polymerization techniques, including, but not limited to, bulk, solution, emulsion, or suspension polymerization. .

The amount of (b) the water-insoluble cationic polymer particles used is large enough so that the image printed on the recording element has a sufficiently high density, but the interconnects formed by the aggregates The amount should be small enough so that the pore structure is not blocked. In a preferred embodiment of the present invention, the mass ratio of (b) water-insoluble cationic polymer particles to (a) particles is from 1: 2 to 1:10,
Preferably, it is 1: 5.

Examples of (b) water-insoluble cationic polymer particles that can be used in the present invention include US Pat.
958,995 are included. Specific examples of these polymers include: Polymer A: copolymer of (vinylbenzyl) trimethylammonium chloride and divinylbenzene (molar ratio 87:13). Polymer B: terpolymer of styrene, (vinylbenzene) dimethylbenzylamine and divinylbenzene (molar ratio 49.5: 49.5: 1.0). Polymer C: terpolymer of butyl acrylate, 2-aminoethyl methacrylate hydrochloride and hydroxyethyl methacrylate (molar ratio 50: 20: 3)
0). Polymer D: styrene, dimethylacrylamide, vinylbenzylimidazole and 1-vinylbenzyl-3-
Hydroxyethyl imidazolium chloride copolymer (molar ratio 40: 30: 10: 20). Polymer E: styrene, 4-vinylpyridine and N-
Copolymer of (2-hydroxyethyl) -4-vinylpyridinium chloride (molar ratio 30:38:32). Polymer F: styrene, (vinylbenzyl) dimethyloctylammonium chloride, isobutoxymethylacrylamide and divinylbenzene (molar ratio 40: 2)
0: 34: 6).

In a preferred embodiment of the invention, the image receiving layer also contains an insufficient amount of a polymeric binder to alter the porosity of the porous receiving layer. In another aspect of the invention, the polymer binder is polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, cellulose ether, polyoxazoline, polyvinyl acetamide, partially hydrolyzed polyvinyl acetate / vinyl alcohol, polyacrylic acid, polyacrylamide, polyacrylamide, Alkylene oxide, sulfonated or phosphorylated polyester and polystyrene, casein, zein, albumin, chitin, chitosan, dextran, pectin, collagen derivative, collodion, agar, arrowroot, guar gum, carrageenan,
It is a hydrophilic polymer such as tragacanth, xanthan, rhamsan, and the like.

In another preferred embodiment of the present invention, the hydrophilic polymer is polyvinyl alcohol, hydroxypropylcellulose, hydroxypropylmethylcellulose, gelatin or polyalkylene oxide. In yet another preferred embodiment, the hydrophilic binder is polyvinyl alcohol. The polymer binder should be selected to be compatible with the particles described above.

The amount of binder used should be sufficient to provide cohesive strength to the ink jet recording element, but must be such that the interconnected pore structure formed by the aggregates is not blocked by the binder. Should be quantity. In a preferred embodiment of the present invention, the weight ratio of the binder to the total amount of the particles is from 1:20 to 1: 5.

[0026] In addition to the image receiving layer, the recording element can also have a base layer next to the support, the function of which is to absorb the solvent from the ink. Useful materials for this layer are (a) particles, (b) particles, a polymer binder, and / or a crosslinking agent.

Since the image receiving layer is a porous layer containing particles, its void volume must be sufficient to absorb all the printing ink. For example, if the porous layer has 60% by volume pores, the image-receiving layer must have a physical thickness of at least 54 μm to immediately absorb 32 cc / m ² of ink.

The support of the ink jet recording element used in the present invention may be any of those commonly used in ink jet receivers, such as resin coated paper, paper, polyester, or Teslin ™ (PPG Industries, Inc., Pittsburgh, USA). Tyvek ™ synthetic paper (DuPont Cor), a polyethylene polymer-containing material sold in Pennsylvania)
p.) and Oppalyte ™ film (Mobil Chemical
Co.) as well as other composite films and the like as described in US Pat. No. 5,244,861. Opaque supports include plain paper, coated paper, synthetic paper, photographic paper support, melt extrusion coated paper, and laminated paper (eg, biaxially oriented support laminates).
Biaxially stretched support laminates are disclosed in U.S. Pat.
Nos. 5,866,282, 5,874,205, 5,888,643, 5,888,681, 5,888,683, and 5,888,714. These biaxially stretched supports are
It includes a paper base and a biaxially oriented polyolefin sheet laminated to one or both sides of the paper base, typically polypropylene.

On the transparent support, glass, cellulose derivatives (for example, cellulose ester, cellulose triacetate,
Cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate), polyesters (eg, polyethylene terephthalate, polyethylene naphthalate, poly 1,4-cyclohexane dimethylene terephthalate, polybutylene terephthalate, and copolymers thereof), polyimide, polyamide, polycarbonate , Polystyrene, polyolefins (eg, polyethylene or polypropylene), polysulfones, polyacrylates, polyetherimides, and mixtures thereof. The above-mentioned paper includes a wide variety of papers from high-end paper (for example, photographic paper) to low-end paper (for example, newsprint).

The support used in the present invention has a thickness of 50 to 500 μm.
m, preferably 75 to 300 μm. If necessary, antioxidants, antistatics, plasticizers and other known additives may be incorporated into the support.
To improve the adhesion of the ink receiving layer to the support, the surface of the support may be subjected to a corona discharge treatment before the application of the image receiving layer.

The coating composition used in the present invention can be prepared by any of a number of well-known methods such as dip coating, wound wire rod coating, doctor blade coating, gravure coating and reverse roll coating, slide coating, bead coating, extrusion coating, curtain coating and the like. It can be applied by techniques. Known coating and drying methods are described in Research Disclosur
e), No. 308119, published December 1989, pp. 1007-1008. Slide coating is preferred,
The base layer and overcoat may be applied simultaneously.
After coating, this layer is generally dried by simple evaporation and can be facilitated by known techniques such as convection heating.

To impart mechanical durability to the ink jet recording element, a small amount of a crosslinking agent acting on the above binder may be added. Such additives improve the cohesion of the layer. Crosslinking agents such as carbodiimides, polyfunctional aziridines, aldehydes, isocyanates, epoxides and polyvalent metal cations can all be used.

To improve colorant fade, UV absorbers, radical quenchers or antioxidants may be added to the image receiving layer, as is known in the art. Other additives include pH improvers, adhesion promoters, rheology improvers, surfactants, biocides, lubricants, dyes, optical brighteners, matting agents,
An antistatic agent and the like are included. In order to obtain sufficient coatability, additives well-known in such fields, for example, surfactants, defoamers, alcohols, and the like can be used. The usual amount of coating aid is 0.0% of the total solution weight.
It is an amount of active coating aid of 1 to 0.30%. These coating aids can be non-ionic, anionic, cationic or amphoteric. A specific example is MCCUTCHEON No. 1.
Volume "Emulsifiers and Dtergents", 1995, North American version.

The coating composition can be coated from water or an organic solvent, with water being preferred. The total solids content should be selected to produce a useful coating thickness in the most economical way. In specific coating formulations, the solids content is typically 10-40%.

[0035] Ink jet inks used to image the recording elements of the present invention are well known in the art. Generally, the ink composition used in inkjet printing is a liquid composition comprising a solvent or carrier liquid, a dye or pigment, a wetting agent, an organic solvent, a detergent, a thickener, a preservative, and the like. The solvent or carrier liquid can be pure water or can be water mixed with other water-miscible solvents such as polyhydric alcohols.
Further, an ink in which an organic material such as a polyhydric alcohol is a main carrier or a solvent liquid may be used. Particularly useful is a mixed solvent of water and a polyhydric alcohol. The dyes used in such compositions are generally
It is a water-soluble direct dye or acid dye. Such liquid compositions include, for example, U.S. Patent Nos. 4,381,946; 4,239,
Nos. 543 and 4,781,758 (which are incorporated herein by reference) are widely described in the prior art.

[0036]

The present invention will be described more specifically with reference to the following examples. The following comparative cationic polymers used are water-soluble. C-1: Poly (vinylbenzyl) trimethylammonium chloride (Chemistat (trademark) 6300H, Sanyo
Chemical Industries). C-2: poly (3-N, N, N-trimethyl) propyl methacrylamide chloride (trade name: Polycare (trademark))
133, Rhone-Poulenc Co.). C-3: polypropylene oxide triamine (trade name)
Jeffamine ™ T-5000, Huntsman, Corp.).

C-4: Polyethylene polyamine resin (trade name: Niccajet (registered trademark) 117, Nicca USA). C-5: Polyethyleneimine (trade name: Lupasol (trademark) P
EI, BASF Corp.). C-6: Poly (diallyldimethylammonium chloride) (trade name: Merquat ™ 100, Calgon Corp.). C-7: poly [N- [3- (dimethylamino) propyl] -N ′-[3-ethyleneoxyethylenedimethylammonio] propyl] urea dichloride] (trade name: Mi
rapol ™ WT, Rhone-Poulenc Co.).

The following comparative (b) cationic particles used are inorganic and water-insoluble. C-8: Inorganic dispersion of alumina-coated colloidal silica (trade name: Ludox (trademark) CL, EI du Pont de Nemours a
nd Co.). The following comparative (b) water-insoluble, cationic, polymer particles used had less than 20 mole percent cationic mordant moieties. C-9: Copolymer of butyl acrylate, 2-aminoethyl methacrylate hydrochloride and hydroxyethyl methacrylate (molar ratio 70/5/25).

The coating solution for the element base layer of the present invention was prepared using fumed alumina (Cab-O-Sperse ™ PG003, Cabot Corp.), polyvinyl alcohol (Gohsenol ™ GH-23A, Nippon Goh).
sei Co., Ltd.) and 2,3-dihydroxy-1,4-
Dioxane (Clariant Corp.) was prepared by mixing at a ratio of 88: 10: 2 to give an aqueous coating formulation with 30% solids by weight.

The coating solution for the image receiving layer was fumed alumina (Cab-O-Sperse® PG003, Cabot C
orp.), polyvinyl alcohol (Gohsenol ™ GH-2)
3A, Nippon Gohsei Co., Ltd.) and 8
It was prepared by mixing at a ratio of 5: 3: 12 to obtain an aqueous coating formulation having a solid content of 10% by mass. Fumed alumina particles have a primary particle size of 7 to 40 nm in diameter, with a maximum of 1
Aggregated to 50 nm. Surfactant Zonyl ™ FSN
(EI du Pont de Nemours and Co.) and Olin ™ 10G (Dixie chemical Co.) were added in small amounts as coating aids.

The above coating solution was applied to a polyethylene-coated paper base previously subjected to a corona discharge treatment for 40 minutes.
At the same time. An image receiving layer was coated on top of the base layer. Then, the coating is forced to
Dry at 0 ° C. until the bottom and top layers have a thickness of 4
Two-layer recording elements of 0 μm (43 g / m ² ) and 2 μm (2.2 g / m ² ) were obtained.

Element 2 of the Invention Element 2 was prepared in the same manner as Element 1, except that Polymer B was used in place of Polymer A. Element 3 of the Invention Element 3 was prepared in the same manner as element 1, except that the ratio of fumed alumina to poly (vinyl alcohol) to polymer A in the image receiving layer was 73: 6: 21.

Comparative Element 1 Except that polymer C-1 was used instead of polymer A,
This element was prepared as for Element 1. Comparative Element 2 Except for using polymer C-2 instead of polymer A,
This element was prepared as for Element 1.

Comparative Element 3 Except for using polymer C-3 instead of polymer A,
This element was prepared as for Element 1. Comparative Element 4 Except for using polymer C-4 instead of polymer A,
This element was prepared as for Element 1.

Comparative Element 5 Except for using polymer C-5 instead of polymer A,
This element was prepared as for Element 1. Comparative Element 6 Except for using polymer C-6 instead of polymer A,
This element was prepared as for Element 1.

Comparative Element 7 Except for using polymer C-7 instead of polymer A,
This element was prepared as for Element 1. Comparative Element 8 Except for using polymer C-8 instead of polymer A,
This element was prepared as for Element 1.

Comparative Element 9 This element was prepared similarly to Element 1, except that the image receiving layer contained only fumed alumina. Comparative Element 10 This element was prepared similarly to Element 1 except that the image receiving layer contained only fumed alumina and poly (vinyl alcohol) (98: 2).

Comparative Element 11 This element was prepared similarly to Comparative Element 10, except that the ratio of fumed alumina to poly (vinyl alcohol) was 90:10. Comparative Element 12 Except for using polymer C-9 instead of polymer A,
This element was prepared similarly to Element 3.

Density Test Images of cyan, magenta, yellow, red, green and blue patches are printed with 100% ink laydown using Epson Stylus ™ Color 740 with the ink of catalog number S020191 or Epson Stylus ™ Color 740. Stylus ™ Photo 870
And printed with ink of catalog number T008201.

After drying at ambient temperature and humidity for 24 hours, the Status A Dmax density was measured using an X-Rite ™ 820 densitometer as follows (for red, green and blue densities, the two components were: The color density was measured and averaged).

[0051]

[Table 1]

[0052]

[Table 2]

The above results show that the recording element of the present invention has a higher print density for most colors as compared to the control element.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Lori Jeanie Shaw-Klein 14613, New York, USA 17F, Rochester, Riverside Street 17F term (reference) 2C056 FC06 2H086 BA15 BA33 BA34 BA46

Claims (1)

[Claims] 1. a) particles having a primary particle size of 7 to 40 nm in diameter which may aggregate up to 300 nm; and b) water-insoluble cationic polymer particles comprising at least 20 mol% of a cationic mordant moiety. An ink jet recording element comprising a support having thereon a porous image receiving layer comprising: