JPH08156398A - Ink image acceptance material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To absorb ink quickly or to take in pencil by a method in which gelatin, a water-soluble alkali metal carboxymethyl cellulose, and an organic polymeric particulate matting agent are incorporated into in an ink imagereceiving layer, and measures are taken for specifying the total amount of these components and others. SOLUTION: An ink receiving material is a matting agent and has a web support in the shape of a sheet and others coated with an ink image-receiving layer containing gelatin as a binder together with a partially protruding water- insoluble particulate organic material. In this case, gelatin, a water-soluble alkali metal carboxymethyl cellulose, and an organic polymeric particulate matting agent are incorporated in the ink image-receiving layer, and the total amount of these components is set up at 75 % or above of the total weight of the layer. The coating amount of the gelatin in the ink image-receiving layer is set up at 0.5-10 g/m<2> , and the alkali metal carboxymethyl cellulose is set up at 1/20-5/1. Moreover, the average particle size of the organic polymeric particulate matting agent is set up at 1-15 μm.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to a pencil-writable, multi-directional image receiving material suitable for use in impact as well as non-impact printing.

BACKGROUND OF THE INVENTION For a long time printing has been carried out by pressure contact of an ink receptive material, usually plain paper, with an inked marker or printing plate. The impact printing method used very often is
It is known as lithographic printing based on the selective acceptance of lipophilic inks on the printing plates made therefor.

At present, various non-impact printing methods have to some extent replaced conventional pressure contact printing.
One of the more important non-impact methods is that the thermoplastic resin-containing toner particles are transferred from the electrostatic charge pattern to the receiving material,
It is electrography, which is fixed on it by heat.

According to other non-impact printing methods, the ink is applied by a pen-plotter or ink jet.

Inkjet printing, which is becoming more and more important, is described in Irvine CA, Via Pal, US 92715, for example.
Atino, 18792, Palatino Press, 1986, Jerome L. Johnson, Principles of Non Imp.
It is described in the act Printing book. In ink jet printing, tiny drops of ink fluid are projected directly onto the ink receiver surface for printing without physical contact between the printing device and the receiver. The placement of each droplet on the printing substrate is electronically controlled. Printing is accomplished by moving the printhead across the paper or vice versa.

Yet another transfer printing method uses a thermal printing or impact printing machine (eg a typewriter) to transfer a waxy layer that is pigmented in its entirety or imagewise onto a receiving material (eg US-type). P592259
3).

High speed printing (whether it is impact printing or non-impact printing) requires a rapid tactile drying of each successive print to avoid smearing when the new prints come into contact with each other. The ink image-receiving layer therefore has a high ink absorption rate (short ink dry time) and the deposited ink (water-based or predominantly organic) is applied to the print stock in contact with the next overlaid sheet. Immediately afterwards, it is especially important that it does not smear, rub and / or stain. Aqueous inks are commonly used in inkjet printing and organic inks are used in offset printing, a method derived from lithographic printing, in which the printing press is first wetted by a roller with water and then the printing plate is wetted. It is guided towards an inking roller from which the greasy or oily ink is imagewise transferred (offset) onto a paper printing stock.

Ink receptive materials, especially for use in high quality ink jet printing, should have as thin an ink image receptive layer as possible in combination with high ink absorbency, so that the absorbed ink dots are spread. It produces a sharp high-density image that does not stain or stain. The ink image-receiving layer, on the one hand, must be easily wet without sloppyness, i.e. without agglomeration of adjacent ink dots, and on the other hand, the ink-absorbing properties of the ink image-receiving layer are:
The deposited ink image should have good waterfastness, i.e. be waterproof.

Furthermore, the ink-receiving material in sheet form should not show any curl or tend to stick to other sheets when stacked before and after printing, even at high printing speeds.

According to US Pat. No. 3,888,270, an ink image receiving layer suitable for use in combination with an aqueous ink is
It preferably contains proteins such as gelatin, albumin or casein, polysaccharides, cellulose or cellulose derivatives, polyvinyl alcohol or copolymers of vinyl alcohol. The image receiving layer containing these polymers can contain hydrophilic silica gel and a white toner.

Improvements in optical density and reduced drying times can be obtained by using particulate material in the polymeric binder. For example, according to US Pat. No. 3,357,846, pigments such as kaolin, talc, barite and TiO ₂ applied in starch and polyvinyl alcohol (PVA) as binders are used for said purpose.

It has good receptivity to inks in ink jet printers and pen plotters, and also has good uptake of drafting pencils, strongly fixing the toner image obtained by electro (photo) graphy on it. A drafting material suitable for use in published European patent applications (EP-
A) 0565154. The drafting film may include (A) gelatin, (B) one or more silica matting agents, (C) opacifying agent, (D) epoxysilane compound,
It contains (E) polyurethane and (F) curing agent. The pencil writability on the drafting film comes mainly from crystalline silica which gives the image-receiving layer a moderate abrasion power to ensure good uptake of pencil graphite. The opacity of the drafting film preferably comes from titanium dioxide particles of anatase crystal deformation.

The image-receiving layer of the drafting material according to EP-A above is coated from an aqueous medium. The use of organic solvents in the coating of the imaging layer is often undesirable from an environmental point of view and unfavorable for reasons of flammability and odor problems.

Recording sheets suitable for use in both ink jet and electrophotographic imaging methods, but which do not have the film-making properties of the drawing, are for example US-
P5254403.

The properties which must be improved in combination for versatile image-receiving materials are the rapid absorption of inks, both aqueous and organic, limited bleeding of printed marks and new printed sheets. It is to prevent rubbing when piled up. Furthermore, the ability of the pencil drawing part to be retouched by erasing with a pencil or an ink eraser and the taking in of a drawing pencil allow for controlled moderate wear of the recording surface and good waterfastness of the printed image. Is required.

OBJECTS AND SUMMARY OF THE INVENTION The object of the invention is to provide a short ink dry time combined with a moderate abrasion of the recording surface for good writing with a pencil and a good waterfastness of the print. All-round including sheet or web-like support coated with an ink image-receiving layer suitable for use in impact and non-impact printing with rapid ink uptake
An object is to provide an ink image receiving material.

It is another object of the present invention to provide such a multi-sided ink receptive material in which the ink receptive layer is applied from an aqueous medium in an environmentally interesting manner.

Other objects and advantages of the invention will be apparent from the following description.

According to the present invention there is provided an ink image receiving material which comprises a water-insoluble particulate organic material called a partially protruding matting agent together with gelatin as a binder. A sheet-like or web-like support coated with, the layer containing (1) gelatin, (2) water-soluble alkali metal carboxymethyl cellulose and (3) organic polymer granular matting agent. 1), (2) and (3) together represent at least 75% of the total weight of said layer, the coverage of gelatin in said layer being in the range 0.5 to 10 g / m ² . The alkali metal carboxymethyl cellulose, expressed as a weight ratio to gelatin, is present in the layer in the range of 1/20 to 5/1 and the particulate polymeric organic matting agent is 1 to 15 μm.
m has an average particle size in the range of at least 2
Consisting essentially of an organic polymer composition having a glass transition value (Tg) of 5 ° C., wherein the weight ratio of said matting agent to gelatin is 1
It is characterized by being in the range of / 5 to 15/1.

The average thickness of the ink image-receiving layer having the partially protruding matting agent particles is preferably in the range of 2 to 15 μm. For particularly good receptivity of aqueous inks, the coverage of gelatin in the layer is preferably in the range 1.0 to 5.0 g / m ² , and the weight ratio of alkali metal carboxymethyl cellulose to gelatin is 1 / 10 to 2/1
And the weight ratio of the matting agent to gelatin is preferably from 1/2 to 5/1.

DETAILED DESCRIPTION OF THE INVENTION Any type of commercially available gelatin can be used in the ink image-receiving layer of the image-receiving element of the present invention. Commercial gelatin is
It is a mixture of proteins with molecular weights varying from 15,000 to 250,000. Preference is given to slightly degraded (by hydrolysis) commercially available gelatin having an average molecular weight of 55,000 or higher.

The distribution of protein components in gelatin as a natural product depends on the source of the raw materials and the treatment they have undergone. Gelatin can advantageously be made starting from so-called lime-treated collagen-containing pig skin, bone or cowhide materials. Swelling in water is minimal at the isoelectric point when using all types of gelatin. The pH of the ink used is substantially different from the pH at the isoelectric point of gelatin present in the image-receiving layer to improve absorption of the aqueous ink in the dried ink-image-receiving layer. Is advantageous to.

Gelatins are distinguished by their gel strength. The ink image-receiving layer having good mechanical strength is
British Standard Institution BS 757: 197
5 Methods for Sampling and Testing Gelatin
It preferably contains gelatin having a gel strength of at least 200 g, measured according to.

The preferred gelatin for use in the ink image-receiving layer of the present invention has a viscosity of ^{1 at} a shear force of 1000 s ^-1.
For a 0% by weight aqueous solution, measured at pH 6 at 36 ° C., at least 20 mPa.s. Characterized by the viscosity of s.

In the ink image-receiving layer of the present invention, the gelatin may harden to some extent, which results in improved bleeding or bleeding of aqueous inks and improved cohesion and abrasion resistance with improved waterfastness. I will provide a.

An example of a suitable gelatin hardener is the Theory of the Photogra, TH James, Macmillan Publishing Co., Inc. 1977, New York.
phicProcess 4th edition, pp. 78-84. In that connection, aldehyde curing agents such as formaldehyde, glyoxal and glutaraldehyde, s-triazines such as 2,4-in the form of water-soluble sodium salts.
Dichloro-6-hydroxy-s-triazines, activated olefins such as bis (vinylsulfonyl) compounds, and carbamoylpyridinium salts are specified.

Water-soluble carboxymethyl cellulose is usually used as a sodium salt. A preferred class of sodium carboxymethyl cellulose for use in accordance with the present invention is in the range 0.5 to 1.3, preferably 0.75.
It has a degree of substitution (DS) in the range of -0.90. Degree of substitution (DS) is related to the -O-CH ₂ -COONa average number of hydroxyl groups in the pyranose ring of the transformed cellulose based (maximum 3).

Such water-soluble sodium carboxymethyl cellulose contributes primarily to the improved absorption of aqueous inks and reduces the drying time of aqueous ink images.

Sodium carboxymethyl cellulose is obtained by the reaction of alkali cellulose with Cl--CH ₂ --COONa and usually contains 50 to 600 bound pyranose rings, the sodium atom of the CH ₂ ONa group of which is It is substituted by -CH ₂ -COONa in whole or in part.

-CH ₂ -CO of carboxymethyl cellulose
ONa content can be measured by titration with a strong acid that converts -COONa groups to carboxylic acid groups, and is equivalent to the equivalent weight of the acid used to convert -CH ₂ -COONa groups to free acid groups. Na per gram
It can be displayed as mg of OH. Compared to fully substituted -CH ₂ -COONa content of cellulose measured -CH ₂
-The degree of substitution can be easily calculated from the COONa content.

Water-insoluble polymeric matting agents that partially project from the recording layer provide fast feel drying of aqueous and non-aqueous inks and prevent sticking of printed sheets that stack immediately upon receipt of their ink. This prevents stains on the printed part. In addition, the matting agent provides strong adhesion of lipophilic inks used in impact printing, and by electro (photo) graphic imaging using triboelectrically charged toner particles containing a heat-softenable thermoplastic resin. It provides strong heat fixing of the resulting toner image.

As described above, the organic matting agent is 1 to 15 μm.
m, preferably in the form of single particles having an average particle size of 3 to 10 μm in the ink receiving layer. The use of the particles in the indicated weight percentages of the matting agent to gelatin gives the ink-receiving layer a certain surface roughness and capillarity which enhances its ink absorption capacity.

The surface roughness of the ink image-receiving layer of the present invention is ANSI Norm ASME B 46.1-1985 in order to obtain sufficient pencil uptake and rapid tactile drying after ink reception.
Accordingly, the Ra value measured by PERTH-O-METER (trade name) is preferably in the range of 0.5 to 3.0 μm.

The preferred particulate organic polymeric matting agent material for use in the image-receiving layer of the ink image-receiving material according to the present invention is in the form of polymeric beads, the glass transition temperature of which is at least 25 ° C, more preferred. Is 40 ° C. or higher. The production of the matting agent is carried out in the liquid medium, which acts as a dispersion medium for the formed polymer obtained as a latex, using the usual polymerization initiator substances of α, β-ethylenically unsaturated monomers. It can be carried out by addition polymerization. The polymer beads can consist of homopolymers or copolymers, and can be graft polymers with different polymer cores and encapsulations. The latter type of graft polymer
The polymer bead structure is preferred because it has microcavities on its surface formed by the grafted pendant polymer that provides good ink retention.

Examples of suitable matting agents are in the form of polymethacrylate or polystyrene beads, made for example by suspension polymerization. These grains are known matting agents or spacer beads in photographic silver halide emulsion materials (see, for example, US Pat. No. 5,057,407). The glass transition temperatures of polymethylmethacrylate and polystyrene are 105 ° C. and 100 ° C., respectively, so that at room temperature these polymers have sufficient hardness to act as mild wear materials for pencils.

Other suitable organic polymeric matting agents having a glass transition temperature (Tg) above 60 ° C., by appropriate selection of the monomer components and the degree of polymerization, are described in US-P 3941727 and FR-P 1545262. Can be manufactured as follows.

Yet another suitable organic polymeric matting agent is published European patent application (EP-A) 0466982.
And 0584407. The last-mentioned delusterants made by EP-A are alkali-soluble.

A preferred organic matting agent which provides a quick feel dryness of the ink image and produces a pencil writable ink image receiving layer is made by US Pat. Nos. 4,287,299 and 4,614,708. According to the methods described therein, micronized solid spherical polymeric beads having an average particle size of about 0.5 to about 15 μm can be made, said beads having a glass transition temperature of at least 40 ° C. . The method described in the US-P specification includes the following steps:

(A) in an aqueous solvent mixture of water and at least one water-miscible polar organic solvent, (1) soluble in its own monomer present in said aqueous solvent mixture, At least one α, β-ethylenically unsaturated monomer capable of forming a polymer that is insoluble in the solvent mixture,
(2) a free radical-forming polymerization initiator that is soluble in an aqueous solvent mixture (eg, potassium, sodium or ammonium persulfate), and (3) a hydrophilic group (eg, sodium or potassium carboxylate that is soluble in the aqueous solvent mixture). Or a sulfonate group, a hydroxide group, an ethylene oxide group, and a graft-polymerizable polymer containing an amide or a cyclic amide group),
The weight ratio of the graft-polymerizable polymer to the monomer is 1.
5: 100 to 8: 100, the weight ratio of polymerization initiator to monomer is 0.1: 100 to 5: 100, and (B) the resulting solution is heated from 50 ° C to its reflux temperature. The homopolymer or copolymer co-agglomeration and its precipitation are initiated from the above monomers by heating to temperatures up to and with continuous stirring to form a small proportion of grafted polymer.

In the preparation of an aqueous homogeneous dispersion of polymer beads for use in an image receiving material according to the present invention, the size of the beads depends on the type of graft polysynthetic polymer, but the reaction temperature and other reactions. It can also be controlled by adjusting parameters such as the concentration of α, β-ethylenically unsaturated monomers, and in particular the ratio between the volumes of water and water-miscible solvent, eg alcohol in the aqueous solvent mixture. 0.5
Polymer beads having an average particle size in the range of -15 μm can be produced by this method.

Prior to the initiation of the polymerization, the reaction medium is a mixture of solvents at room temperature, the graft-polymerizable polymer, the water-soluble free-radical-forming polymerization initiator and at least one α, β-ethylenically unsaturated monomer. It consists mainly of a homogeneous solution of the body.

By heating the reaction medium, the dissolved initiator decomposes and forms free radicals, which are then dissolved via labile hydrogen atoms or via reactive sites. Intervenes in the reaction with and thus forms a living molecule, which, while remaining dissolved in an aqueous solvent mixture, encounters reactive monomers or polymer chains of already grown such monomers. And thus form a graft polymer. Polymer beads are thus formed, which consist of a core and an envelope.

The bead nuclei are twisted polymer chains obtained by the polymerization of monomers which are insoluble in the aqueous solvent mixture, and polymers obtained by the copolymerization of the monomers and the initially dissolved polymer. The polymer chains are interlaced with the polymer chains grafted at one end to the core of the polymer beads, thus forming an envelope for the polymer beads.

The polymer to be encapsulated acts as a dispersion stabilizer by steric hindrance in an aqueous medium. The encapsulated polymer is
It preferably contains hydrophilic groups, such as carboxylic acid groups or carboxylic acid anhydride groups, which provide good adhesion of the ink image-receiving layer to the gelatin matrix.

Suitable α, β-ethylenically unsaturated monomers for use in preparing the nucleus of the polymer beads include, for example, styrene, vinyltoluene and substituted vinyltoluenes such as vinylbenzyl chloride and its homologues, Chlorostyrene, alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and higher methacrylates such as stearyl methacrylate; substituted alkyl methacrylates such as hydroxyethyl methacrylate; butadiene, isobutylene, chlorobutadiene, 2-methylbutadiene; vinyl pyridine such as 2-. And 4-vinylpyridine. Depending on the particular requirements, in particular the Tg, one can select not only a combination of these monomers but also one of them. Monomers other than those mentioned above can also be used provided they meet the solubility and Tg requirement settings.
It is also possible to combine one or more of the aforementioned monomers with other monomers which themselves do not satisfy the requirements described herein for the α, β-ethylenically unsaturated monomers. Vinylidene chloride, vinyl chloride, acrylonitrile and methacrylonitrile, for example, are not solvents for their polymers and therefore cannot be used for the formation of homopolymers. Nevertheless, they can be combined with one or more suitable monomers which meet the requirements mentioned above to form copolymers which are soluble in the latter monomers.

Graft-polymerizable polymers particularly suitable for use in the production of polymeric matting agent encapsulation in the form of encapsulated core microbeads include, for example, polyethylene oxide,
Low molecular weight polyvinyl alcohol, polyvinylpyrrolidone, co (vinyl alcohol / vinyl acetate) containing 12 mol% vinyl acetate units and the same copolymer containing 40 mol% vinyl acetate units, 4
Co (acrylic acid / styrene) sodium or potassium salt containing 0-60 mol% acrylic acid, co (vinyl acetate / crotonic acid), hydroxyalkyl or aminoalkyl (meth) acrylate and copoly (styrene / maleic anhydride) ), Copoly (vinyl acetate /
Maleic anhydride), a reaction product with copoly (ethylene / maleic anhydride) or copoly (N-vinylpyrrolidone / maleic anhydride), and co (styrene / maleic acid monosodium salt), preferably 50 mol% There is the latter copolymer containing maleic acid monosodium salt and 50 mol% styrene, although other graft-polymerizable polymers can be used, but hydrophilic ones are preferred.

In making a polymeric bead encapsulation with grafted co (styrene / maleic acid monosodium salt) consisting of equal amounts of the monomer components, a highly homogenous dispersion with an average particle size of 0.5 to 15 μm is obtained. Beads can be obtained.

The weight ratio of graft-polymerizable core polymer to said monomer is generally comprised between 1.5: 100 and 8: 100. The best proportion to obtain a constant average particle size can easily be determined by doing a few simple tests.

The polymer beads obtained with said co (styrene / maleic acid monosodium salt) by graft polymerization on polymerized methyl methacrylate (core polymer) are especially aqueous ink images of the image receiving material according to the invention. It is particularly suitable for use in a coating composition for making a receiving layer.

In the preparation of polymer beads using co (styrene / maleic acid monosodium salt) as the graft-polymerizable polymer, it was observed that the stability of the dispersion is related to the pH value. When methylmethacrylate is used as the α, β-ethylenically unsaturated monomer and co (styrene / maleic acid monosodium salt) is used as the graft-polymerizable polymer, the resulting beads have a dispersion pH of 4.0 with hydrochloric acid. When reduced to, the polymer is converted to nodules as a result of the conversion of the carboxylic acid groups into insoluble free carboxylic acid groups. However, when the pH value is raised again with sodium hydroxide, a stable dispersion without nodules is restored.

The advantage of the polymer dispersions made according to said US Pat. No. 4,614,708 is that it is sterically stable as a result of the stable arrangement in space of the grafted polymer chains (encapsulation) around the core of the beads. It is to contain a loose solid polymer. The presence of ionic groups in the grafted polymer provides a solvation effect in aqueous media. This solvation action has a stabilizing effect that supplements the steric stability of the bead-encapsulated grafted polymer chains.

As a result of the strong binding of the polymer grafted to the polymer nuclei and the absence of solvent entrapped in the beads, when the dispersion is diluted, a hydrophilic colloid binder, such as gelatin, and the dispersion are combined. Mixing prevents the formation of agglomerates of beads. Furthermore, the presence of ionic or polar groups in the grafted polymer of the encapsulation results in a strong binding of the beads to gelatin, which favors the mechanical strength of the image-receiving layer.

In addition to the above-mentioned components (1), (2) and (3) of the image-receiving layer, ie gelatin, alkali metal carboxymethyl cellulose (CMC) and organic particulate polymer matting agent, the ink image-receiving The layer can contain other types of ingredients that improve one or more of the desired properties such as good ink receptivity (wetting), good ink absorption, fast touch drying and good pencil writing ability.

Ingredients that improve one or more of the above properties include:
For example, hydrophilic binders other than gelatin and CMC, such as (1) hydroxyethyl cellulose; (2) hydroxypropyl cellulose; (3) hydroxyethyl methyl cellulose; (4) hydroxypropyl methyl cellulose; (5) hydroxybutyl methyl cellulose; (6)
(7) Sodium carboxymethyl hydroxyethyl cellulose; (8) Water-soluble ethyl hydroxyethyl cellulose; (9) Cellulose sulfate; (10) Polyvinyl alcohol; (11) Polyvinyl acetate; (12) Polyvinyl acetal; (1)
3) polyvinylpyrrolidone; (14) polyacrylamide; (15) acrylamide / acrylic acid copolymer;
(16) Styrene / acrylic acid copolymer; (17) Ethylene-vinyl acetate copolymer; (18) Vinyl methyl ether / maleic acid copolymer; (19) Poly (2-
Acrylamido-2-methylpropanesulfonic acid);
(20) Poly (diethylenetriamine-coredipic acid); (21) Polyvinylpyridine; (22) Polyvinylimidazole; (23) Quaternized polyimidazoline; (24) Modified polyethyleneimine epichlorohydrin; (25) Ethoxylated polyethyleneimine; (26) Poly (N, N-dimethyl-3,5-dimethylenepiperidinium chloride); (27) Polyethylene oxide; (28) Polyurethane; (29) Melamine resin; (30) Epoxy resin; (31) Urea resin;
(32) Carrageenan; (33) Dextran; (3
4) gum arabic; (35) casein; (36) pectin; (37) albumin; (38) starch; (39) collagen derivative; (40) collodion; (41) agar, and (42) carginic acid and alginate. is there.

The wetting power for aqueous ink is
Especially improved with surfactants which may be any of anionic, amphoteric and nonionic type.

Examples of useful surfactants are alkali metal salts of fatty acids (soap), N-alkyl amino acid salts, alkyl ether carboxylates, acylated peptides, alkyl sulfonates, alkylbenzenes and alkylnaphthalenesulfonates. , Sulfosuccinate, olefin sulfonate, N-acyl sulfonate, sulfonated oil, alkyl sulfonate, alkyl ether sulfonate,
Alkyl allyl ether sulfonate, alkyl amide sulfonate, alkyl phosphate, alkyl ether phosphate, alkyl allyl ether phosphate, alkyl and alkyl allyl polyoxyethylene ether, alkyl allyl formaldehyde condensation salt, alkyl allyl ether Sulfonates, alkylamide sulfonates, alkyl phosphates, alkyl ether phosphates, alkyl allyl ether phosphates, alkyl and alkyl allyl polyoxyethylene ethers, alkyl allyl formaldehyde condensed polyoxyethylene ethers, polyoxypropylene Blocked polymer having, polyoxyethylene polyoxypropylene alkyl ether, glycol ester polyoxyethylene ether, sorbitan ester polio Shi ethylene ether, polyoxyethylene ethers of sorbitol esters, polyethylene glycol fatty acid esters, glycerol esters, sorbitan esters, propylene glycol esters, sugar esters, fluorinated surfactants, such as fluoro C2~C
10 alkyl carboxylic acid, N-perfluorooctane sulfonyl glutamate disodium, 3- (fluoro-
C6-C11 alkyloxy) -1-C3-C4 sodium alkylsulfonate, 3- (ω-fluoro-C6-)
C8 Alkanoyl-N-ethylamino) -1-propanesulfonate sodium, N- [3- (perfluorooctanesulfonamido) -propyl] -N, N-dimethyl-N-carboxymethyleneammonium betaine, fluoro-C11-C20. Alkylcarboxylic acid, perfluoro-C7-C13 alkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoro-
C4 to C12 alkyl sulfonic acid Li, K and Na, N
-Propyl-N- (2-hydroxyethyl) -perfluorooctanesulfonamide, perfluoro-C6-C
There are 10 alkylsulfonamidopropylsulfonylglycinates, bis- (N-perfluorooctylsulfonyl-N-ethanolaminoethyl) -phosphonates, mono-perfluoro-C6-C16 alkyl-ethylphosphonates and perfluoroalkylbetaines.

Particularly useful is, for example, US-P4781.
985 is described in the following structural _{formula: F (CF 2) 4-9 CH} 2 CH 2 SCH 2 CH 2 N + R 3 X - fluorocarbon surfactants having a (wherein R represents hydrogen or alkyl); and are described in US-P5084340, following structural _{formula: CF 3 (CF 2) m} CH 2 CH 2 O (CH 2 CH 2 O) n R ( wherein m is equal to 2 to 10, n is equal to 1 to 18 ,
R represents hydrogen or an alkyl having 1 to 10 carbon atoms). These surfactants are commercially available from DuPont and 3M.

The concentration of the surfactant in the ink image-receiving layer for receiving aqueous inks is typically in the range 0.1 to 2% by weight based on the total dry weight of the layer, preferably 0.
It is in the range of 4 to 1.5% by weight.

Other ingredients are used to improve the waterfastness of the ink layer and to prevent bleeding of the resulting image. These components may be reaction components contained in the ink, such as those described in US Pat. No. 4,694,302, and reaction components that form substances that improve waterfastness, and in US-P above carboxymethylcellulose. In-situ formation of water-insoluble salts of, for example, aluminum salts is described.

Other waterfastness improving compositions are described, for example, in US
-P5206071, according to which
The hydrogel complex binds to the high molecular weight quaternary ammonium salt.

The waterfastness of the dye image is obtained by using a so-called mordant which does not move in the ink image receiving layer. When an acidic or anionic type dye must be mordanted (this is the usual case), the ink image-receiving layer contains a basic or onium type mordant such as a polymer containing ammonium groups. An example of such a polymer is US-P4371.
582, US-P4575465, US-P46490.
64, GB-P1221131, GB-P122119
5, GB-P2210071 and EP423829.

US Pat. No. 4,371,582 describes a basic polymer latex containing a tertiary amino or quaternary ammonium group as a dye fixing agent, and US Pat.
75465 claims an ink image-receiving layer containing a hydrophilic polymer having up to 50% by weight of vinylpyridine / vinylbenzyl quaternary ammonium salt copolymer. Other types of basic or onium type polymer mordants are
Research Disclosure November 1976, item 151
62, and unpublished European patent application no. 9420012
4.9.

When the ink receptive material is intended to be viewed in reflection and the ink receptive layer is applied on a transparent substrate, the ink receptive layer itself may be opacified with a brightener. For that purpose, the TiO ₂ (methyl or anatase) pigment is preferably used in an amount sufficient to produce a transmission density for white light of preferably at least 0.05, and preferably 0.3 or more. The coating amount of the whitening agent is 0.1 to 10
It can be in the range of g / m ² , with 1 to 3 g / m ² being preferred. The brightener slurry may be added by in-line injection or by batch addition just prior to coating the image-receiving layer on the support.

Other useful opacifying pigments, which are inorganic particulate materials having porous properties or capable of forming porous aggregates, include, for example, silica, talc, clay, kaolin, diatomaceous earth, calcium carbonate, magnesium carbonate, water. Aluminum oxide, aluminum oxide, zinc oxide, barium sulfate, calcium sulfate, zinc sulfide, aluminum silicate,
There are calcium silicate and lithopone.

The specific surface area of these inorganic particulate materials is 10
It can vary from ˜200 m ² / g (BET non-surface area) and the oil absorption can be above 150 ml / 100 g, for example as described for silica particles in US Pat. No. 5,213,873.

The ink receptivity of an ink containing a polar solvent is determined by a compound acting as a plasticizer for gelatin, such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethyl ether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate. , Tetrachlorophthalic anhydride, tetrabromophthalic anhydride, urea phosphate, triphenyl phosphate,
Glycerol monostearate, propylene glycol monostearate, tetramethylene sulfone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and polymer latices with low Tg values such as polyethyl acrylate, polomethyl acrylate, etc. Can be improved.

The ink image-receiving layer of the material of the present invention may further contain other additives such as compounds which absorb ultraviolet radiation such as optical brighteners and antistatic agents.

When the ink receiving layer is a silver complex salt diffusion transfer reversal (D
When intended to form a silver image therein by the (TR) method, said layer or an adjacent layer in water permeable relationship therewith can contain physical development nuclei.

Silver Complex Salt Diffusion Transfer Reversal (DTR), which reduces transferred silver complex salt compounds derived from imagewise exposed and developed silver halide emulsion materials to silver metal by the contact action of a reducing agent and physical development nuclei. The law is, for example, Photographic by Andre Rott and Edith Weyde, THe Focal Press, 1972, London and New York.
It is described in the Silver Halide Diffusion Processes book.

Preferred physical development nuclei are colloidal noble metal particles such as silver particles, colloidal heavy metal sulfide particles such as colloidal palladium sulfide, nickel sulfide and mixed silver sulfide-nickel sulfide.

According to a particular example, said nuclei are formed in situ with the reactive components contained in the ink receiving material.

The ink receiving layer may contain physical development nuclei in operative contact with the physical development accelerator, examples of accelerators include:
Published German patent application (DE-OS) 112435
4, US-P4031471, US-P407252
6. Published European patent application (EP-A) 002
There are thioethers described in 6520.

Unpublished European patent application (EP-A) N
o. According to a particular example described in 94201994.4 (filed Jul. 11, 1994), the ink image-receiving layer for ink jet printing comprises a physical development nucleus and a reducible metal contained in the ink. It contains a reducing agent. The ink receptive material of the present invention can be used to act as a receptive material for a reactive ink and can contain, for example, physical development nuclei and a reducing agent, whereby a reduction deposited by inkjet in the receptive layer. The catalytic reduction of the possible metal salts forms a metal image, for example a silver image.

In the image receiving material according to the present invention, the ink receiving layer can be coated on one or both sides on a support material of any kind which is transparent, translucent or opaque, for example metal, glass, resin and paper supports. .

Particularly useful transparent supports include those used in the manufacture of photographic films such as cellulose esters such as cellulose acetate, polyesters such as polyethylene terephthalate, polyethylene naphthalate, and in its structure such as sulfo-isophthalic acid and poly (ethylene phthalate). Polyesters containing hydrophilic moieties derived from oxyalkylene oxides, as well as resins made from polyamides, polycarbonates, polyimides, polyolefins such as polypropylene, polyalkylmethacrylates, polyvinylchlorides, poly (vinylacetals), polyethers and polysulfonamides. There is a support.

Polyester film supports, especially those made of poly (ethylene terephthalate), are preferred because of their excellent dimensional stability. When such polyesters are used as the support material, a subbing layer is usually present to improve the bonding of the gelatin-containing image-receiving layer to the support. Useful subbing layers for this are eg Rese
arch Disclosure November 1989, item 3071
No. 05, a polymer of vinylidene chloride, such as vinylidene chloride / acrylonitrile / allylic acid terpolymers or vinylidene chloride / methyl acrylate / itaconic acid terpolymers. including.

A common opaque support is a paper support, in which case the paper may be coated with a resin layer, for example a polyolefin resin layer, preferably polyethylene coated paper.

In a particular example, a high quality opacifying resin support is used, having internal light-scattering pores obtained, for example, by extrusion of a mixture of poly (ethylene terephthalate) and polypropylene, so-called synthetic papers or paper-like films. Resin supports or brightener-filled polyesters are used [see for example (PCT) WO 94/06849].

The inks used to image the image recording materials of the present invention can be of various types and are not necessarily limited to aqueous inks, because the ink image receiving materials of the present invention are This is because rapid touch drying can be obtained similarly even with an ordinary offset ink that is oily.

The ink composition used in ink jet printing is typically a liquid composition containing a solvent or carrier liquid, a dye or pigment, a humectant, a thickener, a preservative and the like. The solvent or carrier liquid is predominantly water, but inks in which organic materials such as polyhydric alcohols are used as carrier liquid can be used. The dye used in such an inkjet ink composition is typically a water-soluble direct dye or an acid dye (anionic dye). Such a liquid ink composition is disclosed, for example, in US-P 4381946, US
-P4781758 and US-P4994110.

The image-receiving material according to the invention comprises an identification card in the form of a laminate, the so-called I.D., which protects the image information against mechanical damage and counterfeit counterfeiting. D. Suitable for manufacturing cards.

I. As a guarantee document for performing certain activities (driver's license), for entering a certain area, or for confirming the recognition of an individual for engaging in a specific industrial activity. D. Looking at the expanded use of the card,
I. Due to certain changes in its data and / or photographs. D.
It is important to make card counterfeiting impossible.

Laminates according to the present invention are imaged by introducing a black and white and / or dye image obtained, for example, by the diffusion transfer method, and laminating it with a resin support such as a vinyl chloride polymer support using pressure and heat. It includes the image receiving layer described above encapsulated between resin coversheets which are secured to the receiving layer.

The cover sheet can be any hydrophobic thermoplastic resin sheet, for example a polyester resin such as polyethylene terephthalate, a bis-phenol polycarbonate, a polyolefin such as polyethylene or polypropylene, or a vinyl chloride polymer as defined herein. Can be made from According to a particular example, the cover sheet is a polyethylene terephthalate sheet coated with a resinous adhesive layer, for example a polyethylene or polypropylene layer.

Lamination of the resin cover sheet with the imaged image receiving material is carried out at a temperature in the range of 120 to 150 ° C.
It is preferably carried out at 35 [deg.] C. under a pressure of, for example, 10 to 15 kg / cm < ² > by heat sealing between flat steel plates or roller laminating machines. The laminated articles are cooled under pressure to avoid deformation.

The laminate may contain an image-receiving layer on the entire surface of the support or in part thereof, leaving a free edge, for example as described in US Pat. No. 4,425,421.

According to one example, the image receiving layer is coated on an opaque polyvinyl chloride having a thickness of only 0.050 to 0.300 mm. Sheets of that thickness are capable of receiving data printed by mechanical printing methods, such as offset or intaglio printing.

The image-receiving layer can be coated on the support itself and / or on the support containing the combined coverage assurance marks. When using a paper support, the security mark can be in the form of a watermark. Guarantee marks that can be printed on the support or subbing layer include fingerprints, printing patterns known from banc notes, such as braid patterns, coded information such as magnetic binary code information, prominent names, or GB for example. -P1
Containing UV readable printing inks as described in US Pat. No. 5,18,946 and US Pat. No. 4,105,333 or other printed personal data applicable with nacreous pigment inks or liquid crystals as described for example in European Patent (EP) 0400220. By adding a mark, it is other print personal data.

Other possibilities for increasing the security against counterfeiting mean light interference pigments in the image-receiving layer itself and / or pigments, for example pearlescent pigments (thus changing the color by viewing in transmission or reflection). Infrared absorption mark in or on the cover layer for forming the laminate of
Magnetic dots or stripes and eg DE-OS 2639
952, GB-P1502460, and GB-P157.
2442 and U.S. Pat. No. 3,668,795 to include holograms and / or electronic microcircuits with or without UV radiation absorption marks hidden from visibility. Holographic patterns can be obtained in silver halide emulsion layers specially designed for that purpose, usually Lippmann emulsions, and can or cannot be combined with photography in a laminate.

According to an example where the resin sheet used as a support for the laminate must have the required thickness for the identification card which has to be inserted in the slot of the electronic forensic device. , 0.68 mm to 0.
Several sheets of matte polyvinyl chloride are stacked and laminated to reach a final thickness of 84 mm.

The following examples illustrate the invention but do not limit it. All parts, ratios and percentages are by weight unless otherwise stated.

Inventive Examples 1-8 and Non-Inventive Examples 9-12 A polyethylene terephthalate film having a thickness of 100 μm is undercoated on both sides to improve the adhesion to a gelatin-containing layer. Both sides were coated with one of 12 (see Table 1 below). The coating was performed at 36 ° C. The coating layer was cooled at 5 ° C for 20 seconds and finally dried at 35% at 120% relative humidity (RH) conditions for 120 seconds.

The basic components of these coating compositions were water, dissolved gelatin and sodium carboxymethylcellulose (CMC) and dispersed polymer beads (PB), PB made according to Example 1 of US Pat. No. 4,614,708, In this case, the reaction conditions are as in Examples 1, 2, 3, 4,
3.3 for the beads used in 6, 8 and 10
It has an average particle size in the volume of μm and is 4.5 μ in Example 7.
It was applied to obtain polymethylmethacrylate beads grafted with co (styrene / maleic acid monosodium salt) chains having an average particle size in a volume of m. Example 5
And the beads of Examples 9 and 11 had an average particle size at a volume of 6.2 μm. The particle size was measured by COULTER (registered trademark) NANO-SIZER.

In Example 4, the coating composition was a polyvinylpyrrolidone [L having an average molecular weight of 630000.
UVISKOL K90 (trade name of BASF, Germany)] and was applied at a coverage of 1.30 g / m ² .

The gelatin used in each coating composition was 250
It had a gel strength of.

The sodium carboxymethyl cellulose (CMC) used has a DS in the range 6.5-8.5, its 2% aqueous solution being 25-40 mPa.s at 25 ° C. s
It had a viscosity of. Such a type of CMC is marketed by Wolf-Walsrode in Germany and has the trade name
Available on the market at WALOCEL CRT 30 PA / GA.

Further, each coating composition was 0.25 based on 1000 parts by volume of the total coating composition prepared for coating.
Part diisooctyl sulfosuccinate (wetting agent) and 0.17 part formaldehyde were included.

The coating compositions of Examples 1 to 8 in Table 1 are particularly suitable for use as ink receiving materials in ink jet printing and as toner receiving materials in electrophotographic printing and are pencil writable. It was used to make materials 1-8 of the present invention which represent a drafting film.

The coating compositions of Examples 9-12 of Table 1 were used to make comparative non-inventive Examples 9-12.

In Table 1, gelatin, CMC and defined polymer beads were coated in g / m ² .

Table 1 shows the data obtained in the ink absorption test (ABS test) as described below and the surface roughness (Ra value in μm) of the dry image receiving layer.

[0102]

[Table 1]

Ink Receptivity Test (ABS Test) The above coating compositions 1 to 1 before being used for ink jet printing.
The image-receiving element containing 12 was first conditioned at 30% relative humidity (RH) and 25 ° C. for at least 2 hours and then inkjet applied with a test image thereon. Ink is applied by Hewlett-Packard DeskJet 500C (trade name) operated with water-based colored inks cyan, magenta and yellow.
It was done with a multicolor printer.

Ink absorbency was evaluated as follows: An inkjet print was made on the image-receiving material in the form of some solid blocks (blocks) applied with colored inks (yellow, magenta and cyan) and black ink. However, there was a long time between consecutively numbered blocks of applied ink. Immediately after completion of printing, the inked side was placed in contact with normal paper for use in dry toner electrophotography. The sandwich thus obtained was passed through a nip between roller pairs at constant pressure. After peeling off the image receiving material, the optical density of the block on the paper substrate was changed to Macbeth TR-
1224 (trade name) was measured with an optical densitometer.

For each color, the number of blocks corresponding to a reflection density smaller than a certain comparison density was measured. The values for yellow, magenta, cyan and black are shown in Table 1, in which smaller values correspond to faster drying of the ink, thereby causing risk of ink offset and image smearing on the next stacked print sheet. Is less.

The smaller the value, the faster the ink absorption proceeds, and as a result, faster touch drying without image smearing is obtained.

The ink-receptive layers of the image-receptive materials according to the invention (Inventive Examples 1-8) were found to be ink-receptive for the comparative non-inventive Examples 9-12, especially with respect to ink-receptivity and fast-touch drying. It shows a much shorter drying time than the layers.

The electrophotographic laser printer HEWLETT PACKARD LaserJet III (trade name) is used to form a toner image on the ink receiving layers of the image receiving materials 1 to 12 using a commercially available thermoplastic resin toner containing carbon black. )
But I used it.

The adhesiveness of the toner after heat fixing was evaluated by the "tape test" conducted as follows.

Tape Test and Results Electrophotographically prepared dry toner layer representing discrete line patterns and solid areas of transferred and heat-fixed toner was used for transfer onto conditioned (22 ° C., The image receiving material was stored at 30% relative humidity for 2 hours. Transparent pressure-sensitive adhesive tape (SCOTCH BRAN available on the market from
D TAPE) was adhered. The tape was pressed with a fingernail on the toner imaged material for a few seconds and then rapidly peeled away in the direction of the image plane, ie, horizontally. A commercially available transparent toner receptor film material [TRANSPAREX T787 (Agfa-Belgium-Belgium), which measures the optical density of the toner transferred to the tape and has a "good" rating corresponding to the toner that is practically not peeled off. Gevaert NV, trade name)]. The image-receiving materials of Inventive Examples 1-8 had the same rating, while the image-receiving materials of Non-Inventive Examples 9, 11, and 12 had a "bad" rating.

Writability Test and Results In the writability test of the present invention, a crossing line was crossed using a commercial mechanical pencil containing a pencil lead MARS MICROGRAPH Super 15HB2 (trade name of Staedler, Germany) having a hardness of 2. I wrote a solid area with a certain number.

MACB for Inventive Materials 1-8, pencil uptake was measured by measuring optical density.
1.0 when measured with ETH TR-1224 (trade name) densitometer
Above, it was evaluated as good.

Pencil uptake by the non-invention materials 9, 11 and 12 was not able to reach an optical density of 1.0 and was rated as bad.

Offset Printing Tests and Results Aluminum offset printing plates made by the silver complex salt diffusion reversal (DTR) method as described in Example 1 of US Pat.
B. Mounted on a Dick 350 CD, in this case the plate was wet with a lithographic graphic formulation as described in the previous examples and with a fat printing ink as described in Example 1 of US Pat. No. 3,989,522. Used for offset printing. The fat printing ink is a London E
Leonard Hill [Books] Limited 19 in denstreet
Published in 1986, by EA Apps, Printing Ink Technol
The conventional offset printing ink described on page 348 of Ogy, a mixture of lead and cobalt naphthenate as an oxidation drying catalyst and the red azo pigment LAKE RED (C.I. 155).
85) and oxidatively dry styrenated flaxseed oil in aliphatic petroleum having a boiling range of 260-290 ° C.
Based on drilling oil alkyd resin.

Offset printing with the fatty ink did not cause ink smearing on continuously printed sheets of double-sided coated printing stock having the composition defined in Examples 1-8 of the invention, while ink smearing. The stain formed by was found on the back side of non-inventive examples 9, 11 and 12.

Example 13 A coating composition of an image receiving layer material according to Example 1 of the present invention was prepared by using a colloidal nanometer-sized Ag ₂ S. Physical development nuclei in the form of NiS particles were added at a coverage of 5 mg / m ² .

By the silver complex salt diffusion transfer inversion (DTR) method,
A black-and-white silver image was produced on the dried image-receiving layer for the purpose of identification.

On the imaged and dried image receiving layer, 7
A polyethylene terephthalate sheet having a thickness of 100 μm, precoated on one side with a 5 μm polyethylene sheet, was placed and laminated with the polyethylene in contact with the imaged image receiving layer. A hot roll laminator at a temperature of 110 ° C. was used to press the layers together.

The image contained in the laminate thus obtained was protected against forgery and the DTR image contained therein could not be peeled off without destruction.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location B41M 5/40 D21H 19/50 G03C 8/28 D21H 1/26 (72) Inventor Diyan Vertu Ruian Belgian-Mortzel, Septerrato 27, Agfa Gewert Nammrose, in Bennnotchup (72) Inventor Guido Dessi, Belgian-Mortzel, Septerrat, Belgium 27, Agfa-Gewert-Namurrose, Bennnotchup (72) Invention Person Danil Tammelmann, Mortzeer, Belgium, Septestrat 27 Agfa Gewert Nam Ros, in Bennotchup (72) Inventor, Loni de Clerc, Mortzeer, Belgium, Putesutora door 27 Agfa-Gevaert, Namuro Ze Ben notes in Chap

Claims (17)

[Claims] 1. An ink comprising a sheet-like or web-like support coated with an ink image-receiving layer containing gelatin as a binder, together with a partially protruding water-insoluble particulate organic material, called a matting agent. In the image receiving material, the layer contains (1) gelatin, (2) water-soluble alkali metal carboxymethyl cellulose and (3) organic polymer granular matting agent, and the components (1), (2) and (3) ) Represents at least 75% of the total weight of the layer, the coating amount of gelatin in the layer is in the range of 0.5 to 10 g / m ² , and the alkali metal carboxymethylcellulose expressed as a weight ratio to gelatin is It is present in the layer in the range of 1/20 to 5/1 and the granular polymer organic matting agent is 1
Having a mean particle size in the range of ˜15 μm, the matting agent consisting essentially of an organic polymer composition having a glass transition value (Tg) of at least 25 ° C., wherein the weight ratio of matting agent to gelatin is 1 An ink image receiving material having a range of / 5 to 15/1. 2. The ink image receiving material according to claim 1, wherein the average thickness of the ink image receiving layer having the partially protruding matting agent particles is in the range of 2 to 15 μm. 3. The coating amount of gelatin in the image receiving layer is in the range of 1.0 to 5.0 g / m ² , and the weight ratio of the alkali metal carboxymethyl cellulose to gelatin is 1.
3. The ink image receiving material according to claim 1, wherein the weight ratio of the matting agent to gelatin is in the range of 1/2 to 5/1. 4. The ink image receiving material according to claim 1, wherein said gelatin has a gel strength of at least 200 g. 5. The ink image receiving material according to claim 1, wherein the alkali metal carboxymethyl cellulose is sodium carboxymethyl cellulose having a degree of substitution in the range of 0.75 to 0.9. . 6. The ink image receiving material according to claim 1, wherein the organic matting agent particles have an average particle size of 3 to 10 μm. 7. The surface roughness of the image receiving layer is based on ANSI standard.
The ink image-receiving material according to any one of claims 1 to 6, wherein the Ra value measured by ASME B 46.1-1985 is in the range of 0.5 to 3.0 µm. 8. The ink image according to claim 1, wherein the particulate organic polymer matting agent material is in the form of polymer beads having a glass transition temperature of at least 25 ° C. Receptive material. 9. The beads are graft polymers that are made by addition polymerization of α, β-ethylenically unsaturated monomers and include different polymer cores and envelopes to form the envelopes. The ink image receiving material according to claim 8, wherein the polymer contains a hydrophilic group. 10. The beads are formed by the following steps: (A) in an aqueous solvent mixture of water and at least one water-miscible polar organic solvent; (1) its own simple substance present in the aqueous solvent mixture. At least 1 capable of forming a polymer that is soluble in the monomer but insoluble in the aqueous solvent mixture
A species of α, β-ethylenically unsaturated monomer, (2) a free radical-forming polymerization initiator that is soluble in an aqueous solvent mixture (eg potassium, sodium or ammonium persulfate), and (3) a hydrophilic group ( A sodium or potassium carboxylate or sulfonate group, a hydroxide group, an ethylene oxide group, or an amide group or a cyclic amide group), which is soluble in the aqueous solvent mixture and is soluble in the graft-polymerizable polymer, The weight ratio of the graft-polymerizable polymer to the monomer is 1.5: 100.
To 8: 100, and the weight ratio of the polymerization initiator to the monomer is 0.1: 100 to 5: 100, (B) the resulting solution is heated to a temperature from 50 ° C to its reflux temperature. At least 40 made by a process comprising initiating simultaneous agglomeration of homopolymers or copolymers and precipitation thereof from said monomers by heating and continuous stirring to form a small proportion of grafted polymer. The ink image receiving material of claim 8 in the form of micronized solid spherical polymer beads having a glass transition temperature of ° C and an average particle size of 1 to 15 µm. 11. A bead having a polymerized methylmethacrylate core with a polymer encapsulation of grafted co (styrene / maleic acid monosodium salt). Ink image-receiving material of paragraph. 12. The ink image receiving material according to claim 1, wherein the image receiving layer contains polyvinylpyrrolidone and / or polyvinyl alcohol. 13. The ink image receiving material according to claim 1, wherein the image receiving layer contains a surfactant that improves the wetting power of the ink image receiving layer with respect to an aqueous ink. . 14. The ink image receiving material according to claim 1, wherein the gelatin in the image receiving layer is hardened to a certain extent. 15. The image-receiving layer contains physical development nuclei, whereby a silver image can be formed in the layer by the silver complex salt diffusion transfer reversal (DTR) method.
14. The ink image receiving material according to any one of 14 above. 16. The ink image receiving material according to claim 15, wherein the image receiving layer contains a reducing agent. 17. The image-receiving layer after image formation therein forms part of a laminate, wherein said layer is fixed to the image-receiving layer by laminating using pressure and heat, and The ink image receiving material according to any one of claims 1 to 16, wherein the ink image receiving material is covered between resin supports.