JPH043066A - Transfer recording medium - Google Patents

Abstract

PURPOSE:To securely bind microcapsules to a base and to obtain bright images which have a high transfer density and less unequalness and staining by providing a photosensitive layer contg. a specific ratio of a binder and a layer contg. a polymer making interaction with the binder in the photosensitive layer between a base and the ptosensitive layer. CONSTITUTION:This recording medium has the photosensitive layer contg. the binder at 10 to 25wt.% of the weight of the contents of the photosensitive microcapsules on a base and the layer contg. the polymer making the interaction with the binder in the photosensitive layer between the base and the photosensitive layer. Namely, the binder is incorporated into the photosensitive layer to the extent of preventing the permeation of oxygen and of not hindering the transfer of the inclusions in the capsules in pressure transfer. The polymer with which the bright images having the high transfer density and the lessened unequalness and staining are obtainable and which makes the interaction with the binder is used in this way and, therefore, the binding property between the microcapsules and the base is enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a transfer recording medium that performs recording by transferring the contents of microcapsules onto a recording material using pressure.

"Prior Art" Transfer recording media using microcapsules (photosensitive microcapsules) containing photosensitive elements whose transfer characteristics change depending on the amount of exposure are disclosed in Japanese Patent Application Laid-open Nos. 58-88740 and 61-
It is described in each publication No. 275742 and No. 61-275742. The transfer recording medium described in JP-A No. 58-88740 has a photosensitive layer having microcapsules containing a photopolymerization initiator, a color image forming substance, and a polymerizable compound on a support. The transfer recording medium is imagewise exposed, the polymerizable compound is polymerized and hardened by this exposure, and then the uncured capsule is destroyed by bringing it into close contact with the image-receiving material and applying pressure, thereby transferring the color image-forming substance to the image-receiving material. It is used in a method of obtaining a transferred image on an image-receiving material.

On the other hand, JP-A-61-275742 and JP-A-61-27
The transfer recording medium described in Japanese Patent No. 8849 has a photosensitive layer having microcapsules containing a small amount of silver halide, a reducing agent, a color image forming substance, and a polymerizable compound on a support. After the transfer recording material (photosensitive material) is imagewise exposed to form a latent image, this is heat developed to polymerize a polymerizable compound in the area where the latent image was formed, and further the photosensitive material is It is used in a method in which the polymerizable compound is superimposed on an image-receiving material, and pressure is applied in this state to transfer the unpolymerized polymerizable compound to the image-receiving material, thereby obtaining a transferred image on the image-receiving material.

By the way, when including photosensitive microcapsules in the photosensitive layer in such a transfer recording medium, it is important to include a binder in the photosensitive layer in terms of binding between the photosensitive microcapsules and the support. preferable. A photosensitive material characterized in that a binder is included in the photosensitive layer is described in JP-A-1-216336. Furthermore, the photosensitive microcapsules can be firmly bound to the support by providing a layer containing a polymer between the photosensitive layer and the support. A transfer recording medium characterized in that a layer containing a polymer is contained between a layer containing exposed microcapsules and a support is disclosed in Japanese Patent Application Laid-Open No. 62-1768.
No. 93, No. 63-67178, No. 63-74047 and No. 63-8! There are descriptions in each publication of No. 077.

"Problems to be Solved by the Invention" In JP-A-1-216336, a binder known in the photographic technology is used. It has been found that when a binder is included in the photosensitive layer according to the description in this patent, the binding between the microcapsules and the support is improved, but the transfer density on the image-receiving material is significantly lowered. On the other hand, when using a transfer recording medium provided between a support and a photosensitive layer containing microcapsules in which the polymer-containing layer described above is exposed, the transfer density is high because the microcapsules are exposed, or It was found that the contents of the capsule did not harden sufficiently, possibly due to polymerization inhibition caused by oxygen, resulting in uneven and smeared images.

An object of the present invention is to provide a transfer recording medium in which photosensitive microcapsules are firmly bound to a support, and which provides a clear image with high transfer density and less unevenness and staining.

"Means for Solving the Problems" These problems are solved by a photosensitive layer containing a photosensitive microcapsule on a support and a binder in an amount of 10% to 25% by weight based on the contents of the capsule, a support and a photosensitive layer. The problem was solved by a transfer recording medium having a layer between the layers containing a polymer that interacts with the binder in the photosensitive layer.

"Effect of the Invention J According to research by the present inventor, the reduction in transfer density when using the transfer recording medium containing a binder in the photosensitive layer described above is due to a large amount of binder covering the surface of the microcapsules. It is presumed that this is because of this.

In other words, during pressure transfer, the oil-based liquid containing the color image-forming substance contained in the microcapsules becomes difficult to move through the binder, resulting in a significant decrease in the transfer rate, which appears as a decrease in transfer density. Seem.

On the other hand, if the binder in the photosensitive layer is reduced, the transfer density will increase, but the binding between the microcapsules and the support will deteriorate.
The microcapsules peel off from the support, resulting in uneven images and stains.

Furthermore, when using a transfer recording medium in which a layer containing the above-mentioned polymer is provided between the photosensitive layer and the support, unevenness and stains can be avoided.
This is thought to be due to inhibition of polymerization by oxygen in the air.

That is, in the polymerization process during light irradiation or development,
Since the binder does not cover the microcapsules at all, oxygen in the air penetrates into the microcapsules, inhibiting polymerization, and the contents of the capsules are not sufficiently cured, which appears as unevenness and stains.

In the present invention, the transfer recording medium includes a relatively small amount of binder in a photosensitive layer containing photosensitive microcapsules, and a layer containing a polymer is provided between the photosensitive layer and the support. Here, the photosensitive layer contains a binder to the extent that it prevents the penetration of oxygen and does not inhibit the transfer of the capsule contents in pressure transfer. This makes it possible to obtain clear images with high transfer density and less unevenness and stains.

Furthermore, since a polymer that interacts with the binder in the photosensitive layer containing microcapsules is used between the photosensitive layer and the support, the binding between the microcapsules and the support is good, and the capsules themselves are supported during transfer. It rarely comes off from the body. The interaction between the binder and the polymer includes electrostatic interaction, dipole-dipole interaction, hydrophobic interaction, etc., and in the present invention, any interaction may be used.

The binder used in the photosensitive layer of the present invention or the polymer contained in the layer provided between the photosensitive layer and the support is not particularly limited, and polymers known in the photographic technology and the like can be used.

The molecular weight of this polymer is generally 1000 to 10
Approximately 1,000,000 is preferable. In addition, the molecular weight is 10,000 to 500
More preferably, it is in the range of 10,000.

The amount of the binder used in the photosensitive layer is preferably about 10% to 25% by weight based on the contents of the capsule.

Further, the amount of polymer contained in the layer provided between the photosensitive layer and the support is preferably about 0.01 g/ba to 20 g/d, and preferably about 0.1 g/rrr to 10 g/r&. More preferred.

Preferred examples of the polymer contained as a binder in the photosensitive layer of the transfer recording medium of the present invention or in a layer provided between the photosensitive layer and the support include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, and polyvinyl pyrrolidone. Nonionic polymers such as acryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-coacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, and methylcellulose, amphoteric polymers such as ceratin, or polystyrene sulfinate, styrene fluoride, etc. Copolymers of phinate salts, polystyrene sulfonates, styrene sulfonic acid copolymers, polyvinyl sulfate ester salts, polyvinyl sulfonates, maleic anhydride/styrene copolymers, maleic anhydride/isobutylene copolymers, etc. Anionic polymers, polyethyleneimine, aminoacrylic acrylate-modified polyvinyl alcohol, polyvinylpyridine hydrochloride, cationically modified polyacrylamide, water-soluble aniline resin hydrochloride, polythiourea hydrochloride, water-soluble cationized amine resin, etc. Mention may be made of cationic polymers.

In the present invention, it is necessary for the binder in the photosensitive layer containing microcapsules to interact with the polymer contained in the layer between the photosensitive layer and the support.

For example, if an ionic binder is included in the photosensitive layer containing microcapsules, a polymer with an opposite charge to the binder may be included in the layer between the photosensitive layer and the support to prevent static electricity. Because of this interaction, it is possible to improve the binding between the microcapsules and the support.

Furthermore, the cohesiveness of microcapsules can also be improved by utilizing dipole-dipole interaction. An example of utilizing dipole-dipole interaction is a combination of anionic polymers such as polyvinylpyrrolidone and polystyrene sulfonate.

The binder in the photosensitive layer may be added during the process of producing photosensitive microcapsules, or may be added during the process of first coating a polymer on a support and arranging microcapsules thereon. .

"Detailed Description of the Invention" Below, the photopolymerization initiator, silver halide, reducing agent, color image forming substance, polymerizable compound, base precursor, microcapsule, support and The image receiving material will be explained in detail.

This transfer recording medium includes a first embodiment having microcapsules containing at least a photopolymerization initiator, a color image forming substance, and a polymerizable compound on a support, and a microcapsule containing at least /% A second embodiment is included having microcapsules containing silver halogenide, a reducing agent, a color image-forming material, and a polymerizable compound. Note that the transfer recording medium having the above structure will be simply referred to as a "photosensitive material" hereinafter.

First, the main components of the photosensitive material of the first embodiment, such as a photopolymerization initiator, a color image-forming material, a polymerizable compound, a microcapsule, a support, and an image-receiving material, will be explained.

Examples of preferred photopolymerization initiators include α-alkoxyphenyl ketones, polycyclic quinones, benzophenones and substituted benzophenones, xanthones, thioxanthones, 710-genated compounds (e.g., chlorosulfonyl, chloromethyl, etc.). aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, and fluorenones), haloalkanes, α-halo α-phenylacetophenones, photoreducible dyes - reducing redox couples, halogenated paraffins (e.g. brominated or chlorinated paraffins), benzoyl alkyl ethers,
and lophine dimer-mercapto compound couples, and organic boron compound anion salts of organic cationic compounds described in JP-A-62-143044.

Specific examples of preferred photoinitiators include benzoylbutyl, 2,2-dimethoxy-2-phenylacetophenone, 9,10-anthraquinone, benzophenone, Michler's ketone, 4,4'-diethylaminobenzophenone, xanthone, chloroxanthone, thioxanthone,
Chlorothioxanthone, 2,4-diethylthioxanthone, chlorosulfonylthioxanthone, chlorosulfonylanthraquinone, chloromethylanthracene, chloromethylbenzothiazole, chlorosulfonylbenzoxazole, chloromethylquinoline, chloromethylbenzophenone, chlorosulfonylbenzophenone, fluorenone, tetrabromide Carbon, benzoin butyl ether, benzoin isopropyl ether, 2,2'-bis(θ-chlorophenyl)-4,4', 5. 5'-tetraphenylbiimidazole and 2-mercapto-5-methylthio-
Examples include combinations of 1°3.4-thiadiazole.

As the photopolymerization initiator, the above-mentioned compounds may be used alone, or several types may be used in combination.

In the photosensitive material of the present invention, the photopolymerization initiator is preferably used in an amount of 0.5 to 30% by weight based on the polymerizable compound used. A more preferable usage range is
2 to 20% by weight.

There are no particular restrictions on the color image-forming substance that can be used in the photosensitive material, and various types can be used. In other words, substances that themselves are colored (dyes and pigments), and substances that are colorless or light in color but are affected by external energy (heating, pressure, light irradiation, etc.) or other components (color developers). Substances that develop color upon contact (color formers) are also included in color image forming substances.

Incidentally, general photosensitive materials using color image-forming substances are described in the above-mentioned Japanese Patent Laid-Open No. 73145/1983. Regarding photosensitive materials using dyes or pigments as color image forming substances, see Japanese Patent Application Laid-Open No. 187346/1987, Japanese Patent Application No. 1-205879, and Japanese Patent Application No. 1-205880 regarding photosensitive materials using leuco dyes. is published in Japanese Patent Application Publication No. 1986-
209436, JP-A-62-251741 for photosensitive materials using triazene compounds, and JP-A-62-288827 and JP-A-62-288828 for photosensitive materials using yellow coloring leuco dyes.
JP-A No. 63-53542 describes photosensitive materials using cyan color-forming leuco dyes. Dyes and pigments, which are substances that color themselves, are available commercially as well as in various literature (for example, "Dye Handbook" edited by the Organic Synthetic Chemistry Association, published in 1970; "Latest Pigment Handbook" edited by the Japan Pigment Technology Association; The publicly known one described in ``Published in 1972'' can be used. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, examples of substances that develop color due to some kind of energy such as heating, pressure, or light irradiation include thermochromic compounds,
Piezochromic compounds, photochromic compounds, and leuco compounds such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes are known. All of these develop color upon heating, pressurization, light irradiation, or air oxidation.

Examples of substances that develop color upon contact with another component include various systems that develop color due to acid-base reactions, redox reactions, coupling reactions, chelate formation reactions, etc. between two or more components.

For example, Hiroyuki Moriga's ``Introductory Chemistry of Special Papers''
Known coloring systems such as pressure-sensitive copying paper (pages 29-58), azography (pages 87-95), thermal coloring by chemical change (pages 118-120), or Kinki Kagaku Use the coloring system etc. described in the proceedings of the seminar sponsored by the industry association, "Latest Pigment Chemistry - Attractive Utilization and Confidentiality as Functional Pigments", pages 26-32 (June 19, 1980). I can do it. Specifically, the coloring system consists of coloring agents with partial structures such as lactones, lactams, and spiropyrans used in pressure-sensitive paper, and acidic substances (coloring agents) such as acid clay and phenols; aromatic diazonium salts and Systems that utilize azo coupling reactions between diazotate, diazosulfonates, naphthols, anilines, active methylenes, etc.; reactions between hexamethylenetetramine and ferric ions and gallic acid; and reactions between phenolphthalein and combreculanes. Chelate-forming reactions such as reactions with alkaline earth metal ions, redox reactions such as reactions between ferric nistearate and pyrogallol, and reactions between silver behenate and 4-methoxy-1-naphthol can be used.

The color image forming substance is used in an amount of 0.00 parts by weight per 200 parts by weight of the polymerizable compound. It is preferably used in a proportion of 5 to 60 parts by weight. In addition, when a color developer is used, approximately 0.0% is used per 1 part by weight of the color developer. It is preferably used in a proportion of 3 to 80 parts by weight.

In addition, when using two types of substances that cause a color-forming reaction when in contact as the solid color image-forming substances described above, one of the substances that cause the above-mentioned color-forming reaction and a polymerizable compound are contained in microcapsules. However, a color image can be formed on the photosensitive layer by allowing other substances among the substances that cause the color-forming reaction to exist outside the microcapsules containing the polymerizable compound. Regarding photosensitive materials that can obtain color images without using an image-receiving material as mentioned above,
There is a description in JP-A-62-209444.

Polymerizable compounds used in photosensitive materials generally have addition polymerizability or ring-opening polymerizability. Examples of the compound having addition polymerizability include compounds having an ethylenically unsaturated group, and compounds having ring-opening polymerizability include compounds having an epoxy group, and compounds having an ethylenically unsaturated group are particularly preferred.

Compounds with ethylenically unsaturated groups that can be used in photosensitive materials include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, and maleic anhydride. Examples include acids, maleic esters, itaconic esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof.

Specific examples of polymerizable compounds that can be used in photosensitive materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxy acrylate. Ethyl acrylate, tricyclodecanyloxyacrylate, nonylphenyloxyethyl acrylate, 1,3-dioxolane acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, tricyclodecane dimethylol diacrylate, trimethylolpropane triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylated bisphenol A diacrylate, 2-(2-hydroxy-
1,1-dimethylethyl)-5-hydroxymethyl-5
-ethyl-1,3-dioxane diacrylate, 2~(
2-hydroxy-1,l-dimethylethyl)-5,5-
Examples include dihydroxymethyl-1,3-dioxane triacrylate, triacrylate of a propylene oxide adduct of trimethylolpropane, polyacrylate of hydroxypolyether, polyester acrylate, and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, Methacrylate and dimethacrylate of polyoxyalkylenated bisphenol A can be mentioned.

The above polymerizable compounds may be used alone or in combination of two or more. A photosensitive material using a combination of two or more types of polymerizable compounds is described in JP-A-62-210445. In addition, a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the above-mentioned reducing agent can also be used as a polymerizable compound.

Next, the sensitizer, which is an optional component that can be used in the photographic material of the first embodiment, will be explained.

Preferred sensitizers are those that increase sensitivity when used in combination with the photopolymerization initiator or photopolymerization initiation system described above, and examples thereof include compounds having active hydrogen in the molecule. Specific examples include N-phenylglycine, trimethylbarbital acid, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and the following general formula (di):
Or, a compound represented by (II) can be mentioned.

In the formula, R1 represents an alkyl group, an alkylthio group or a mercapto group.

In the formula, R2 represents a hydrogen atom or an alkyl group, and R1
represents an alkyl group or an aryl group.

In the image forming method of the present invention, the sensitizer is preferably used in an amount of 0.5 to 100% by weight based on the polymerizable compound used. A more preferred range is 2 to 80% by weight.

Various known techniques can be applied to the microcapsules of the present invention without particular limitations.

Examples include U.S. Pat.
No. 800458. Method using coacervation of most hydrophilic wall-forming material; US Pat. No. 32871
54 and British Patent No. 990443, and the interfacial polymerization method described in Japanese Patent Publication Nos. 38-19574, 42-446, and 42-771; specifications of U.S. Patent Nos. 3418250 and 3660304. Method by precipitation of most polymers; U.S. Pat. No. 3,796
669; Methods using isocyanate wall materials described in U.S. Pat. No. 3,914,511; U.S. Pat.
No. 001140, No. 4087376, No. 4089
No. 802 and No. 4025455, JP-A-62-2
No. 09439, JP-A-64-91131, JP-A-1-
There is a method using amino aldehyde resins described in No. 154140 and Japanese Patent Application No. 63-241635.

Examples of amino aldehyde resins include urea formaldehyde resin, urea-formaldehyde resorcin resin,
Melamine-formaldehyde resin, acetoguanamine-
Examples include formaldehyde resin, benzoguanamine-formaldehyde resin, and the like.

Also, Japanese Patent Publication No. 36-9168 and Japanese Patent Publication No. 51-90
In 5it by polymerization of monomers described in each revolution in No. 79
U method; British Patent No. 927807 and British Patent No. 96507
Polymerization dispersion cooling method described in each specification of No. 4; US Patent No. 311
1407 and the spray drying method described in British Patent No. 930422. Although the method for microcapsulating oil droplets of a polymerizable compound is not limited to the above, a preferred method is to emulsify a core substance and then form a polymer film as a microcapsule wall. Regarding photosensitive materials using microcapsules with outer shells made of polyamide resin and/or polyester resin, Japanese Patent Application Laid-Open No. 62-209437 describes microcapsules with outer shells made of polyurea resin and/or polyurethane resin. Regarding the photosensitive material used, see JP-A No. 62-209438, and about the photosensitive material using microcapsules having an outer shell made of gelatin, see JP-A No. 62-209440. Regarding a photosensitive material using microcapsules having a composite resin outer shell containing polyamide resin and polyurea resin, see JP-A-62-209447. In JP-A-62-2, a photosensitive material using microcapsules having a composite resin outer shell containing polyurethane resin and polyester resin is disclosed.
Each of these is described in the 09442 publication.

In the present invention, it is particularly preferable to use a melamine formaldehyde resin, since it is possible to obtain highly dense capsules.

In addition, Japanese Patent Application No. 1-37782 discloses that in order to obtain capsules with particularly excellent wall density, a reaction product of a water-soluble polymer having a sulfinic acid group and a polymerizable compound having an ethylenically unsaturated group is used. A microcapsule is disclosed in which a polymer wall of a high molecular compound is provided around a membrane.
It is preferably used in the present invention.

In addition, when using aminoaldehyde-based microcapsules, it is preferable to keep the amount of residual aldehyde below a certain value, as in the photosensitive material described in JP-A-63-32535.

The average particle diameter of the microcapsules is preferably 3 to 20 μm. It is preferable that the particle size distribution of the microcapsules is uniformly distributed over a certain value, as in the photosensitive material described in JP-A No. 63-5334. In addition, the film thickness of the microcapsule is
As in the photosensitive material described in Publication No. 6, it is preferable that the particle diameter is within a certain range.

Although there are no particular restrictions on the support for the photosensitive material of the present invention,
It is preferable to use a material that can withstand the processing temperature during development.

Materials that can be used for the support include glass, paper, high quality paper, baryta paper, coated paper, cast coated paper,
Synthetic paper, metals and their analogs, polyester, polyethylene, polypropylene, cellulose acetate, cellulose ester, polyvinyl acetal, polystyrene,
Examples include films such as polycarbonate, polyethylene terephthalate, and polyimide, and papers laminated with resin materials and polymers such as polyethylene.

In addition, when using a porous support such as paper, Japanese Patent Application Laid-Open No. 62
-209529, 63-38934, 63-8
No. 1339, No. 63-81340, No. 63-9794
Supports described in publications such as No. 1, No. 64-88543, and No. 64-88544 can be used.

The image receiving material will be explained below.

The image-receiving material may be a support only, or an image-receiving layer may be provided on the support.

Supports for image-receiving materials are not particularly limited, but like the supports for photosensitive materials, glass, paper, high-quality paper, baryta paper, coated paper, cast-coated paper, synthetic paper, metals and their analogues, and polyester can be used. , polyethylene, polypropylene, acetylcellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate,
Examples include films such as polyethylene terephthalate, and papers laminated with resin materials and polymers such as polyethylene.

Note that when a porous material such as paper is used as the support for the image-receiving material, it is preferable that the support has a certain level of smoothness as in the image-receiving material described in JP-A-62-209530. Further, an image receiving material using a transparent support is described in JP-A-62-209531.

The image-receiving layer of the image-receiving material is composed of a white pigment, a binder, and other additives, and the white pigment itself or the voids between the particles of the white pigment increase the receptivity of the polymerizable compound.

Examples of white pigments used in the image-receiving layer include inorganic white pigments such as oxides such as silicon oxide, titanium oxide, zinc oxide, magnesium oxide, and aluminum oxide, magnesium sulfate, barium sulfate, calcium sulfate, magnesium carbonate, and barium carbonate. , alkaline earth metal salts such as calcium carbonate, calcium silicate, magnesium hydroxide, magnesium phosphate, magnesium hydrogen phosphate, etc., as well as aluminum silicate, aluminum hydroxide, zinc sulfide, various clays, talc, kaolin, zeolite, Examples include acid clay, activated clay, and glass.

As organic white pigments, polyethylene, polystyrene,
Examples include benzoguanamine resin, urea-formalin resin, melamine-formalin resin, and polyamide resin.

These white pigments may be used alone or in combination, but those with high oil absorption for polymerizable compounds are preferred.

Further, as the binder used in the image-receiving layer of the present invention, water-soluble polymers, polymer latexes, polymers soluble in organic solvents, and the like can be used. As a water-soluble polymer,
For example, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose, proteins such as gelatin, phthalated gelatin, casein, and ovalbumin, starches such as dextrin and etherified starch, polyvinyl alcohol, polyvinyl alcohol partial acetal, and poly-N- vinylpyrrolidone,
Polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole,
Examples include synthetic polymers such as polystyrene sulfonic acid, locust bean gum, pullulan, gum arabic, and sodium alginate.

Examples of the polymer latex include styrene-butadiene copolymer latex, methyl methacrylate-butadiene copolymer latex, acrylic ester and/or methacrylic ester polymer or copolymer latex, and ethylene/vinyl acetate copolymer latex. etc.

Examples of polymers soluble in organic solvents include polyester resins, polyurethane resins, polyvinyl chloride resins, polyacrylonitrile resins, and the like.

As for how to use the above-mentioned binders, two or more types can be used in combination, and furthermore, the two types of binders can also be used in combination in such a ratio that phase separation occurs. An example of such usage is described in Japanese Patent Application Laid-open No. 1-154789.

The average particle size of the white pigment is 0. 1 to 20μ, preferably 0.1 to 10μ, and the coating amount is 0.1g to 60μ
g, preferably in the range of 0.5 g to 30 g. The weight ratio of the white pigment to the binder is preferably in the range of 0.01 to 0.4, and preferably 0.03 to 0.3.
The range of is more preferable.

In addition to the binder and the white pigment, the image-receiving layer can contain various additives as described below.

For example, when using a coloring system consisting of a color former and a color developer, the image receiving layer can contain the color developer. Typical color developers include phenols, organic acids or their salts, or esters, but when a leuco dye is used as a color image forming substance, zinc salts of salicylic acid derivatives are preferred; Among them, 3,5-di-α-
Zinc methylbenzylsalicylate is preferred.

The color developer is preferably contained in the image-receiving layer in a coating amount in the range of 0.1 to 50 g/m.

More preferably, it is in the range of 0.5 to 20 g/d.

Below, the silver halide, reducing agent, and base precursor used in the photosensitive material of the second aspect of the present invention will be explained in detail.

In the photosensitive material of the second embodiment, the color image forming substances, polymerizable compounds, microcapsules, supports, and image-receiving materials described in the photosensitive material of the first embodiment can be used in the same manner.

The light-sensitive material of the present invention includes silver chloride, silver chloride,
Any grains of silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and dodecahedrons, those with irregular crystal systems such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.01 micron or less, or large grains with a projected area diameter of up to about 10 microns, and may be used in polydisperse emulsions or in U.S. Pat.
Monodisperse emulsions such as those described in British Patent No. 574,628, British Patent No. 3.6.55,394 and British Patent No. 1,413.748 may also be used.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
enee and Engjneering), 14th
Volume 248-257 (1910); U.S. Patent No. 4,4
34゜226, 4,414,310, 4,43
3.048, 4,439.520, and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. Furthermore, two or more types of silver halide grains having different halogen compositions, crystal habits, grain sizes, etc. can also be used together.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Nα17643
(December 1978), pp. 22-23, 4■, Emulsion preparation and
types)”.

and Nα19716 (November 1979), 64
It can be prepared using the method described on page 8, etc.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and Nα18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive type RD17643 RD18716
Chemical sensitizers Page 23 Page 648 Right column Sensitivity increasing agents Same as above The silver halide grains mentioned above include JP-A No. 63-6
It is preferable to use silver halide grains having a relatively low fog value, such as the light-sensitive material described in Japanese Patent No. 8830.

In order to uniformly contain silver halide in the microcapsules, it is preferable to dissolve a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit in the polymerizable compound.For details, see Japanese Unexamined Patent Publication 1986-20
There are descriptions in Japanese Patent Application No. 9450, No. 63-287844, and Japanese Patent Application No. 1-37782.

The amount of silver halide contained in the photosensitive layer ranges from 0.1 to Lo in terms of silver, including organic silver salt, which is an optional component described below.
It is preferable to set it in the range of g/rrr. Also, when converting silver halide only to silver, it is 1g/rr? It is preferable to set it to the following, and it is especially preferable to set it to the range of 1 to 500 .

In addition, when storing silver halide in microcapsules, the average particle size of the silver halide grains mentioned above is preferably one-fifth or less, and preferably one-tenth or less, of the average size of the microcapsules. is even more preferable. By setting the average grain size of the silver halide grains to one-fifth or less of the average size of the microcapsules, a uniform and smooth image can be obtained.

When silver halide is contained in microcapsules, it is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsules. Regarding photosensitive materials containing silver halide in the wall material of microcapsules, JP-A-62
There is a description in the publication No.-169147.

The reducing agent that can be used in the light-sensitive material of the present invention has a function of reducing silver halide and/or a function of promoting (or suppressing) polymerization of a polymerizable compound. There are various types of reducing agents that have the above functions. The reducing agents include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-
Amino-5-pyrazolones, 5-aminouracils, 4
゜5-dihydroxy-6-aminopyrimidines, reductones, amyl reductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamidonaphthols, 2,4-disulfonamidophenols,
2.4-Disulfonamide naphthols, 0- or p
-Acylaminophenols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3
-Sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, hydrazines, and the like. By adjusting the type, amount, etc. of the reducing agent, it is possible to polymerize the polymerizable compound in either the area where the silver halide latent image is formed or the area where no latent image is formed. In addition, in a system in which a polymerizable compound is polymerized in a portion where a silver halide latent image is not formed, l-phenyl-3-pyrazolidones, hydroquinones, and sulfonamidophenols are particularly preferred as reducing agents.

Regarding various reducing agents having the above functions, please refer to JP-A-61-183640, JP-A No. 61-188535, and JP-A-61-188535.
Publications No. 1-228441 and JP-A-62-7
No. 0836, No. 62-86354, No. 62-8635
No. 5, No. 62-206540, No. 62-2640.4
No. 1, No. 62-109437, No. 63-254442
No., Japanese Patent Application Publication No. 1-267536, Patent Application No. 1983-2967
No. 74, No. 63-296775, Patent Application No. 1-2717
No. 5, No. 1-54101, No. 1-91.162, No. 1-90087, and other publications and specifications. The above reducing agents (including those described as developing agents or hydrazine conductors) are also described in "The Theory of the Photo" by T. James.
ra-phic Process'' 4th edition, 291-3
34 pages (1977) Research Disclosure Magazine Vol.

170. No. 17029 of June 1978 (9-15
page), and the same magazine Vol. l 76. 1978 12
There is also a description in Monthly No. 17643 (pages 22-31).

Furthermore, as in the photosensitive material described in JP-A No. 62-210446, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. good. The reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literature can also be effectively used in the photosensitive material used in this specification. Therefore, "reducing agent J" in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literature.

Among these reducing agents, those having basicity that form salts with acids can also be used in the form of salts with appropriate acids.

These reducing agents may be used alone, but as described in each of the above specifications, two or more types of reducing agents may be used in combination. When two or more types of reducing agents are used together, the interaction of the reducing agents is, first, to promote the reduction of silver halide (and/or organic silver salt) through so-called superadditivity; , silver halide (
The oxidized form of the first reducing agent produced by the reduction of the first reducing agent (and/or organic silver salt) causes the polymerization of the polymerizable compound (or suppresses the polymerization) through a redox reaction with other reducing agents coexisting. ), etc. are possible. However, in actual use, the reactions described above can occur simultaneously, so it is difficult to specify which effect is occurring.

Specific examples of the above reducing agent are shown below.

H NHCOC+s H33 OCl-H33 H OC,,H33 H c<no(t) CH3 C2H.

The amount of reducing agent added can vary widely, but is generally 0.1 to 1500 mol% based on the silver salt, preferably IO
to 31) 0 mol%.

The base precursors that can be used in the photosensitive material of the present invention include base precursors of inorganic bases and organic bases (
(decarboxylation type, thermal decomposition type, reaction type, complex salt forming type, etc.) can be used.

Preferred base precursors include JP-A-59-18
No. 0549, No. 59-180537, No. 59-195
No. 237, No. 61-32844, No. 61-36743
No. 61-5], No. 140, No. 61-52638,
No. 61-52639, No. 61-53631, No. 61
No. 53634, No. 61-53635, No. 61-536
No. 36, No. 61-53637, No. 61-53638, No. 61-53639, No. 61-53640, No. 6
No. 1-55644, No. 61-55645, No. 61-5
No. 5646, No. 61-84640, No. 61-1072
No. 40, No. 61-219950, No. 61-25184
No. 0, No. 61-252544, No. 61-313431
No. 63-316740, No. 64-68746, and JP-A No. 1-54452.
No. 9-157637, No. 59-166943, No. 63
-96159, a compound that eliminates a base by heating is mentioned.

The base precursor of the present invention is 50°C to 20°C.
It is preferable to release the base at 0°C, and between 80°C and 18°C.
It is more preferable to release at 0°C.

Further, a method of releasing a base using a reaction is described in Japanese Patent Application Laid-open No. 25208/1982 and Japanese Patent Application No. 3282/1999. Furthermore, a method of generating a base by electrolysis is described in JP-A-61-232451.

The base precursor used in the photosensitive material of the present invention is preferably a base precursor consisting of a salt of a carboxylic acid and an organic base as shown below and having a solubility in water at 25° C. of 1% or less.

(a) A base precursor is a salt of a carboxylic acid and an organic base, and the organic base has a partial structure corresponding to an atomic group obtained by removing one or two hydrogen atoms from an amidine represented by the following formula (1). It is a diacid to tetradisperse base consisting of from four to four linking groups of the partial structure.

[In the above formula (1), the second unit, R+2, R-th and R11 each consist of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic residue. represents a monovalent group selected from the group (each group may have one or more substituents), and any two groups selected from Rl, Rl 2, R+ 1 and R. may combine with each other to form a three- or six-membered nitrogen-containing heterocycle.] (bl) The base precursor consists of a salt of a carboxylic acid and an organic base, and the organic base is represented by the following formula (2). It is a diacid to tetradisperse base consisting of two to four partial structures corresponding to an atomic group obtained by removing one or two hydrogen atoms from guanidine, and a linking group of the partial structures.

Specific examples of these base precursors are shown below, but the invention is not limited thereto.

[In the above formula (2), R21, R22, R21, R
2+ and R'' are each a hydrogen atom, an alkyl group,
represents a monovalent group selected from the group consisting of an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic residue (each group may have one or more substituents), And R”, R22, R+1,
Any two groups selected from R" and R25 may be bonded to each other to form a three- or six-membered nitrogen-containing heterocycle. For the base precursors (a) and fb) above, , respectively, JP-A No. 63-31670,
It is described in detail in Japanese Patent No. 64-68746.

CH.

CH.

CH.

CH2 Oo) H H When the base precursor is accommodated in microcapsules in the present invention, a photosensitive composition in which the base precursor is directly solid-dispersed in a polymerizable compound may be used (as disclosed in JP-A No. 64-32251, It is particularly preferable to use a photosensitive composition in which a base precursor is dispersed in water and emulsified in a polymerizable compound. (Japanese Unexamined Patent Publication No. 63-218964, Japanese Patent Application No. 1-160148) Here, when dispersing the base precursor in water, it is preferable to use a nonionic or amphoteric water-soluble polymer.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroquinethyl methacrylate-coacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, and Examples include methylcellulose.

Moreover, gelatin can be mentioned as an amphoteric water-soluble polymer.

The above water-soluble polymer has 0
．． It is preferably contained in a proportion of 1 to 100% by weight, and more preferably contained in a proportion of 1 to 50% by weight. In addition, the base precursor is 5% for the dispersion.
It is preferable that the content is 60% by weight, and 10 to 50% by weight.
More preferably, it is contained in a weight percent. In addition, the base precursor is 2 to 50% by weight based on the polymerizable compound.
It is preferably contained in a proportion of 5 to 30% by weight.
It is more preferable that the content be in a proportion of .

In the production of the photosensitive microcapsules of the present invention, when an oily liquid containing a base precursor and a color image-forming substance is dispersed in an aqueous medium to form the outer shell of the capsule, a nonionic water-soluble It is preferable that the polymer contains a polymer with a high molecular weight. In this case, the oily liquid is preferably 10 to 120% by weight, more preferably 20 to 90% by weight, based on the aqueous medium.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polymethyl vinyl ether, polyacryloylmorpholine, polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate-coacrylamide, hydroxyethylcellulose, hydroxypropylcellulose, and methylcellulose. etc. can be mentioned.

In addition, in order to efficiently disperse a hydrophobic core substance containing an oily liquid into microdroplets in an aqueous medium, it is necessary to use an anionic water-soluble polymer in combination with the above-mentioned nonionic water-soluble polymer. preferable.

In this case, the concentration of the anionic water-soluble polymer in the aqueous medium is preferably in the range of 0.01 to 5% by weight, more preferably 0.01 to 5% by weight. It is in the range of 1 to 2% by weight.

Examples of anionic water-soluble polymers include polystyrene sulfinic acid, styrene sulfinate copolymers,
Examples include polystyrene sulfonate, styrene sulfonic acid copolymer, polyvinyl sulfate ester salt, polyvinyl sulfonate, maleic anhydride/styrene copolymer, maleic anhydride/imbutylene copolymer, and the like.

In the above case, it is particularly preferable to use a nonionic water-soluble polymer and a water-soluble polymer having a small amount of sulfinic acid groups together.

The pigment and polymerizable compound that can be used in the photosensitive material of the second embodiment are the same as those of the first embodiment described above. In the photographic material of the second embodiment, the polymerizable compound is preferably used in an amount of 5 to 120,000 parts by weight, more preferably 120,000 parts by weight, based on 1 part by weight of silver halide.
to 12,000 parts by weight. The pigment is preferably used in an amount of 5 to 120 parts by weight, more preferably 10 to 60 parts by weight, based on 100 parts by weight of the polymerizable compound.

Next, components that can be optionally used in the photosensitive material of the second embodiment, such as an organic silver salt, a radical generator, a thermal solvent,
A compound having an oxygen removing function, a thermal polymerization initiator, and a photopolymerization initiator will be explained in order.

In the present invention, an organic metal salt can be used as an oxidizing agent together with photosensitive silver halide.

Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the organic silver salt oxidizing agent described above include U.S. Pat.
These are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Furthermore, silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235, and JP-A-61-24904
Acetylene silver described in the publications No. 4 and No. 64-57256 is also useful. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
It can be used in combination with silver halide in an amount ranging from 0.01 to 10 mol, preferably from 0.01 to 1 mol.

A radical generator that participates in the above-mentioned polymerization acceleration (or polymerization inhibition) reaction of the reducing agent may be added to the photosensitive layer.

A photosensitive material using silver triazene as the radical generator is described in JP-A-62-195639, and a photo-sensitive material using silver diazotate is described in JP-A-62-1956.
No. 195640 describes a photosensitive material using an azo compound, and JP-A-62-195641 describes a photosensitive material using an azo compound.

Useful examples of the thermal solvent include compounds that can serve as solvents for reducing agents, and compounds with high dielectric constants that are known to accelerate the physical development of silver salts. Useful thermal solvents include:
Polyethylene glycols described in U.S. Patent No. 3,347,675, derivatives such as oleic acid esters of polyethylene oxide, beeswax, monostearin, -5O
Compounds with high dielectric constant having 2- and/or -C〇- groups, polar substances described in U.S. Pat. No. 3,667,959, 1,10-decane described in Research Disclosure magazine, December 1976 issue, pages 26-28 Diol, methyl anisate, diphenyl perate, etc. are preferably used. Incidentally, a photosensitive material using a heat solvent is described in JP-A-62-86355.

A compound having an oxygen removing function can be used for the purpose of eliminating the influence of oxygen (oxygen has a polymerization inhibiting effect) during development. Examples of compounds having an oxygen removing function include compounds having two or more mercapto groups. Incidentally, a photosensitive material using a compound having two or more mercapto groups is described in JP-A-622'09443.

Further, development may be performed by applying a liquid having an oxygen blocking effect to the photosensitive layer of the outer shell of the microcapsule. A specific example of the liquid is water.

Thermal polymerization initiators that can be used in photosensitive materials are generally compounds that are thermally decomposed under heating to generate polymerization initiating species (particularly radicals), and are commonly used as radical polymerization initiators. Thermal polymerization initiators are described in pages 6 to 18 of "Addition Polymerization/Ring-Opening Polymerization J, 1983, Kyoritsu Shuppan," edited by the Editorial Committee of Polymer Experiments, The Polymer Society of Japan.Initiation of thermal polymerization Specific examples of the agent include azobisisobutyronitrile, 1,1'-azobis(1-cyclohexanecarbonitrile), dimethyl-2°2'-
Azo compounds such as azobisisobutyrate, 2.2-azobis(2-methylbutyronitrile), azobisdimethylvaleronitrile, benzyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl Examples include organic peroxides such as hydroperoxide and cumene hydroperoxide, inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, and sodium p-toluenesulfinate. The thermal polymerization initiator is preferably used in an amount of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound. In addition, in a system in which a polymerizable compound is polymerized in a portion where a silver halide latent image is not formed, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Furthermore, a photosensitive material using a thermal polymerization initiator is described in JP-A-62-70836.

In the photosensitive layer of the photosensitive material, similar to the above-mentioned thermal polymerization initiator,
In addition to being used as a system for polymerizing a polymerizable compound in areas where a silver halide latent image is not formed, the photosensitive material of the first embodiment is used for the purpose of polymerizing unpolymerized polymerizable compounds after image transfer. Photoinitiators as mentioned in the description may be added. Regarding photosensitive materials using photoinitiators,
It is described in JP-A-62-161149.

Also, water release agents may be used.

Common matters regarding the photosensitive materials of the first embodiment and the second embodiment will be explained below. It is a main component in the photosensitive material of the first embodiment. The photopolymerization initiator, the pigment, and the polymerizable compound, or the silver halide, the reducing agent, the pigment, and the polymerizable compound, which are the main components in the second embodiment, are used in a microencapsulated state. The photosensitive material is composed of a photosensitive layer containing the microcapsules and a support, and the above-mentioned or below-mentioned "components that can be optionally used" may be present in the microcapsules in the photosensitive layer. However, it may be present in the photosensitive layer outside the microcapsules.

In addition to the above-mentioned components, optional components that can be used in photosensitive materials include polymerization inhibitors, oils, surfactants, fluorescent whitening agents, antifading agents, dyes or pigments for preventing halation or irradiation, and heating. Or pigments, matting agents, anti-smudge agents, which have the property of decolorizing when exposed to light,
These include plasticizers, binders, solvents for polymerizable compounds, etc.

First, as preferred polymerization inhibitors, known compounds can be used, and specific examples include p-methoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, naphthylamine, β-naphthol, nitrobenzene, Examples include dinitrobenzene and p-toluidine.

The preferred range of use is 0.001 to 10 of the polymerizable compound.
% by weight, more preferably from 0.01 to 1% by weight.

Next, preferred oxygen scavengers include organic phosphines, organic phosphonates, organic phosphites, and stannous salts. The preferred usage range is 1 to 50% by weight.

As the oil, a high boiling point organic solvent used as a solvent for emulsifying and dispersing hydrophobic compounds can be used.

Surfactants are used as coating aids, to improve peelability, to improve slipperiness,
Various compounds can be used for purposes such as antistatic agents and development acceleration. Specifically, pyridinium salts, ammonium salts, and phosphonium salts described in JP-A-59-74547, polyalkylene oxides as described in JP-A-59-57231, and surfactants as described in JP-A-62-173463. and surfactants described in JP-A-62-183457.

A dye or pigment may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. JP-A-63-29748 describes a photosensitive material in which a white pigment is added to the photosensitive layer.

Further, a pigment having a property of decolorizing by heating or light irradiation may be included in the microcapsules. The dye having the property of being decolored by heating or light irradiation can function as a yellow filter in conventional silver salt photography. Regarding photosensitive materials using dyes having the property of decolorizing by heating or light irradiation as described above, Japanese Patent Application Laid-Open No. 63-97940
There is a description in the bulletin.

The anti-smudge agent used in the photosensitive material is preferably a particulate material that is solid at room temperature. As a specific example, British Patent No. 1
Starch particles described in the specification of No. 232347, fine polymer powders described in the specification of US Pat. No. 3,625,736, etc., microcapsule particles containing no color former as described in the specification of British Patent No. 1,235,991, etc., and US Pat. No. 2,711,375. Examples include inorganic particles such as cellulose fine powder, talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina. The average particle size of the particles is preferably in the range of 3 to 50 μm, more preferably in the range of 5 to 40 μm in volume average diameter. It is more effective for the particles to be larger than microcapsules.

When a solvent for a polymerizable compound is used in a photosensitive material, it is preferable to encapsulate it in a microcapsule separate from the microcapsule containing the polymerizable compound. Regarding photosensitive materials using organic solvents that are miscible with polymerizable compounds encapsulated in microcapsules, Japanese Patent Application Laid-Open No. 62-2095
There is a description in Publication No. 24.

Various hardening agents can be used in photosensitive materials.

Specific examples include aldehyde hardeners, aziridine hardeners, epoxy hardeners, vinylsulfone hardeners, N-methylol hardeners, and polymer hardeners.

For more information on these, see U.S. Patent No. 4,678,73.
No. 9, column 41, JP-A-59-116655, JP-A No. 62
-245261, 61-18942, 62-2
There are descriptions in various publications such as No. 34157.

In addition to the above-mentioned examples of optional components that can be included in the photosensitive layer and how they are used, see the application specifications for the series of photosensitive materials mentioned above, and Research Disclosure Magazine Vol. 1.176, June 1978. No. 17029 (pages 9-15).

The photosensitive layer of the photosensitive material comprising the above-mentioned components preferably has a pH value of 7 or less, as in the photosensitive material described in JP-A-62-275235.

Layers that can be optionally provided on the photosensitive material include a heating layer, an antistatic layer, an anticurl layer, a peeling layer, a cover sheet or protective layer, a layer containing a base or a base precursor, a base barrier layer, and an antihalation layer. (colored layer), etc.

Regarding photosensitive materials using a heat generating layer, Japanese Patent Application Laid-open No. 1983
For photosensitive materials provided with a cover sheet or a protective layer, see JP-A No. 62-210447, and for photosensitive materials provided with a layer containing a base or base precursor, see JP-A No. 62-253140. A photosensitive material provided with a colored layer as an antihalation layer is described in JP-A-63-101842. Further, a photosensitive material provided with a base barrier layer is also described in the above-mentioned Japanese Patent Application Laid-Open No. 62-253140. Furthermore, examples of other auxiliary layers and their usage are also described in the applications relating to the above-mentioned series of light-sensitive materials.

The method of using the photosensitive material will be described below.

First, the method of using the photosensitive material of the first embodiment will be described.

In the image recording method of the present invention, the core substance is transferred onto the image-receiving material by pressing the image-formed photosensitive material and the image-receiving material at a pressure exceeding 500 kg/cri.

Various means can be used as the exposure method of the present invention. In general, commonly used light sources such as sunlight, strobes, flashes, tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser beams, and CRT light sources, plasma light sources, fluorescent tubes,
A light emitting diode or the like can be used as a light source. It is also possible to use an exposure means that combines a micro-shutter array using an LCD (liquid crystal), PLZT (lanthanum-doped lead titanium zirconate), etc., and a linear light source or a planar light source.

As a pressurizing method in the image forming method of the present invention, a conventionally known method can be used.

For example, the photosensitive material and the image-receiving material may be sandwiched between press plates such as a presser, or pressure may be applied while conveying using a pressure roller such as a nip roll. Pressure may be continuously applied using a dot impact device or the like.

Alternatively, highly pressurized air can be blown with an air gun or the like, or the pressure can be applied with an ultrasonic generator, a piezoelectric element, or the like.

The pressurizing pressure is preferably over 500 kg/csl, more preferably 700 kg/Cr1 or more.

Next, a method of using the second embodiment of the photosensitive material will be described.

The photosensitive material can be used simultaneously with imagewise exposure or after imagewise exposure.
Perform development processing and use.

Although various exposure means can be used as the above-mentioned exposure method, a latent image of silver halide is generally obtained by imagewise exposure to radiation including visible light. The type of light source and amount of exposure
Sensitive wavelength of silver halide (if dye sensitization is performed,
It can be selected depending on the sensitized wavelength) and sensitivity. Further, the original image may be a black and white image or a color image.

The photosensitive material is developed at the same time as the imagewise exposure or after the imagewise exposure.

The development process is a heat development process. This heat development treatment is described in JP-A-61-69062.

As the heating method in the above heat development treatment, various conventionally known methods can be used. Further, for example, the image receiving material or photosensitive material may be brought into direct contact with a hot plate such as a hot plate or a drum, or may be heated while being conveyed using a heat roller.

Heating can also be performed using air heated to a high temperature, high frequency heating, or a laser beam.

Depending on the nature of the imaged material, heating can also be done using an infrared heater. Furthermore, a method of heating using overcurrent generated by electromagnetic induction can also be applied.

Alternatively, the imaged material may be heated in a bath containing a heated inert liquid, such as a fluorine-based liquid. Further, as in the photosensitive material described in Japanese Patent Application Laid-open No. 61-294434, the photosensitive material may be provided with a heating layer and used as a heating means. Also, JP-A-61-2104
As in the image forming method described in Japanese Patent No. 61, heat development may be performed while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature generally ranges from 50°C to 200°C, preferably from 60°C to 150°C.

The heating time is generally 1 second or more, preferably from 1 second to 5 minutes, and more preferably from 1 second to 1 minute.

Furthermore, as in the image forming method described in Japanese Patent Application No. 1-3282, the above development is carried out by including a liquid in the photosensitive layer in an amount of 10 to 400% by weight of the polymerizable compound. The heat treatment may be performed at a temperature of 50° C. or higher.

Incidentally, instead of including the above-mentioned base or base precursor in the photosensitive material, the development treatment may be carried out while or immediately after the addition of the base or base precursor to the photosensitive layer. As a method for adding a base or a base precursor, a method using a sheet (base sheet) containing a base or a base precursor is easiest and preferred. An image forming method using the above base sheet is described in JP-A-63-32546.

The photosensitive material can be thermally developed as described above to polymerize the polymerizable compound in the area where the silver halide latent image is formed or the area where the silver halide latent image is not formed. In light-sensitive materials, the polymerizable compound in the area where the latent image of silver halide is generally polymerized in the heat development process described above.
As in the photosensitive material described in Japanese Patent No. 70836, by adjusting the type, amount, etc. of the reducing agent, it is also possible to polymerize the polymerizable compound in the area where the silver halide latent image is not formed.

The image thus obtained is transferred onto the image-receiving material by pressing the photosensitive material and the image-receiving material in a superimposed state.

As for this pressurizing method, a method similar to that of the first embodiment described above is used.

After forming an image on the image-receiving material as described above, the image-receiving material may be heated as in the image forming method described in JP-A-61-210459.

The above method also has the advantage that the unpolymerized polymerizable compound transferred onto the image-receiving material is polymerized and the storage stability of the obtained image is improved.

Photosensitive materials include black and white or color photography and printing photosensitive materials, printing photosensitive materials, printing plates, X-ray photosensitive materials, medical photosensitive materials (for example, ultrasonic diagnostic CRT photosensitive materials), computer graphic hard copy photosensitive materials, It has many uses, such as photosensitive materials for copying machines.

The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited thereto.

"Example" Example 1 Preparation of silver halide emulsion (ER-1) 20 g of seratin and 0.8 g of sodium chloride were added to an aqueous gelatin solution (1,600 ml of water, and the pH was adjusted to 3.4 with IN sulfuric acid.
(adjusted to 45°C), potassium bromide 6
200 - of an aqueous solution containing 5 g and an aqueous solution of silver nitrate (20
(dissolved 100g of silver nitrate in 0d) at the same time 30
Added at equal flow rates over a period of minutes. One minute after this addition was completed, the sensitizing dye (SR-1) was added, and from 15 minutes after the addition of the sensitizing dye, an aqueous solution containing 2.00 g of potassium iodide and a silver nitrate aqueous solution (100 g of water) were added. - in which 0.022 g of silver nitrate was dissolved) was added at an equal flow rate over 5 minutes. To this emulsion, 1.2 g of poly(isobutylene-monosodium co-maleate) was added, precipitated, washed with water, and desalted. 3.5 g of seratin was added and dissolved, and an additional 0.45 g of sodium thiosulfate was added. In addition, chemical sensitization was performed at 55°C for 20 minutes, and the average particle size was 0.
．． 440 g of a monodispersed tetradecahedral silver iodobromide emulsion (ER-1) having a 13 μm variation coefficient of 24% was prepared.

Sensitizing dye (SR-1) 3% aqueous solution of gelatin in a 300-ml dispersion container
0 g, 40 g of base precursor (BG-4) and 2001 nI of glass beads with a diameter of 0.5-0.75 mo! was added and dispersed for 30 minutes at 3000 revolutions per minute using a Dyno Mill to obtain a solid dispersion (KB-1) with a particle size of 1.0 μm or less.
) was obtained.

Preparation of Material (GC-1) 255 g of the polymerizable compound (MN-1) was mixed with 45 g of Microlith Blue 4GA (trade name, manufactured by Ciba Geigy), and mixed using an Eiger Motor Mill (manufactured by Eiger Engineering). The mixture was stirred at 5000 revolutions per minute for 1 hour to obtain a dispersion (GC-1).

Polymerizable compound (MN-1) Product name: Kayalad R684 (Nippon Kayaku (squeezed) feeling
Copolymer (I) was added to 45.0 g of pigment dispersion (GC-1) of
F-1) (SV-1) 9.0 g of 20% by weight solution was dissolved. In this solution, 2.3 g of (RD-1), (RD-2)
) and 0.005 g of (FF-3) were added to obtain an oily liquid.

3.8 g of silver halide emulsion (ER-1) and 24.0 g of solid dispersion (KB-1) were added to this solution, and the mixture was stirred at 10,000 rpm for 5 minutes using a homogenizer while keeping the temperature at 60°C. , W10 emulsion photosensitive composition (
PR-1) was obtained.

Copolymer (I P-1) CH, CH3 +CH+ C+la +CH+ C+ r+C
O□Ct1. CH=C)I2CO,H(SV-1) CH, -CH-CI(, OCR.

H (RD-1) (FF-3) (RD-2) C,,H,,0 Preparation of photosensitive microcapsule liquid (CR-1) 4.0 g of a 15% aqueous solution of polymer (2P-1) and polymer ( A mixed solution of 96° Og of 5.0% aqueous solution of 2P-2) was adjusted to pH 5.0. The above photosensitive composition (PR-1) was added to this mixed solution, and the mixture was stirred at 60° C. and 6,000 rpm for 20 minutes using a Daysilver to obtain an emulsion in the form of a W10/W emulsion.

Separately, 20.0 g of a 37% formaldehyde aqueous solution and 76.3 g of distilled water were added to 14.8 g of melamine, heated to 60° C., and stirred for 40 minutes to obtain a transparent aqueous solution of melamine/formaldehyde initial condensate.

37.5 g of the aqueous solution of this initial condensate and 7.5 g of distilled water were added to the W/○/W emulsion (146 g), and the pH was adjusted to 5.0 using 2N sulfuric acid. This was then heated to 60°C and stirred for 60 minutes. Furthermore, the pH was adjusted to 6.5 using a 2N aqueous sodium hydroxide solution, and a photosensitive microcapsule dispersion (CR-1: capsule content 27% by weight, binder concentration 2.2% by weight) was prepared.

Polymer (2P-1) Potassium polyvinylbenzenesulfinate polymer (2
F-2) A 5% aqueous solution of sodium polyvinylbenzene sulfonate prepared for polyvinylpyrrolidone with -90 (GAF Co., Ltd.) for raw use was coated on a polyethylene terephthalate film (100 μm thick) at a coating amount of 100 g/ba, and heated at approximately 60°C. The support (1) according to the present invention was prepared.

Next, the photosensitive microcapsule dispersion (CR-
1. 27% by weight of capsule contents, binder concentration 2.
2% by weight), 4.0g of a 5% aqueous solution of Emarex NP-8 (Nippon Emulsion Co., Ltd.), polymer (2% by weight),
4.6 g of 20.0% aqueous solution of P-2) and 21 g of distilled water
．． 4 g was added and stirred well to prepare a coating solution.

This coating liquid was applied onto the support (1) in an amount of 80 g/rn'.
The photosensitive material (1) according to the present invention (the amount of binder in the photosensitive layer was 15% by weight based on the contents of the capsule) was prepared by coating at a temperature of about 60°C and drying at about 60°C.

Example 2 Preparation of photosensitive microcapsule dispersion (CR-2) Photosensitive microcapsule dispersion (OR-2) of Example (1)
A photosensitive microcapsule dispersion according to the present invention (CR-2+ capsule content 27% by weight,
A binder concentration of 2.2% by weight was prepared.

Preparation of Support (2) The sodium polyvinylbensene sulfonate used in the preparation of Support (1) in Example (1) was replaced with aminoacrylic acrylate-modified polyvinyl alcohol (trade name:
A support (2) according to the present invention was prepared in the same manner as in Example (It) except that C-318-2A (manufactured by Kuraray Co., Ltd.) was used.

Grave Pillar Decoration Association 9 Creation The photosensitive microcapsule dispersion (CR-1) used in the production of the photosensitive material (1) in Example 1 was replaced with the photosensitive microcapsule dispersion (CR-2), and the polymer ( The photosensitive material (2) (capsules) according to the present invention was prepared in the same manner as in Example (1) except that 2P-2) was replaced with sodium polyvinylbenzenesulfonate and support (1) was replaced with support (2). The amount of binder in the photosensitive layer was 15% by weight based on the contents.

Example 3 Initiator (Irgacure 651
1 (manufactured by Ciba-Geigi Co., Ltd.) was dissolved to obtain a photosensitive composition.

Po I) -v -(2P -1) +7) 15X aqueous solution 4
．． A mixed solution of 96.0 g of a 5.0'X aqueous solution of po')mer (2P-2) was adjusted to pH 5.0. The above-mentioned photosensitive composition was added to this mixed solution, and the mixture was stirred at 60° C. and 3000 revolutions per minute for 30 minutes using a Daysilver to obtain an emulsion in the form of a 0/W emulsion.

Separately, 20.0 g of a 37% formaldehyde aqueous solution and 76.3 g of distilled water were added to 14.8 g of melamine, heated to 60° C., and stirred for 40 minutes to obtain a transparent aqueous solution of melamine/formaldehyde initial condensate.

37.5 g of an aqueous solution of this initial condensate and 7.5 g of water were added to the above 0/W emulsion (146 g), and the pH was adjusted to 5.0 with a 2N aqueous sulfuric acid solution. Then,
This was heated to 60°C and stirred for 60 minutes. Furthermore, 2
Using a specified sodium hydroxide aqueous solution, pl (6.5
The photosensitive microcapsule dispersion according to the present invention (C
R-3 = 27% weight of cell contents, binder concentration 2
．． 2% by weight) was prepared.

Except for replacing the photosensitive microcapsule dispersion <cR-x) used in the preparation of photosensitive material (1) in Example 1 with g-photosensitive microcapsule dispersion (CR-3). The photosensitive material (3) according to the present invention was prepared in the same manner as in Example (1) (the amount of binder in the photosensitive layer was 15% by weight based on the content of the capsule).
)It was created.

Comparative Example 1 Creation of Ω to the forklift body In the production of the support (1) of Example 1, sodium polyvinylbenzenesulfonate was mixed with polyvinyl alcohol (
Example 1 except that PVA205 (manufactured by Kuraray Co., Ltd.) was used.
A comparative support (A) was prepared in the same manner as above.

Formation of Photosensitive Layer (A) In preparing the photosensitive material (1) of Example 1, the support (1
A comparative photosensitive material (A) was prepared in the same manner as in Example 1 (the amount of binder in the photosensitive layer was 15% by weight based on the contents of the capsule), except that the support (A) was used instead of the support (A).

Comparative Example 2 Preparation of photosensitive material (B) In preparing a coating solution for photosensitive material (1) of Example 1, 4.6 g of a 20.0% aqueous solution of polymer (2P-2) was
．． A comparative photosensitive material (B) was prepared in the same manner as in Example 1, except that Og was replaced with 11.0 g of distilled water (21.4 g of distilled water was replaced with 11.0 g) (the amount of binder in the photosensitive layer was 30% by weight based on the content of the capsule). )It was created.

Comparative Example 3 Preparation of Photosensitive Material (C) In preparing the coating solution for photosensitive material (1) in Example 1, no 20.0% aqueous solution of polymer (2P-2) was added, and 21% of distilled water was added. Other than replacing 4g with 26.0g,
A comparative photosensitive material (C) was prepared in the same manner as in Example 1 (the amount of binder in the photosensitive layer was 8% by weight based on the contents of the capsule).

Comparative Example 4 Preparation of "Okido Kuba" Dan and L Produced in the same manner as in Example 2 except that the support (2) used in the preparation of the photosensitive material (2) of Example 2 was replaced with the support (A). A comparative photosensitive material (D) (the amount of binder in the photosensitive layer was 15% by weight based on the contents of the capsule) was prepared.

Comparative Example 5 In preparing the coating solution for the photosensitive material (2) of Example 2, 4.6 g of a 20% aqueous solution of sodium polyvinylbenzenesulfonate was replaced with 15.0 g. Also, distilled water 21.
4g to 11. A comparative photosensitive material (E) (30% by weight of the binder in the photosensitive layer based on the contents of the capsule) was prepared in the same manner as in Example 2, except that Og was used instead.

Comparative Example 6 In preparing the coating solution for the photosensitive material (2) of Example 2, the exception was that the 20% aqueous solution of potassium polyvinylbenzenesulfonate was not added and 21.4 g of distilled water was replaced with 26.0 g. A comparative photosensitive material (F) was prepared in the same manner as in Example 2 (the amount of binder in the photosensitive layer was 8% by weight based on the content of the capsule).

! ” ■ L Rikyoku Intuitive Calcium Carbonate (PC700, manufactured by Shiraishi Kogyo ■) 80g,
Mix 1.6 g of surfactant (Poise 520, Kao (Keg)), and 221.4 g of water, and use a Polytron dispersion machine (PT
200 per minute using a 10/35 model (manufactured by Kinematica)
Dispersion was carried out for 20 minutes at 0 rotations. 60g of this dispersion and 8%
Mix 32.5 g of polyvinyl alcohol (PVA-117, manufactured by @'7-y) aqueous solution, and then add 42.6 g of water.
was added to prepare a coating solution for forming an image-receiving layer.

This coating solution was applied to a paper support (JIS-P
A paper support using a base paper having a fiber length distribution defined by -8207 that is 30 to 60% of the sum of the weight percent of the 24 mesh residue and the weight percent of the 42 mesh residue. (See JP-A No. 63-186239)]) was coated uniformly at 110 g/rd and dried at 60° C. to prepare an image-receiving material (B).

Evaluation of transferred images The photosensitive materials (1), (2), (A) to (F) were passed through a filter with a transmission density of 0 to 3.0 using a tungsten light bulb to a color temperature of 4800, 20001 ux, 1 second. After exposure under the exposure conditions, the photosensitive material was placed on a hot plate heated to 140°C, and the photosensitive layer surface was brought into close contact with the photosensitive material for 10 minutes.
Developed by heating for seconds. Next, the photosensitive material is coated with an image receiving material (B
) were piled up and passed through a pressure roller of 500 kHz/crl in that state. Then, the image receiving material is peeled off from the photosensitive material,
A cyan positive image was obtained on the receiving material.

In addition, the photosensitive material (3) was heated using a 200W high-pressure mercury lamp.
Imagewise exposure was carried out for 20 seconds from a distance of 30 AO. Next, when layered with image-receiving material (B) and passed through a pressure roller of 500 kg/cd to separate the photosensitive material and image-receiving material, a positive cyan image was obtained on the image-receiving material.The above results are shown in Table 1. Ta.

/ / From the results shown in Table 1, it can be seen that the photosensitive material according to the present invention ((1
) to (3)) have a high maximum concentration because they have a binder that prevents oxygen from permeating into the photosensitive layer and does not inhibit the transfer of the capsule contents in pressure transfer.
It can be seen that clear images with low minimum density are provided. Furthermore, since the binder in the photosensitive layer interacts with the polymer between the photosensitive layer and the support, the microcapsules do not peel off during pressure transfer, giving images with less unevenness and dirt. I understand.

Claims (4)

[Claims] (1) In a transfer recording medium in which recording is performed by transferring the contents of microcapsules containing a photosensitive element whose transfer characteristics change depending on the amount of exposure onto an image-receiving material, at least the microcapsules and the 1 for capsule contents
1. A transfer recording medium comprising a photosensitive layer containing 0 to 25% by weight of a binder, and a layer containing a polymer that interacts with the binder in the photosensitive layer between the support and the photosensitive layer. (2) Claim (1) characterized in that the polymer contained in the layer between the support and the photosensitive layer and the binder in the photosensitive layer have electrostatic interaction or dipole-dipole interaction.
) Transfer recording medium. (3) The transfer recording medium according to claim (1), wherein the microcapsules contain at least silver halide, a reducing agent, a color image forming substance, a polymerizable compound, and a base precursor. (4) The transfer recording medium according to claim (1), wherein the microcapsules contain at least a photopolymerization initiator, a color image forming substance, and a polymerizable compound.