JPH0734112B2 - Photosensitive microcapsule and photosensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive microcapsule and a photosensitive material using the same. More specifically, the present invention relates to a photosensitive microcapsule containing silver halide and a polymerizable compound, a photosensitive microcapsule containing a photopolymerizable composition and a photopolymerizable compound, and a photosensitive material using these.

BACKGROUND OF THE INVENTION A photosensitive material used in a method of forming an image by polymerizing a polymerizable compound by the action of a reducing agent in a portion where a latent image of silver halide is formed is disclosed in Japanese Examined Patent Publication No. 45-11149. Same as 47
No. 20741, No. 49-10697, JP-A Nos. 57-138632, 58-169143, and the like, the image forming methods are disclosed.

Further, as an improvement, a method capable of forming a polymer compound by a dry process has been proposed (Japanese Patent Laid-Open No. 61-690).
62, or 61-73145). These methods are
Recording in which a photosensitive layer comprising a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound) and a binder or a color image forming substance as a constituent component is carried on a support. This is a method of exposing a material (photosensitive material) imagewise to form a latent image, and then heating the latent image to polymerize a polymer (polymerizable compound) in the portion where the latent image is formed.

Incidentally, there is already known a method capable of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed (JP-A-61-260241). This method is a method of suppressing the polymerization of the portion of the silver halide on which a latent image is formed, and at the same time promoting the polymerization of the other portion (area where the latent image is not formed).

An image forming method using a photosensitive material having a photosensitive layer containing a photopolymerizable composition or a photopolymerizable compound on a support is a method of forming a polymer (polymer compound) on an exposed portion by imagewise exposure. . For the image forming method and the light-sensitive material used therefor, see JP-A-52-89915 and JP-A-57-179.
836, 58-88739, 58-88740, and 60-2594
It is described in each publication such as No. 90.

In the image forming method using the light-sensitive material having the above-mentioned constitution, after the polymer compound is imagewise formed on the light-sensitive material as described above, the light-sensitive material is further superposed on an image-receiving material having an image-receiving layer, A method is generally used in which pressure is applied in the state to transfer an unpolymerized polymerizable compound (or a photopolymerizable composition or a photopolymerizable compound, the same applies hereinafter) to an image receiving material to obtain a transferred image on the image receiving material. Further, in the above image forming method, a light-sensitive material comprising silver halide and a polymerizable compound contained in microcapsules (JP-A-61-262).
75742 and 61-278849), or a light-sensitive material in which a photopolymerizable composition or a photopolymerizable compound is housed in microcouples is preferably used. Good images can be obtained by introducing microcapsules.

Various resins can be used for the wall material of the microcapsules. Among them, the polyurea resin and / or the polyurethane resin are relatively rich in elasticity, and also have denseness and toughness, and therefore, the above-mentioned photosensitive material is used for the reason of improving storage stability or facilitating handling. It is preferably used for the production of (for example, see JP-A-62-209438).

However, according to the study by the present inventor, when the above-mentioned image forming method is carried out by using a light-sensitive material containing a microcapsule composed of an outer shell formed by resinification of a polyisocyanate compound, the image portion of the transferred image is In some cases, the density of the (highest density portion) was lowered, or the white background portion (background; lowest density portion) was colored, and the contrast of the entire image was lowered.

SUMMARY OF THE INVENTION It is an object of the present invention to provide photosensitive microcapsules that can be suitably used for producing a photosensitive material that gives an image with good contrast.

In particular, it is an object of the present invention to provide a light-sensitive material capable of suppressing the exudation of the contents (core substance) contained in the capsule during heat development and obtaining an image with high contrast.

The present invention provides a photosensitive microcapsule in which an outer shell made of a resin produced from a raw material containing an isocyanate having an isocyanurate ring structure is formed around a core substance containing a silver halide and a polymerizable compound. To do.

Further, the present invention has a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support, and the silver halide and the polymerizable compound are contained in microcapsules. Provided is a light-sensitive material having an outer shell made of a resin wall produced from a raw material containing an isocyanate having an isocyanurate ring structure.

Furthermore, the present invention provides a photosensitive material comprising a photopolymerizable composition or a core material containing a photopolymerizable compound, and an outer shell made of a resin produced from a raw material containing an isocyanate having an isocyanurate ring structure, formed around the core material. To provide sex microcapsules.

Furthermore, the present invention has, on a support, a photosensitive layer containing a photopolymerizable composition or a photopolymerizable compound, and the photopolymerizable composition or the photopolymerizable compound is contained in microcapsules. Provided is a light-sensitive material in which the outer shell of the microcapsule comprises a resin wall formed from a raw material containing an isocyanate having an isocyanurate ring structure.

The photosensitive microcapsules and the photosensitive material of the present invention preferably have the following embodiments.

(1) The above-mentioned isocyanate is a compound having an isocyanurate ring structure selected from the group consisting of hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate and tolylene diisocyanate.

(2) An isocyanate having an isocyanurate ring structure is contained in an amount of 2 to 50% by weight based on the core substance.

(3) The above resin is a polyurea resin produced from a raw material containing an isocyanate having an isocyanurate ring structure and water or a polyamine.

(4) The core material contains a reducing agent.

(5) The core substance contains a reducing agent, and the reducing agent is a phenolic compound.

(6) The core substance contains a reducing agent, and the reducing agent is a hydrazine compound.

(7) An antifoggant is contained in the core substance, and the antifoggant is a 5-membered or 6-membered nitrogen-containing heterocyclic compound,
Alternatively, it is a thiol derivative.

(8) A color image forming substance is contained in the core substance.

(9) The average particle size of the photosensitive microcapsules is
0.5 to 50 μm.

[Effects of the Invention] According to the research conducted by the present inventor, the microcapsules comprising the outer shell made of the polyurea and / or the polyurethane resin described above (JP-A-62-209438) show that tolylene diisocyanate is used as the outer shell forming material. It was found that a resin wall having a desired high glass transition point cannot be obtained even when prepared using an aromatic isocyanate (isocyanate monomer) such as nato or diphenylmethane diisocyanate. Since these isocyanates have high reactivity, they easily react with the contents of the capsule (functional group contained in the polymerizable compound or the reducing agent (usually the reducing agent is contained in the core substance)) when the outer shell is formed. Therefore, it is considered that the glass transition point of the prepared resin is considerably lower than the glass transition point to be originally formed. Therefore, when the development processing is carried out at the heat development temperature (normal heating temperature 110 to 155 ° C.) in the above-mentioned image forming method,
It was found that the capsule wall was loosened and the core substance (polymerizable compound, etc.) contained in the capsule was easily exuded.
Particularly, in order to shorten the development processing time, when the development processing temperature is set higher than usual (140 to 180 ° C.) and the development processing is performed, the above-mentioned bleeding tends to be further promoted.
It was also found that these are the causes of lowering the image contrast described above.

When microcapsules are prepared using a raw material containing an isocyanate having an isocyanurate ring structure (isocyanurate ring modified product) according to the present invention, heat resistance is imparted by trimerization of an isocyanate monomer, resulting in It was found that a resin wall having a high glass transition point can be prepared. Further, the modified isocyanurate ring also has a lower reactivity with the contents than the above aromatic isocyanate (isocyanate monomer), and therefore, it is considered that the resin formation proceeds and the decrease in the glass transition point is suppressed.

From the above, by using a capsule prepared using a modified isocyanurate ring as a photosensitive material,
Even when heat development is performed at a high temperature, exudation of the monomer in the capsule is suppressed, and a clear image can be obtained by a short development process.

DETAILED DESCRIPTION OF THE INVENTION The outer shell of the photosensitive microcapsule of the present invention is made of a resin produced from a raw material containing an isocyanate having an isocyanurate ring structure.

The isocyanate having an isocyanurate ring structure according to the present invention is obtained by modifying (trimerization reaction) a known isocyanate (a polyvalent isocyanate monomer / a single monomer or a combination of different monomers). It can be used (hereinafter referred to as isocyanurate ring-modified product).

Examples of the polyvalent isocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate and 2,6.
-Tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyldi Isocyanate, 3,3'-
Dimethyldiphenylmethane-4,4'-diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexa Methylene diisocyanate, propylene-1,2-diisocyanate, ethylidine diisocyanate, cyclohexylene-1.2-diisocyanate, cyclohexylene-1,4-diisocyanate, isophorone diisocyanate, tetramethylxylylenediene Diisocyanates such as isocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, toluene 2,4,6-triisocyanate, triisocyanates such as polymethylene polyphenyl isocyanate, 4 , 4'-Dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate Mention may be made of tetra-isocyanate, such as theft.

The preferred specific examples are described below.

Of these, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate modified isocyanurate ring are preferable.

These isocyanates are commercially available from Nippon Polyurethane Industry Co., Ltd., Sumitomo Bayer Urethane Co., Ltd., Takeda Pharmaceutical Co., Ltd., Dainippon Ink Co., Ltd., Mitsui Toatsu Co., Ltd., and the like.

The photosensitive microcapsule of the present invention can be produced, for example, by the following method using the above isocyanurate ring modified product.

After preparing a hydrophobic liquid (hereinafter referred to as a photosensitive composition) comprising a photosensitive silver halide and a polymerizable compound described below, or a core substance such as a reducing agent and a color image forming substance, if necessary, the composition is prepared. The above-mentioned modified isocyanurate ring is dissolved in. Next, the resulting mixture is dispersed in water or an aqueous medium containing a polyamine into fine droplets to prepare a dispersion liquid.
In addition, a catalyst (for example, dibutyltin dilaurate) that accelerates the polycondensation reaction between the isocyanurate ring-modified product and water or polyamine may be present in this dispersion liquid.

When the dispersion liquid prepared as described above is heated at a temperature in the range of 40 to 90 ° C., a polyurea resin which is a reaction product of the isocyanurate ring-modified product and water or polyamine is formed at the interface of the microdroplets.

Various methods for producing microcapsules using a polyurea resin as an outer shell material are already known, and any of these methods can be used for producing the photosensitive microcapsules of the present invention.

Examples of the polyamine used for forming the outer shell of the photosensitive microcapsules as described above will be described below.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-
Examples thereof include methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxytrimethylenediamine, diethylenetriamine, triethylenetetraamine, diethylaminepropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds.

In the present invention, the modified isocyanurate ring is contained in an amount of 2 to 50% by weight (more preferably 4% by weight) based on the core substance.
To 30% by weight). Further, in the preparation of microcapsules, it is particularly preferable to constitute only the above isocyanurate ring modified product, but the isocyanate monomer described in JP-A-62-209438 or the above isocyanurate ring modified product is particularly preferable. It can also be used in combination with the isocyanate monomer used to produce the. In this case, the amount of the isocyanurate ring-modified product according to the present invention is preferably 30% by weight or more, more preferably 50% by weight, based on the total amount of the isocyanate used.
That is all.

In addition, when preparing the resin wall of the microcapsule prepared by using the modified isocyanurate ring of the present invention, a polyol or a polyamide may be used. Thereby, the microcapsule can be used as a composite resin wall (including a resin wall having a two-layer structure). Further, by further forming a melamine-formaldehyde resin or a urea-formaldehyde resin (outer layer) around the resin wall (inner layer) prepared by using the isocyanate having an isocyanurate ring structure according to the present invention. It can also have a two-layer structure. For capsules prepared by using a melamine-formaldehyde resin for the outer layer, see, for example, U.S. Pat.No. 4,353,809, JP-A-56-102935 and
62-209439 and Japanese Patent Application Nos. 62-105099 and 63
-152778. Further, for capsules prepared by using urea-formaldehyde resin in the outer layer, for example, JP-A-55-119438 and 62-
No. 209438.

When the silver halide and the polymerizable compound are introduced into the hydrophobic liquid of the core material, the silver halide is usually produced as an emulsion (silver halide emulsion) using water as a dispersion medium, and then this is treated with a hydrophobic solvent. The method of mixing is generally used. Since the aqueous medium of the silver halide emulsion moves to the aqueous phase of the dispersion medium during the preparation of the emulsion dispersion for producing microcapsules, there is almost no water inside the core of the resulting photosensitive microcapsules. Further, as described above, when the silver halide emulsion is transferred to the aqueous phase of the aqueous medium, the silver halide grains are accompanied by water from the core substance phase (oil phase) to the dispersion medium phase (aqueous phase). Because of the tendency of migration, silver halide tends to collect near the interface between the core material phase and the dispersion medium phase. Therefore, when the silver halide is introduced into the core substance by utilizing the silver halide emulsion, the silver halide grains are often present in the vicinity of the outer shell or inside the outer shell at a high concentration. It is preferable that the silver halide grains are in the above-mentioned position because exposure is facilitated and sensitivity is improved.

The introduction of silver halide grains into the core substance may be carried out not as a silver halide emulsion as described above but as a dispersion liquid in which silver halide grains are dispersed in an organic solvent.
Alternatively, a method of simply mixing the silver halide grains obtained as a powder with a polymerizable compound can be used.

From the aqueous liquid containing the photosensitive microcapsules obtained by the method as described above, the photosensitive microcapsules can be separated by using a known separation method such as evaporation of the aqueous solvent, filtration, or centrifugation. it can.

The average particle size of the microcapsules obtained as described above is preferably in the range of 0.5 to 50 μm, more preferably 2 to 15 μm. The particle size distribution of the microcapsules is preferably a uniform value or more, as in the light-sensitive material described in JP-A-63-5334. Further, the film thickness of the microcapsules is preferably within a certain range with respect to the particle diameter, as in the light-sensitive material described in JP-A-63-81336.

When the silver halide is contained in the microcapsules, the average grain size of the silver halide grains is preferably 1/5 or less, more preferably 1/10 or less of the average size of the microcapsules. preferable. By setting the average grain size of the silver halide grains to be one fifth or less of the average size of the microcapsules, a uniform and smooth image can be obtained.

The light-sensitive material of the present invention has, on a support, a light-sensitive layer containing the light-sensitive microcapsules prepared as described above. The light-sensitive material of the present invention includes two modes depending on the constitution of the core substance contained in the capsule. The first embodiment has a constitution in which, of the silver halide, the reducing agent and the polymerizable compound, a photosensitive layer containing the silver halide and the polymerizable compound in photosensitive microcapsules is provided on a support. In addition, the second aspect is a structure having a photosensitive layer containing a photopolymerizable composition or a photopolymerizable compound in photosensitive microcapsules on a support.

Hereinafter, the first aspect will be mainly described.

Photosensitive materials include silver chloride, silver bromide,
Any grain of silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used.

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having a multiple structure having different compositions on the surface and inside, JP-A-57-154232, JP-A-58-108533, and JP-A-59-48755
No. 59-52237, US Pat. No. 4433048, and European Patent No. 100984. Further, silver halide grains having a high ratio of silver iodide in the shell portion may be used as in the light-sensitive material described in JP-A-62-183453.

There is also no particular limitation on the crystal habit of the silver halide grains. For example, tabular grains having an aspect ratio of 3 or more as in the light-sensitive material described in JP-A-62-210455 may be used.

Incidentally, as the above silver halide grains, JP-A-63-68830
It is preferable to use silver halide grains having a relatively low fog value, as in the light-sensitive material described in JP-A No.

Two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like can be used in combination with the silver halide used in the light-sensitive material.

The grain size distribution of silver halide grains is not particularly limited. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used as in the light-sensitive material described in JP-A-62-210448.

In the light-sensitive material, the average grain size of silver halide grains is preferably 0.001 to 5 μm, and more preferably 0.001 to 2 μm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 10 g / m ^{2 in} terms of silver including an organic silver salt which is an optional component described later.
It is preferable to set it as the range. Further, in terms of silver equivalent of silver halide alone, it is preferably 1 g / m ² or less, and particularly preferably 1 mg to 500 mg / m ² .

The reducing agent that can be used in the light-sensitive material has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. There are various kinds of substances as the reducing agent having the above function. Examples of the reducing agent include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-
Pyrazolones, 5-aminouracils, 4,5-dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2
-Sulfonamidoindanones, 4-sulfonamido-
5-pyrazolones, 3-sulfonamidoindoles,
Examples include sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines. By adjusting the type and amount of the reducing agent, it is possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image is not formed. In addition,
In the system in which the polymerizable compound in the portion where the latent image of silver halide is not formed is polymerized, it is particularly preferable to use 1-phenyl-3-pyrazolidones as the reducing agent.

Regarding various reducing agents having the above functions, see
61-183640, 61-188535, 61-228441, and JP-A-62-70836, 62-86354, 62-8
6355, Japanese Patent Application No. 60-227528, Japanese Patent Application Laid-Open No. 62-198849, and the like, and descriptions (including those described as a developer or a hydrazine derivative). Regarding the reducing agent, see “The Theory of the Photographic Pr” by T. James.
ocess "4th edition, pages 291-334 (1977), Research Disclosure Vol. 170, June 1978, No. 17029 (9)
Pp. 15), and Vol. 176, December 1978, No. 17643 (p. 22-31). In addition, JP-A-62-210446
Instead of the reducing agent, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base may be used instead of the reducing agent as in the light-sensitive material described in Japanese Patent Laid-Open Publication No. The reducing agent and reducing agent precursor described in the above-mentioned publications, specifications and literatures can be effectively used for the light-sensitive material in the present specification. Therefore, the “reducing agent” in the present specification includes the reducing agents and reducing agent precursors described in the above-mentioned publications, specifications and literatures. These reducing agents may be used alone, or as described in each of the above specifications, two or more reducing agents may be mixed and used. When two or more reducing agents are used in combination, the reducing agent interactions include:
First, to promote the reduction of silver halide (and / or organic silver salt) by so-called superadditivity, and secondly,
Inducing polymerization of a polymerizable compound through an oxidation-reduction reaction with another reducing agent in which an oxidized product of the first reducing agent produced by reduction of silver halide (and / or organic silver salt) coexists (or It may be possible to suppress the polymerization). However, in actual use, it is difficult to specify which of the above actions because the above reactions can occur simultaneously.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 1-phenyl-4-methyl-4.
-Hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenylsulfonyl Amino-4-t-butyl-
5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-octadecylcarbamoyl) -4-sulfonylaminonaphthol, 1-acetyl-2-phenylhydrazine , 1-acetyl-2-{(p
Or o) -aminophenyl} hydrazine, 1-formyl-2-{(p or o) -aminophenyl} hydrazine, 1-acetyl-2-{(p or o) -methoxyphenyl} hydrazine, 1-lauroyl-2 -{(P or o) -aminophenyl} hydrazine, 1-trityl-
2- (2,6-dichloro-4-cyanophenyl) hydrazine, 1-trityl-2-phenylhydrazine, 1-phenyl-2- (2,4,6-trichlorophenyl) hydrazine, 1- {2- (2 , 5-di-t-pentylphenoxy)
Butyroyl} -2-{(p or o) -aminophenyl} hydrazine, 1- {2- (2,5-di-t-pentylphenoxy) butyroyl} -2-{(p or o) -aminophenyl} hydrazine -Pentadecyl fluorocaprylate, 3-indazolinone, 1- (3,5-dichlorobenzoyl) -2-phenylhydrazine, 1-trityl-2-[{(2-N-butyl-N-octylsulfamoyl) -4-Methanesulfonyl} phenyl] hydrazine, 1- {4- (2,5-di-t-pentylphenoxy)
Butyroyl} -2-{(p or o) -methoxyphenyl} hydrazine, 1- (methoxycarbonylbenzohydryl) -2-phenylhydrazine, 1-formyl-2-
[4- {2- (2,4-di-t-pentylphenoxy) butylamido} phenyl] hydrazine, 1-acetyl-2
-[4- {2- (2,4-di-t-pentylphenoxy)
Butylamido} phenyl] hydrazine, 1-trityl-
2-[{2,6-dichloro-4- (N, N-di-2-ethylhexyl) carbamoyl} phenyl] hydrazine, 1-
(Methoxycarbonylbenzohydryl) -2- (2,4-
Dichlorophenyl) hydrazine, 1-trityl-2-
[{2- (N-ethyl-N-octylsulfamoyl)
-4-Methanesulfonyl} phenyl] hydrazine, 1-
Benzoyl-2-tritylhydrazine, 1- (4-butoxybenzoyl) -2-tritylhydrazine, 1- (2,
4-dimethoxybenzoyl) -2-tritylhydrazine, 1- (4-dibutylcarbamoylbenzoyl) -2
-Tritylhydrazine, and 1- (1-naphthoyl)
-2-Trityl hydrazine etc. can be mentioned.

In the light-sensitive material, the reducing agent is preferably used in the range of 0.1 to 1500 mol% with respect to 1 mol of silver (including the above-described silver halide and an organic silver salt which is an optional component).

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and known polymerizable compounds can be used. As a method of using the light-sensitive material, when a heat development process is planned, a high boiling point (for example, a boiling point of 80 ° C.) that is hard to volatilize during heating is used.
It is preferable to use the above compounds). Further, in the embodiment in which the photosensitive layer contains a color image forming substance as an optional component described later, the color image forming substance is immobilized by polymerizing and curing the polymerizable compound. A crosslinkable compound having a polymerizable functional group is preferable. Further, as will be described later, when a transfer image is formed using an image receiving material, it is preferable to use a highly viscous substance as the polymerizable compound, as in the photosensitive material described in Japanese Patent Application No. 61-150079. preferable.

The polymerizable compounds that can be used in the light-sensitive material are described in the application specifications for a series of light-sensitive materials described above and below.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable.

Compounds having an ethylenically unsaturated group that can be used in the light-sensitive material include acrylic acid and salts thereof, acrylic acid esters, acrylamides, methacrylic acid and salts thereof, methacrylic acid esters, methacrylamides, maleic anhydride. Acids, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N-vinyl heterocycles, allyl ethers,
There are allyl esters and their derivatives.

Specific examples of the polymerizable compound that can be used in the light-sensitive material include acrylic acid esters such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, dicyclohexyloxy. Ethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate,
Diacrylate of polyoxyethylenated bisphenol A, diacrylate of condensate of 2,2-dimethyl-3-hydroxypropionaldehyde and trimethylolpropane, triacrylate of condensate of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol , Hydroxypolyether polyacrylates, polyester acrylates and polyurethane acrylates.

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

The polymerizable compounds may be used alone or in combination of two or more. A light-sensitive material containing two or more polymerizable compounds in combination is described in JP-A-62-210445.
A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the above-mentioned reducing agent or an optional component described later, which is a color image forming substance, can also be used as the polymerizable compound. Needless to say, use of a substance that serves as both a reducing agent and a polymerizable compound or a color image forming substance and a polymerizable compound as described above is also included in the embodiment of the light-sensitive material.

In the light-sensitive material, the polymerizable compound is preferably used in the range of 50 to 120,000 parts by weight with respect to 1 part by weight of silver halide. A more preferred range of use is 12 to 12000 parts by weight.

The light-sensitive material comprises a support and a light-sensitive layer containing the components described above. The support is not particularly limited, but when heat development processing is planned as a method of using the light-sensitive material, it is preferable to use a material that can withstand the processing temperature of the development processing. Examples of materials that can be used for the support include glass, paper, high-quality paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene. Examples thereof include films such as terephthalate, and paper laminated with a resin material or a polymer such as polyethylene.

When the support is made of a porous material such as paper, it has a certain smoothness according to a prescribed method due to waviness like the support used in the photosensitive material described in JP-A-62-209529. It is preferable to have. Further, when a paper support is used, a paper support having a low water absorption like the light-sensitive material described in JP-A-63-38934 and a constant light-sensitive material like the light-sensitive material described in JP-A-63-47754. Paper support having Beck's smoothness, a paper support having a low shrinkage ratio such as the light-sensitive material described in JP-A-63-81339, and air permeability such as the light-sensitive material described in JP-A-63-81340. It is also possible to use a paper support having a low pH, a paper support having a pH value of 5 to 9 such as the light-sensitive material described in JP-A-63-97941.

A photosensitive layer containing a photopolymerizable composition may be used instead of the structure of the photosensitive layer containing silver halide, a reducing agent and a polymerizable compound as described above.

As the photopolymerizable composition, a mixture of a photopolymerization initiator and a polymerizable compound can be used. The polymerizable compound that can be used in the photopolymerizable composition is the same as the above-mentioned polymerizable compound.

Examples of preferred photopolymerization initiators include α-alkoxyphenyl ketones, polycyclic quinones, benzophenones and substituted benzophenones, xanthones, thioxanthones, halogenated compounds (eg, chlorosulfonyl and chloromethyl, etc.). Aromatic compounds, chlorosulfonyl and chloromethyl heterocyclic compounds, chlorosulfonyl and chloromethylbenzophenones, and fluorenones), haloalkanes, α-halo-α-phenylacetophenones, photoreducible dye-reducing redox Couples, halogenated paraffins (eg, brominated or chlorinated paraffins), benzoylalkyl ethers, and lophine dimer-mercapto compound couples can be mentioned.

Specific examples of preferred photopolymerization initiators 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)-
Examples include a combination of 4,4 ', 5,5'-tetraphenylbiimidazole and 2-mercapto-5-methylthio-1,3,4-thiodiazole.

As the photopolymerization initiator, the compounds described above may be used alone or in combination of several kinds.

In the light-sensitive material of the present invention, the photopolymerization initiator is preferably used in the range of 0.5 to 30% by weight based on the polymerizable compound used. A more preferable range of use is 2 to 20% by weight.

Further, instead of the photopolymerizable composition, a photopolymerizable compound exhibiting photopolymerizability by itself may be used.

Examples of the photopolymerizable compound include acrylamide, barium acrylate, glycerin triacrylate, N, N'-
Examples thereof include methylene bis acrylamide, polyethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, vinylcarbazole and silicic acid ester of polyvinyl alcohol. Moreover, the compound which introduce | transduced the photosensitive group into the polymeric compound as mentioned above can also be used as a photopolymerizable compound.

Hereinafter, various aspects of the light-sensitive material, optional components that can be contained in the light-sensitive layer, auxiliary layers that can be optionally provided in the light-sensitive material, and the like will be sequentially described.

As an optional component that can be contained in the photosensitive layer of the photosensitive material, a color image forming substance, a sensitizing dye, an organic silver salt, a radical generator, various image forming accelerators, a thermal polymerization inhibitor, a thermal polymerization initiator, Development stopper, fluorescent whitening agent, anti-fading agent, dye or pigment for preventing halation or irradiation, dye having a property of decolorizing by heating or light irradiation, matting agent, anti-smudge agent, plasticizer, water releasing agent, Examples include binders, photopolymerization initiators, solvents for polymerizable compounds, water-soluble vinyl polymers and the like.

The photosensitive material can obtain a polymer image by the constitution of the photosensitive layer described above, but a color image can also be formed by including a color image forming substance as an optional component in the photosensitive layer.

The color image-forming substance that can be used in the light-sensitive material is not particularly limited, and various types can be used. That is, a substance that is itself colored (dye or pigment), or energy that is colorless or pale but is external (heat, pressure, light irradiation, etc.) or another component (developing agent) A substance (color former) that develops a color upon contact is also included in the color image forming substance. Incidentally, the general light-sensitive material using a color image forming substance is described in the above-mentioned JP-A-61-73145. Further, for a light-sensitive material using a dye or a pigment as a color image forming substance, JP-A-62-187346, for a light-sensitive material using a leuco dye, there is a JP-A-62-209436, a triazene compound is used. Japanese Patent Laid-Open No. 62-251741 discloses a light-sensitive material, and Japanese Patent Laid-Open Nos. 62-288827 and 62-288828 use a cyan-colored leuco dye for a light-sensitive material using a yellow-colored leuco dye. The light-sensitive materials described above are described in JP-A-63-53542. Dyes and pigments, which are themselves colored substances, are commercially available as well as various documents (eg, "Handbook of Dyes" edited by the Society of Synthetic Organic Chemistry, published in 1970, "Handbook of Latest Pigments" edited by the Japan Pigment Technology Association, Known ones described in 1977 can be used. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, examples of the substance that develops color by some energy such as heating, pressurization, and light irradiation are thermochromic compounds,
Known are piezochromic compounds, photochromic compounds, and leuco bodies such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. All of them develop color by heating, pressurizing, light irradiation or air oxidation.

Examples of the substance that develops a color upon contact with another component include various systems that develop a color by an acid-base reaction between two or more components, a redox reaction, a coupling reaction, a chelate formation reaction and the like. For example, pressure-sensitive copying paper (pages 29-58), azography (pages 87-95), described in "Introduction to Special Paper Chemistry" by Hiroyuki Moriga (published in 1975).
Known coloring systems such as thermosensitive coloring due to chemical changes (pages 118-120), or the proceedings of the seminar "Latest dye chemistry-Attractive utilization and new development as functional dyes-" sponsored by the Kinki Chemical Industry Association 26-32 Page, (June 19, 1980), the coloring system etc. which can be used. Specifically, a color-developing system composed of a colorant having a partial structure such as lactone, lactam, and spiropyran used for pressure-sensitive paper and an acidic substance (developing agent) such as acid clay or phenol; an aromatic diazonium salt or System utilizing azo coupling reaction of diazotate, diazosulfonates with naphthols, anilines, active methylenes; reaction of hexamethylenetetramine with ferric ion and gallic acid and phenolphthalein-complexons A chelate forming reaction such as a reaction with an alkaline earth metal ion; a redox reaction such as a reaction between ferric stearate and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

The color image-forming substance is 0.5 per 100 parts by weight of the polymerizable compound.
It is preferably used in a proportion of from 20 to 20 parts by weight, preferably from 2 to 7
It is more preferable to use it in a ratio of parts by weight. When a color developer is used, it is about 0.
It is preferably used in a proportion of 3 to 80 parts by weight.

When two types of substances that cause a color reaction in a contact state are used as the above-mentioned color image forming substances, one of the substances that cause the color reaction and the polymerizable compound are contained in microcapsules. Then, a color image can be formed on the photosensitive layer by allowing another substance among the substances that cause the above-mentioned color forming reaction to exist outside the microcapsules containing the polymerizable compound. A light-sensitive material capable of obtaining a color image without using an image receiving material as described above is described in JP-A-62-209444.

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and a silver halide sensitizing dye known in the photographic art can be used. The sensitizing dye, methine dye, cyanine dye, merocyanine dye, complex cyanine dye, holopolar cyanine dye, hemicyanine dye,
Examples include styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. In particular, for the purpose of supersensitization, it is common to use a combination of sensitizing dyes. Further, together with the sensitizing dye, a dye which does not have a spectral sensitizing effect itself, or a substance which does not substantially absorb visible light but exhibits supersensitization may be used together. The addition amount of the sensitizing dye is generally about 10 ^{-8 to} 10 ^-2 mol per mol of silver halide.

The sensitizing dye is preferably added at the stage of preparing a silver halide emulsion described below. Regarding a light-sensitive material obtained by adding a sensitizing dye in the step of forming silver halide grains, JP-A-62-947 discloses a sensitizing dye of a silver halide emulsion after formation of silver halide grains. For the light-sensitive material obtained by adding it in the preparation stage, see JP-A-62-2
Each is described in Japanese Patent No. 10449. Further, specific examples of sensitizing dyes that can be used in the light-sensitive material are also described in JP-A-62-947 and JP-A-62-210449. Further, as in the light-sensitive material described in Japanese Patent Application No. 61-208786, an infrared-sensitive sensitizing dye may be used in combination.

Addition of an organic silver salt to a light-sensitive material is particularly effective in heat development processing. That is, when heated to a temperature of 80 ° C. or higher, the organic silver salt is considered to participate in the redox reaction using the latent image of silver halide as a catalyst. in this case,
It is preferable that the silver halide and the organic silver salt are in contact with or in close proximity to each other. As the organic compound that constitutes the organic silver salt, an aliphatic or aromatic carboxylic acid,
Examples thereof include thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Among them, benzotriazole is particularly preferable. The organic silver salt is generally a silver halide 1
It is used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol. The same effect can be obtained by adding an organic compound (for example, benzotriazole) constituting the organic silver salt to the photosensitive layer instead of the organic silver salt. A light-sensitive material using an organic silver salt is described in JP-A-62-3246. The organic silver salt as described above is 0.
It is preferably used in the range of 1 to 10 mol, more preferably 0.01 to 1 mol.

The above-mentioned radical generator which participates in the polymerization acceleration (or polymerization suppression) reaction of the reducing agent may be added to the photosensitive layer.
As the radical generator, a light-sensitive material using silver triazene is disclosed in JP-A-62-195639, and a light-sensitive material using silver diazotate is disclosed in JP-A-62-195640. For the material, see JP-A-62
-195641 gazette, there is a description, respectively.

Various image formation accelerators can be used in the light-sensitive material. The image forming accelerator includes a silver halide (and / or an organic silver salt) and a reducing agent for promoting the redox reaction between the redox agent and the photosensitive material to the image receiving material or image receiving layer (these will be described later). It has the function of promoting the movement of image forming substances. The image formation accelerator is a base, a base precursor, an oil, a surfactant, a
It is further classified into a compound having an antifoggant function and / or a development promoting function, a hot solvent, a compound having an oxygen removing function, and the like. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Therefore, the above classification is convenient, and in fact, one compound often has a plurality of functions.

Examples of various image formation accelerators are shown below.

Examples of preferable bases include alkali metal or alkaline earth metal hydroxides as inorganic bases; alkali metal or alkaline earth metal tertiary phosphates, borates,
Carbonates, metaborates; combinations of zinc hydroxide or zinc oxide with chelating agents such as sodium picolinate;
Ammonium hydroxides; quaternary alkyl ammonium hydroxides; hydroxides of other metals, and the like, and organic bases include aliphatic amines (trialkylamines,
Hydroxylamines, aliphatic polyamines); Aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis [p-
(Dialkylamino) phenyl] methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, and the like, with a pKa of 7 or more being particularly preferable.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heating, compounds that release amines by reactions such as intramolecular nucleophilic substitution reaction, Rossen rearrangement, Beckmann rearrangement, etc. Compounds that release and generate a base by electrolysis are preferably used. Specific examples of the base precursor include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, phenylsulfonylacetic acid guanidine, 4-chlorophenylsulfonylacetic acid guanidine, and 4-methyl-. Examples thereof include guanidine sulfonylphenylsulfonylacetate and guanidine 4-acetylaminomethylpropiolate.

The base or base precursor can be used in a wide range of amount in the light-sensitive material. The base or base precursor is suitably used in an amount of 100% by weight or less, more preferably 0.1% by weight to 4% by weight of the coating film of the photosensitive layer.
A range of 0% by weight is useful. In the present invention, the base and /
Alternatively, the base precursor may be used alone or as a mixture of two or more kinds.

A light-sensitive material using a base or a base precursor is described in Japanese Patent Application No. 60-227528. Further, regarding a photosensitive material using a tertiary amine as a base, JP-A-62-170954 discloses a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound having a melting point of 80 to 180 ° C. JP-A-62-209523 discloses a light-sensitive material using a guanidine derivative having a solubility of 0.1% or less.
Japanese Patent Application No. 61-96341 describes the light-sensitive material using a hydroxide or salt of an alkali metal or an alkaline earth metal.

Further, regarding a light-sensitive material using an acetylide compound as a base precursor, JP-A-63-24242 discloses that a propiolic acid salt is used as a base precursor, and silver, copper, a silver compound or a copper compound is used as a catalyst for a base formation reaction. JP-A-63-46446 discloses a light-sensitive material containing the same, JP-A-63-81338 discloses a light-sensitive material containing the propiolic acid salt and the silver, copper, a silver compound or a copper compound isolated from each other. Japanese Patent Laid-Open No. 63-9
7942, using a propiolic acid salt as a base precursor, for a light-sensitive material further containing a heat-meltable compound as a reaction accelerator of the base formation reaction, JP-A-63-46447, sulfonyl acetate as a base precursor. The photosensitive material containing a heat-fusible compound as a reaction accelerator for a base-forming reaction is disclosed in JP-A-63-48543, and a photosensitive material using a compound in which an isocyanate or isothiocyanate is bound to an organic base is used as a base precursor. The materials are described in JP-A-63-24242.

When using a base or a base precursor for the light-sensitive material,
It is preferable that a silver halide, a reducing agent and a polymerizable compound are contained in the microcapsules described above, and a base or a base precursor is present in the photosensitive layer outside the microcapsules. Alternatively, a base or a base precursor may be contained in another microcapsule as in the light-sensitive material described in JP-A-62-209521. In addition to the above specification, a light-sensitive material using a microcapsule containing a base or a base precursor is also a light-sensitive material containing a base or a base precursor dissolved or dispersed in an aqueous solution of a water retention agent in a microcapsule.
JP-A-209522 discloses a photosensitive material containing solid fine particles carrying a base or a base precursor in a microcapsule. JP-A-62-209526 discloses a microcapsule containing a base compound having a melting point of 70 ° C to 210 ° C. The light-sensitive materials used are described in JP-A-63-65437. Further, instead of the microcapsules containing the base or the base precursor, particles containing the base or the base precursor and the hydrophobic substance in a compatible state may be used as in the light-sensitive material described in JP-A-63-97943. .

The base or base precursor is described in JP-A-62-25314.
It may be added to an auxiliary layer (layer containing a base or a base precursor described later) other than the photosensitive layer as described in JP-A No. Further, as described in JP-A-63-32546, the above-mentioned support may be made porous, and a base or a base precursor may be contained in this porous support.

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

As the surfactant, pyridinium salts described in JP-A-59-74547, ammonium salts, phosphonium salts,
Examples thereof include polyalkylene oxides described in JP-A-59-57231.

The compound having an antifoggant function and / or a development promoting function can be used for the purpose of obtaining a clear image (image having a high S / N ratio) having a high maximum density and a low minimum density. For a photosensitive material using an antifoggant as a compound having an antifoggant function and / or a development accelerating function, Japanese Patent Application Laid-Open No. 62-151838 discloses a photosensitive material using a compound having a cyclic amide structure. JP-A-61-151841, JP-A-62-151842 for photosensitive materials using thioether compounds, JP-A-62-151843 for photosensitive materials using polyethylene glycol derivatives, thiol For a light-sensitive material using a derivative, see JP-A-62-151844, and for a light-sensitive material using an acetylene compound, JP-A-62-17823.
JP-A No. 62-183450 discloses a photosensitive material using a sulfonamide derivative, and JP-A No. 63-91653 discloses a photosensitive material using a quaternary ammonium salt. .

As the hot solvent, a compound which can be a solvent for the reducing agent, a compound which is a substance having a high dielectric constant and is known to accelerate the physical development of the silver salt, and the like are useful. As a useful thermal solvent,
Polyethylene glycols described in U.S. Patent No. 3347675, derivatives of acids such as oleic acid esters of polyethylene oxide, beeswax, glycerol monostearate, -SO ₂ - high dielectric constant compounds having and / or -CO- groups, U.S. Patent No. The polar substances described in Japanese Patent No. 3667959, 1,10-decanediol, methyl anisate, biphenyl suberate and the like described in Research Disclosure, December 1976, pages 26 to 28 are preferably used. The photosensitive material using a hot solvent is described in JP-A-62-86355.

The compound having a function of removing oxygen can be used for the purpose of eliminating the influence of oxygen during development (oxygen has a polymerization inhibiting action). Examples of the compound having an oxygen removing function include compounds having two or more mercapto groups. A light-sensitive material using a compound having two or more mercapto groups is described in JP-A-SHO
It is described in JP-A-62-209443.

The thermal polymerization initiator that can be used in the light-sensitive material is generally a compound that thermally decomposes under heating to generate a polymerization initiation species (particularly a radical), and is usually used as an initiator of radical polymerization. The thermal polymerization initiator is described on pages 6 to 18 of “Addition Polymerization / Ring-Opening Polymerization,” 1983, Kyoritsu Shuppan, edited by the Society of Polymer Science, Japan, Editorial Committee for Polymer Experiments. The thermal polymerization initiator is preferably used in the range of 0.1 to 120% by weight with respect to the polymerizable compound, preferably 1 to 1
More preferably, it is used in the range of 0% by weight. In addition,
In a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Further, a light-sensitive material using a thermal polymerization initiator is described in JP-A-62-70836.

A development terminator that can be used in a light-sensitive material is a compound that interacts with a compound or silver and a silver salt that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop development after proper development. Is a compound that suppresses development. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, a nitrogen-containing heterocyclic compound, and a mercapto compound. Examples of acid precursors include JP-A-60-10883.
Examples thereof include oxime esters described in JP-A Nos. 7 and 60-192939 and compounds releasing an acid by Rossen rearrangement described in JP-A-60-230133. Examples of electrophilic compounds that undergo a substitution reaction with a base upon heating include the compounds described in JP-A-60-230134.

Dyes or pigments may be added to the photosensitive layer of the photosensitive material for the purpose of preventing halation or irradiation. A light-sensitive material having a white pigment added to the light-sensitive layer for the purpose of preventing halation or irradiation is described in JP-A-63-29748.

A dye having a property of being decolorized by heating or light irradiation may be contained in the microcapsule. The dye having the property of being decolorized by heating or light irradiation can function as a yellow filter in a conventional silver salt photographic system. A light-sensitive material using a dye having the property of being decolorized by heating or irradiation with light as described above is described in JP-A-63-97940.

As the anti-smudge agent used in the light-sensitive material, solid particles at room temperature are preferable. The average particle size of the particles is preferably in the range of 3 to 50 μm in volume average diameter,
The range of 5 to 40 μm is more preferable. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the microcapsules.

The binder that can be used in the light-sensitive material can be contained in the light-sensitive layer alone or in combination. It is preferable to mainly use a hydrophilic binder. A transparent or semitransparent hydrophilic binder is typical as the hydrophilic binder. The photosensitive material using a binder is described in JP-A-61-69062. A light-sensitive material using a binder together with microcapsules is described in JP-A-62-209525.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing the unpolymerized polymerizable compound after image transfer. A light-sensitive material using a photopolymerization initiator is described in JP-A-62-161149.

When a solvent for a polymerizable compound is used in the light-sensitive material, it is preferably used by enclosing it in a microcapsule different from the microcapsule containing the polymerizable compound. The photosensitive material using an organic solvent miscible with the polymerizable compound encapsulated in microcapsules is described in JP-A-62-209524.

A water-soluble vinyl polymer may be adsorbed on the above-described silver halide grains for use. A light-sensitive material using a water-soluble vinyl polymer as described above is described in JP-A-63-91652.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and usage thereof are also described in the application specification regarding the series of photosensitive materials described above, and Research Disclosure Magazine Vol. 170, June 1978. 17029 (pages 9 to 15).

The light-sensitive layer of the light-sensitive material comprising the components described above has a p-like property as in the light-sensitive material described in JP-A-62-275235.
The H value is preferably 7 or less.

Examples of layers that can be optionally provided in the light-sensitive material include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer,
Examples thereof include a cover sheet or a protective layer, a layer containing a base or a base precursor, a base barrier layer, and an antihalation layer (colored layer).

Instead of using an image receiving material described later as a method of using the photosensitive material, the image receiving layer may be provided on the photosensitive material and an image may be formed on this layer. The image receiving layer provided on the photosensitive material may have the same structure as the image receiving layer provided on the image receiving material. Details of the image receiving layer will be described later.

For the photosensitive material using the heating element layer, see JP-A-61-2.
In JP 94434, JP-A-62-210447 discloses a photosensitive material provided with a cover sheet or a protective layer, and JP-A-62-253140 discloses a photosensitive material provided with a layer containing a base or a base precursor. For a light-sensitive material provided with a colored layer as an antihalation layer, see JP-A-63-101842.
Each of these is described in Japanese Patent Publication No. Further, regarding a light-sensitive material provided with a base barrier layer, the above-mentioned JP-A-62-25314 is also used.
It is described in Japanese Patent Publication No. 0. Further, examples of other auxiliary layers and usage modes thereof are also described in the specification of the series of photosensitive materials described above.

The method for producing the photosensitive material will be described below.

Although various methods can be used as a method for producing a light-sensitive material, a general production method is to prepare a coating solution by dissolving, emulsifying or dispersing the components of the photosensitive layer in an appropriate solvent, and applying the solution. It comprises a step of obtaining a light-sensitive material by applying the liquid to the support as described above and drying.

Generally, the coating solution is prepared by preparing a liquid composition containing each component for each component, and then mixing each liquid composition. The liquid composition may be prepared so as to contain a plurality of components. A part of the components of the photosensitive layer may be added and used at the stage of preparing the liquid composition or the coating solution or after the preparation. Furthermore, as described below, a method of preparing a secondary composition by emulsifying an oily (or aqueous) composition containing one or more components in an aqueous (or oily) solvent can also be used. .

With respect to the main components contained in the photosensitive layer, a method for preparing a liquid composition and a coating liquid is shown below.

The halogenated emulsion can be prepared by any known method such as an acidic method, a neutral method or an ammonia method.

As the reaction mode of the soluble silver salt and the soluble halogen salt,
Either a one-sided mixing method, a double-sided mixing method or a combination thereof may be used. The back-mixing method in which grains are formed under conditions of excess silver ions and the controlled double-jet method in which pAg is kept constant can also be adopted. Further, in order to accelerate the grain growth, the addition concentration, the addition amount or the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-158124 and JP-A-5-158124).
5-158124, and U.S. Pat. No. 3,650,757).

The silver halide emulsion used for producing the light-sensitive material may be either a surface latent image type in which a latent image is mainly formed on the surface of a grain or an internal latent image type in which a latent image is formed inside the grain. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Internal latent image type emulsions suitable for this purpose are described in U.S. Pat. Nos. 2,592,250 and 3,761,276, JP-B-58-3534, JP-A-58-136641, and the like. Preferred nucleating agents to be combined with the above emulsions are U.S. Pat. Nos. 3,227,552, 4,245,037, 4,255,511, 42,66013, 4,276,364 and West German Published Patent (OL).
S) No. 2635316 is described in each specification.

In the preparation of a silver halide emulsion used for producing a light-sensitive material, it is preferable to use a hydrophilic colloid as a protective colloid. Examples of hydrophilic colloids are gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose hydrochloride, etc., sodium alginate, sugar derivatives such as starch derivatives, and polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole. Examples thereof include various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinylpyrazole. Of these, gelatin is preferred. As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin or oxygen-processed gelatin may be used, and a hydrolyzate or enzymatic decomposition product of gelatin may also be used.

The silver halide emulsion contains ammonia, an organic thioether derivative (see JP-B-47-386) and a sulfur-containing compound (see JP-A-53-144319) as a silver halide solvent in the step of forming silver halide grains. Etc. can be used. Further, in the process of grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt or the like may be allowed to coexist. Further, water-soluble iridium salts such as iridium chloride (III or IV) and hexachloroiridium ammonium for the purpose of improving high illumination failure and low illumination failure,
Alternatively, a water-soluble rhodium salt such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after formation of a precipitate or after physical ripening. In this case, it can be carried out according to the Nudel washing method or the sedimentation method. The silver halide emulsion may be used as it is without being post-ripened, but it is usually chemically sensitized before use. In the emulsion for a conventional type photosensitive material, known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-1).
26526 and 58-215644).

When a sensitizing dye is added to the silver halide emulsion,
It is preferably added at the stage of preparing a silver halide emulsion as in the light-sensitive materials described in JP-A-62-947 and Japanese Patent Application No. 61-55510. When a nitrogen-containing heterocyclic compound is added as the compound having the fog-preventing function and / or the development-accelerating function, it should be added in the step of forming silver halide grains or the ripening step in the preparation of a silver halide emulsion. Is preferred. The method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added at the stage of forming silver halide grains or at the stage of ripening is described in JP-A-62-161144.

When the above-mentioned organic silver salt is contained in the photosensitive layer, the organic silver salt emulsion can be prepared by a method similar to the method for preparing the silver halide emulsion.

In the production of a light-sensitive material, the polymerizable compound can be used as a medium for preparing the composition of other components in the light-sensitive layer. For example, a silver halide (including a silver halide emulsion), a reducing agent, a color image-forming substance and the like can be dissolved, emulsified or dispersed in a polymerizable compound and used for producing a light-sensitive material. In particular, when a color image forming substance is added, it is preferable to include it in the polymerizable compound. In addition, components such as wall materials necessary for microencapsulation may be included in the polymerizable compound.

The photosensitive composition containing a polymerizable compound containing silver halide can be prepared using a silver halide emulsion.
In addition to the silver halide emulsion, a silver halide powder prepared by freeze-drying or the like can be used for the preparation of the photosensitive composition. The photosensitive composition containing these silver halides can be obtained by stirring with a homogenizer, blender, mixer, or other commonly used stirrer.

In addition, in the polymerizable compound used for preparing the photosensitive composition, it is preferable to dissolve a copolymer composed of a hydrophilic repeating unit and a hydrophobic repeating unit. For a photosensitive composition containing the above copolymer, see JP-A-62-2
It is described in the 09449 publication.

Further, instead of using the above copolymer, microcapsules containing a silver halide emulsion as a core substance may be dispersed in a polymerizable compound to prepare a photosensitive composition. The photosensitive composition containing microcapsules containing the above silver halide emulsion as a core substance is described in JP-A-62-164041.

The polymerizable compound (including those containing other constituents such as the above-mentioned photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. In addition, JP-A-61-2
When the oil droplets of the polymerizable compound are microencapsulated as in the light-sensitive material described in Japanese Patent No. 75742, a wall material necessary for microencapsulation is added to this emulsion, and the outer shell of the microcapsule is further added. The forming treatment can also be carried out at this emulsion stage. Further, a reducing agent or any other component may be added at the stage of the above emulsion.

When the polymerizable compound is a photosensitive composition containing silver halide in the emulsion of the polymerizable compound (including the microcapsule liquid subjected to the microencapsulation treatment) described above, the coating liquid for the photosensitive material is used as it is. Can be used as Emulsions other than the above can be mixed with the composition of other components such as a silver halide emulsion and optionally an organic silver salt emulsion to prepare a coating solution. Other components may be added at the stage of this coating solution as in the case of the above emulsion.

A photosensitive material is manufactured by coating the support with the coating solution for the photosensitive layer prepared as described above and drying. The coating of the coating liquid on the support can be easily carried out according to known techniques.

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

The light-sensitive material may be imagewise exposed at the same time or after imagewise exposure.
It is used after being developed.

Although various exposing means can be used as the exposing method, a latent image of silver halide is generally obtained by imagewise exposure of radiation including visible light. The type of light source and the amount of exposure are
Sensitive wavelength of silver halide (when dye sensitization is performed,
It can be selected according to the sensitized wavelength) and the sensitivity. The original image may be a monochrome image or a color image.

The photosensitive material is subjected to development processing simultaneously with the imagewise exposure or after the imagewise exposure. However, in the second aspect,
It is used after imagewise exposure. The photosensitive material is Japanese Patent Publication No. 45-111
You may perform the development processing using the developing solution described in Japanese Patent Laid-Open No. 49, etc. Incidentally. As described above, the heat development treatment is carried out.
Since the method described in JP 61-69062 A is a dry process, it has advantages that the operation is simple and the process can be performed in a short time. Therefore, the latter is particularly excellent in the development processing of the photosensitive material.

As a heating method in the heat development treatment, various conventionally known methods can be used. Further, like the light-sensitive material described in JP-A-61-294434, the light-sensitive material may be provided with a heating element layer and used as a heating means. Further, as in the image forming method described in JP-A-62-210461, the heat development treatment may be carried out while suppressing the amount of oxygen present in the photosensitive layer. Heating temperature is generally 80 ℃ to 200 ℃
C., preferably 100 to 160.degree. The heating time is generally 1 second or longer, preferably 1 second to 5 minutes, and more preferably 1 second to 1 minute.

Instead of incorporating the above-mentioned base or base precursor into the light-sensitive material, development processing may be carried out while adding the base or base precursor to the light-sensitive layer or immediately after the addition. As a method for adding a base or a base precursor, a method using a sheet containing a base or a base precursor (base sheet) is the easiest and preferable. An image forming method using the above-mentioned base sheet is described in JP-A-63-32546.

The light-sensitive material can be subjected to the heat development treatment as described above to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. In the light-sensitive material, the polymerizable compound in the portion where the latent image of silver halide is formed is generally polymerized in the above heat development treatment.
It is also possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed, by adjusting the kind and amount of the reducing agent as in the light-sensitive material described in JP-A-36.

As described above, the photosensitive material can obtain a polymer image on the photosensitive layer. Further, a dye or a pigment may be fixed to the polymer to obtain a dye image.

When the light-sensitive material is constituted like the light-sensitive material described in the above-mentioned JP-A-62-209444, the light-sensitive material subjected to the developing treatment is pressed to destroy the microcapsules and cause a color-forming reaction. It is possible to form a color image on the light-sensitive material by bringing these substances into contact with each other.

Further, the image receiving material can be used to form an image on the image receiving material.

Next, the image receiving material will be described. For general image forming methods using an image receiving material or image receiving layer, see
It is described in Japanese Patent No. 61-278849.

As the support for the image receiving material, in addition to the support that can be used for the light-sensitive material described above, variator paper can be used. When a porous material such as paper is used as the support of the image receiving material, it is preferable that the image receiving material has a certain smoothness like the image receiving material described in JP-A-62-209530. An image receiving material using a transparent support is described in JP-A-62-209531.

The image receiving material generally has an image receiving layer provided on a support. The image receiving layer is in accordance with the coloring system of the color image forming substance described above,
Various compounds can be used to make up any form. When a polymer image is formed on an image receiving material, a dye or a pigment is used as a color image forming substance, the image receiving material may be composed of only the above support.

For example, when a color-developing system comprising a color-developing agent and a color-developing agent is used, the image-receiving layer may contain the color-developing agent. Further, the image receiving layer may be formed as at least one layer containing a mordant. The mordant can be selected from compounds known in the photographic art and the like in consideration of conditions such as the type of color image forming substance and used. If necessary, a plurality of mordants having different mordant powers may be used to form two or more image receiving layers.

The image receiving layer preferably contains a polymer as a binder. As the binder, the binder that can be used in the photosensitive layer of the photosensitive material described above can be used. Further, a polymer having low oxygen permeability may be used as a binder as in the image receiving material described in JP-A-62-209454.

The image receiving layer may contain a thermoplastic compound. When the image receiving layer contains a thermoplastic compound, it is preferable that the image receiving layer itself is formed as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above-described structure has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after the image formation. The thermoplastic compound is not particularly limited and can be arbitrarily selected and used from known plastic resins (plastics) and waxes. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200 ° C. or lower. Regarding the image-receiving material having the image-receiving layer containing the thermoplastic compound fine particles as described above, JP-A-62-280071 is used.
No. 62-280739.

The image receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material,
The color image forming substance is transferred together with the unpolymerized polymerizable compound as described later. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of smoothly proceeding the curing treatment (fixing treatment) of the unpolymerized polymerizable compound. An image receiving material having an image receiving layer containing a photopolymerization initiator is disclosed in JP-A-62-161149, and an image receiving material having an image receiving layer containing a thermal polymerization initiator is disclosed in JP-A-62-161149.
-210444 gazette describes each.

The dye or pigment may be contained in the image receiving layer for the purpose of writing characters, symbols, frames, etc. on the image receiving layer or for the purpose of making the background of the image a specific color. Further, a dye or a pigment may be included in the image receiving layer for the purpose of facilitating the front / back discrimination of the image receiving material. As the dye or pigment, various known substances including dyes or pigments that can be used in image formation can be used, but the dye or pigment may impair the image formed in the image receiving layer. In some cases, it is preferable to lower the dyeing density of the dye or pigment (for example, the reflection density is 1 or less), or to use the dye or pigment having the property of being decolorized by heating or light irradiation.
An image receiving material having an image receiving layer containing a dye or pigment having the property of being decolorized by heating or light irradiation is described in JP-A-62-251741.

Further, when a white pigment such as titanium dioxide or barium sulfate is added to the image receiving layer, the image receiving layer can function as a white reflective layer. When the image receiving layer functions as a white reflective layer, the white pigment is 10 g to 1 g per 1 g of the thermoplastic compound.
It is preferably used in the range of 00 g.

When the dye or pigment as described above is contained in the image receiving layer, it may be uniformly contained or may be partially distributed. For example, a support described below is made of a material having a light-transmitting property, and a part of the reflection image can be a projection image by including the white pigment in a part of the image receiving layer. By doing so, unnecessary image information in the projected image can be written as a reflected image in the image receiving layer portion containing the white pigment.

The image receiving layer may be composed of two or more layers depending on the functions as described above. The thickness of the image receiving layer is 1 to 10
The thickness is preferably 0 μm, more preferably 1 to 20 μm.

A protective layer may be further provided on the image receiving layer. Further, a layer made of an aggregate of fine particles of a thermoplastic compound may be further provided on the image receiving layer. An image receiving material having a layer comprising an aggregate of fine particles of a thermoplastic compound provided on the image receiving layer is described in JP-A-62-210460.

Further, a layer containing an adhesive or an adhesive and release paper may be sequentially laminated on the surface of the support opposite to the surface on which the image receiving layer is provided. The sticker-shaped image receiving material having the above structure is described in JP-A-63-24647 by the present applicant.

The photosensitive material is subjected to development processing as described above, and by pressing the image receiving material in a state of being superposed, the unpolymerized polymerizable compound is transferred to the image receiving material, and a polymer image can be obtained on the image receiving material. it can. Regarding the pressing means,
Various conventionally known methods can be used.

Further, in the embodiment in which the photosensitive layer contains a color image-forming substance,
By carrying out a developing treatment in the same manner, the polymerizable compound is polymerized and cured, and thereby the color image forming substance in the cured portion is immobilized. Then, by pressing the photosensitive material and the image receiving material in a superposed state, the color image forming substance in the uncured portion is transferred to the image receiving material, and a color image can be obtained on the image receiving material.

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-62-210459. The above method also has an advantage that the unpolymerized polymerizable compound transferred onto the image receiving material is polymerized and the storability of the obtained image is improved.

Also, various patent applications have already been filed for various image recording apparatuses suitable for carrying out the above-described series of image forming methods using a light-sensitive material (JP-A-62-147461).

Photosensitive materials include black-and-white or color imaging and printing materials, printing materials, printing plates, X-ray materials, medical materials (for example, ultrasonic diagnostic machine CRT imaging materials) computer graphic hard copy materials, copy materials. There are many uses such as machine sensitizers.

The present invention will be described more specifically by the following examples. However, the present invention is not limited to these.

[Example 1] [Preparation of light-sensitive material] Preparation of silver halide emulsion (A-1) (blue sensitivity) A gelatin aqueous solution (16 g of gelatin and 0.5 g of sodium chloride were added to 1500 ml of water, and the pH was adjusted to 3 with 1N sulfuric acid. Adjust to .2, 5
300 ml of an aqueous solution containing 71 g of potassium bromide and an aqueous solution of silver nitrate (a solution of 0.59 mol of silver nitrate dissolved in 300 ml of water) were simultaneously added to the solution kept at 0 ° C.) over 50 minutes at an equal flow rate. One minute after completion of this addition, 43 ml of a 1% methanol solution of the following sensitizing dye (1) was added, and 15 minutes after the addition of the sensitizing dye, an aqueous solution containing 2.9 g of potassium iodide 10 was added.
0 ml and an aqueous solution of silver nitrate (0.018 mol of silver nitrate dissolved in 100 ml of water) were added at an equal flow rate over 5 minutes. To this emulsion was added 1.2 g of poly (isobutylene-co-monomaleate monosodium), which was allowed to settle, washed with water and desalted.
Gelatin (12 g) was added and dissolved, and sodium thiosulfate (0.5 mg) was further added, and chemical sensitization was performed at 60 ° C for 15 minutes to obtain a monodisperse tetradecahedral silver iodobromide emulsion (A-1) having an average grain size of 0.22 µm.
1000 g was prepared.

Sensitizing dye (1) Preparation of silver halide emulsion (A-2) (green-sensitive) 20 g of gelatin and 0.5 g of sodium chloride were added to 1600 ml of water and the pH was adjusted to 3.2 with 1N sulfuric acid.
200 ml of an aqueous solution containing 71 g of potassium bromide and an aqueous solution of silver nitrate (a solution of 0.59 mol of silver nitrate dissolved in 200 ml of water) were simultaneously added to the mixture (which was kept at 2 ° C.) at an equal flow rate for 30 minutes. One minute after completion of this addition, 48 ml of a 1% methanol solution of the sensitizing dye (2) shown below was added, and 10 minutes after the addition of the sensitizing dye, an aqueous solution containing 2.9 g of potassium iodide 10 was added.
0 ml and an aqueous solution of silver nitrate (0.018 mol of silver nitrate dissolved in 100 ml of water) were added at an equal flow rate over 5 minutes. To this emulsion, 1.2 g of poly (isobutylene-co-monomaleate monosodium) was added, allowed to settle, washed with water and desalted, gelatin 18 g was added and dissolved, and further 0.7 mg of sodium thiosulfate was added, Chemical sensitization for 15 minutes at 60 ℃,
1000 g of monodisperse tetradecahedral silver iodobromide emulsion (A-2) having an average grain size of 0.12 μm was prepared.

Sensitizing dye (2) Preparation of silver halide emulsion (A-3) (red-sensitive) Gelatin aqueous solution (20g of gelatin and 0.5g of sodium chloride were added to 1600ml of water, pH was adjusted to 3.5 with 1N sulfuric acid and kept at 45 ° C) And an aqueous solution containing 71 g of potassium bromide 2
00 ml and an aqueous solution of silver nitrate (0.59 mol of silver nitrate dissolved in 200 ml of water) were simultaneously added at an equal flow rate for 30 minutes. One minute after this addition was completed, 48 ml of a 0.5% methanol solution of the following sensitizing dye (3) was added, and 15 minutes after the addition of the sensitizing dye, 100 ml of an aqueous solution containing 3.65 g of potassium iodide and an aqueous solution of silver nitrate. (0.022 mol of silver nitrate dissolved in 100 ml of water) was simultaneously added at an equal flow rate for 5 minutes. To this emulsion, 1.2 g of poly (isobutylene-co-maleate monosodium) was added, precipitated, washed with water, desalted, and then dissolved by adding 10 g of gelatin, and further adding 0.45 mg of sodium thiosulfate. Chemical sensitization was carried out at 20 ° C. for 20 minutes to prepare 1000 g of a monodisperse tetradecahedral silver iodobromide emulsion (A-3) having an average grain size of 0.13 μm.

Sensitizing dye (3) Preparation of Photosensitive Composition (A-1) (Blue Sensitivity) The following polymerizable compounds (Kayarat R604, Nippon Kayaku Co., Ltd.)
Manufactured by K.K.), 0.32 g of p-toluenesulfonamide and 14.9 g of the following yellow image forming substance were dissolved. 0.92 g of the following copolymer, 6.5 g of the following developing agent (reducing agent (I)), and hydrazine derivative (reducing agent (I
I)) 2.37 g, 0.01 g of the following antifoggant and surfactant (Emarex NP-8, manufactured by Nippon Emulsion Co., Ltd.) 1.
8 g was added, and 20 g of methylene chloride was further dissolved to prepare an oily solution.

To 10 g of the above silver halide emulsion (A-1), 2.3 ml of a 10% aqueous solution of potassium bromide was added and stirred for 5 minutes. While adding the mixed solution containing this silver halide emulsion to the above homogeneous oily solution and keeping it at 25 ° C, use a homogenizer every minute.
The mixture was stirred at 15,000 rpm for 5 minutes to obtain a photosensitive composition (A-1) in the form of a W / O emulsion.

(Polymerizable compound) (Copolymer) (Reducing agent (I)) (Reducing agent (II)) (Antifoggant) (Yellow image forming substance) Preparation of Photosensitive Composition (A-2) The silver halide emulsion (A-2) described above was used in place of the silver halide emulsion (A-1) used in the preparation of the photosensitive composition (A-1). , The same as the photosensitive composition (A-1) except that the following magenta image-forming substance was used instead of the yellow image-forming substance.
2) was prepared.

(Magenta image forming substance) Preparation of Photosensitive Composition (A-3) (Red Sensitivity) Instead of the silver halide emulsion (A-1) used in the preparation of the photosensitive composition (A-1), the silver halide emulsion (A -3) is the same as the photosensitive composition (A-1) except that the following cyan image forming substance is used instead of the yellow image forming substance.
3) was prepared.

(Cyan image forming substance) Preparation of Photosensitive Microcapsule Dispersion Liquid (A-1) (Blue Sensitivity) In the above photosensitive composition (A-1), hexamethylene diisocyanate isocyanurate ring modified product (trade name: Coronate EH, Nippon Polyurethane) 18.3 g of Kogyo Co., Ltd. was added, and the mixture was stirred at 5000 rpm for 1 minute. This mixed solution
Water 9.4 g of polyvinyl alcohol (trade name; PVA-205, manufactured by Kuraray Co., Ltd.) and 4.71 g of carboxymethyl cellulose (serogen 7A, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) adjusted to pH 5.5 with a 20% aqueous phosphoric acid solution. The mixture was added to an aqueous solution dissolved in 139 g, stirred at 1200 rpm for 5 minutes using a homogenizer, and finally water was added to obtain a W / O / W emulsion having a total amount of 376 g. The solution is heated to 60 ° C, stirred for 90 minutes, and adjusted to pH with 10% aqueous sodium hydroxide solution.
Is adjusted to 6.5 and the photosensitive microcapsule dispersion (A-
1) was prepared.

Preparation of Photosensitive Microcapsule Dispersion Liquid (A-2) (Green Sensitivity) In the preparation of the photosensitive microcapsule dispersion liquid (A-1), a photosensitive composition was used instead of the photosensitive composition (A-1). A photosensitive microcapsule dispersion liquid (A-2) was prepared in the same manner except that the product (A-2) was used.

Preparation of Photosensitive Microcapsule Dispersion Liquid (A-3) (Red Sensitivity) In the preparation of the photosensitive microcapsule dispersion liquid (A-1), a photosensitive composition was used instead of the photosensitive composition (A-1). A photosensitive microcapsule dispersion (A-3) was prepared in the same manner except that the product (A-3) was used.

Preparation of paper support 20 parts of LBSP and LBKP80 were refined to 290 cc of Canadian Freeness (CSF) using a refinery, 0.3 parts of alkyl ketene dimer (Acorbel 12, manufactured by Dick Hercules) as a neutral sizing agent, and polyamide polyamine epichlorohydrin as a fixing agent. (Kaymen 557, manufactured by Dick Hercules) 0.5 part, and cation-modified polyacrylamide (trade name; Polystron 70) as a paper-strengthening agent.
5 and 0.5 parts of Arakawa Chemical Co., Ltd. were added at an absolute dry weight ratio of pulp. Then, using a Fourdrinier paper machine, the above stock material was made into a base paper having a basis weight of 60 g / m ² and a thickness of 66 μm.

A coating liquid for forming a moisture-proof layer made of polyvinylidene chloride resin on the surface (felt surface) of the base paper produced as described above, and 100 parts of SBR latex (trade name ;: SN-304, Sumitomo Nogatak Co., Ltd.), 1 part of sodium polyacrylate (trade name: Aron T40, manufactured by Toagosei Kagaku Kogyo Co., Ltd.), 200 parts of clay (trade name: UW-90, manufactured by Engelhard), and petroleum resin (trade name: Carbumeur R) , manufactured by Dick Hercules Inc.) coating composition consisting of 100 parts of moisture-proof layer coating solution were each prepared, the coating liquid in order in each coating amount of basis weight ^{16g / m 2, 5g / m} 2 by an air knife coater Then, a paper support was prepared.

Preparation of Base Precursor Solid Dispersion 20 g of the following base precursor was added to polyvinyl alcohol (P
VA-205, manufactured by Kuraray Co., Ltd., was added to 80 g of a 4% aqueous solution and dispersed using a Dynomill at 20 ° C. until the average particle size became 2 μm or less, to prepare a base precursor solid dispersion liquid.

(Base precursor) Preparation of photosensitive material (A) Each photosensitive microcapsule dispersion liquid (A-1),
For (A-2) and (A-3), (A-
1) 11.6g, (A-2) 10.2g, (A-3) 11.6g
g, 6.8 g of the above base precursor solid dispersion, 9 ml of 20% aqueous solution of sorbitol and 10 ml of 10% dispersion of starch
Were mixed. This mixture was further mixed with 5 of the following surfactants.
% Aqueous solution 4 ml and water were added to prepare a coating solution with a total amount of 74 g.

This coating solution was coated on the above paper support at a coating amount of 50 g / m ² and dried at about 60 ° C. to prepare a light-sensitive material (A) according to the present invention.

(Surfactant) [Example 2] Photosensitive microcapsule dispersion liquids (B-1) and (B-2)
And preparation of (B-3) The photosensitive microcapsule dispersion liquid (A-1) of Example 1,
In the preparation of (A-2) and (A-3), a modified isocyanurate ring of isophorone diisocyanate (Desmodur Z4370, Sumitomo Bayer Urethane Co., Ltd.) is used instead of the modified isocyanurate ring of hexamethylene diisocyanate. )) Was used in the same manner as in Example 1 except that 26.1 g of the photosensitive microcapsule dispersion liquid (B-1),
(B-2) and (B-3) were prepared, respectively.

Preparation of Photosensitive Material (B) In the preparation of the photosensitive material (A) of Example 1, the photosensitive microcapsule dispersion liquids (A-1), (A-2) and (A) were prepared.
-3) In the same manner as in Example 1 except that the photosensitive microcapsule dispersions (B-1), (B-2) and (B-3) obtained above were used in the same amounts, respectively. A light-sensitive material (B) according to the present invention was prepared.

[Example 3] Photosensitive microcapsule dispersion liquids (C-1) and (C-2)
Preparation of (C-3) The photosensitive microcapsule dispersion liquid (A-1) of Example 1,
In the preparation of (A-2) and (A-3), a modified isocyanurate ring of 2,4-tolylene diisocyanate is replaced with a modified isocyanurate ring of hexamethylene diisocyanate (Sfrasec 3240, Nippon Polyurethane). A photosensitive microcapsule dispersion (C-1) was prepared in the same manner as in Example 1, except that 45.7 g of Kogyo Co., Ltd. was used.
(C-2) and (C-3) were prepared, respectively.

Preparation of Photosensitive Material (C) In the preparation of the photosensitive material (A) of Example 1, the photosensitive microcapsule dispersions (A-1), (A-2) and (A) were prepared.
-3) In the same manner as in Example 1 except that the photosensitive microcapsule dispersions (C-1), (C-2) and (C-3) obtained above were used in the same amounts, respectively. A light-sensitive material (C) according to the present invention was prepared.

[Comparative Example 1] Photosensitive microcapsule dispersion liquids (X-1) and (X-2)
Preparation of (X-3) and the photosensitive microcapsule dispersion liquid (A-1) of Example 1,
In the preparation of (A-2) and (A-3), instead of the isocyanurate ring-modified hexamethylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate (Coronate HL, Nippon Polyurethane Industry Co., Ltd. )) Was used in the same manner as in Example 1 except that 24.4 g of the photosensitive microcapsule dispersion liquid (X-1),
(X-2) and (X-3) were prepared, respectively.

Preparation of Photosensitive Material (X) In preparation of the photosensitive material (A) of Example 1, the photosensitive microcapsule dispersion liquids (A-1), (A-2) and (A) were prepared.
In the same manner as in Example 1 except that the photosensitive microcapsule dispersions (X-1), (X-2) and (X-3) obtained above were used in the same amounts instead of -3). A photosensitive material (X) for comparison was prepared.

[Comparative Example 2] Photosensitive microcapsule dispersion liquids (Y-1) and (Y-2)
And (Y-3) Preparation of the photosensitive microcapsule dispersion liquid (A-1) of Example 1,
In the preparation of (A-2) and (A-3), instead of an isocyanurate ring-modified product of hexamethylene diisocyanate, a trimethylolpropane adduct of xylylene diisocyanate (Takenate D110N, Takeda Pharmaceutical Co., Ltd.) (Manufactured by Mitsui Chemicals Co., Ltd.) was used in the same manner as in Example 1 except that 24.4 g was used.
2) and (Y-3) were prepared.

Preparation of Photosensitive Material (Y) In the preparation of the photosensitive material (A) of Example 1, the photosensitive microcapsule dispersion liquids (A-1), (A-2) and (A) were prepared.
In the same manner as in Example 1 except that the same amounts of the photosensitive microcapsule dispersions (Y-1), (Y-2) and (Y-3) obtained above were used instead of -3). A light-sensitive material (Y) for comparison was prepared.

[Evaluation as Microcapsule and Photosensitive Material] Each photosensitive microcapsule produced as described above,
And each light-sensitive material using them was evaluated by the following methods.

(1) Evaluation as photosensitive microcapsules Using samples prepared as described below, evaluation was performed by measuring the "bleeding temperature" of the contents in the microcapsules.

Measurement of exudation temperature The coating amount of each photosensitive microcapsule dispersion is 21 ml / m.
Samples for evaluating "bleeding temperature" were prepared by uniformly coating each of the following image-receiving materials so as to have a value of ² and drying. "Exudation temperature" is the content (core substance) contained in the capsule when the above sample is heated at 80, 100, 120, 140 and 180 ° C for 10 seconds.
The densities of color development caused by bleeding were measured using a Macbeth reflection densitometer, and these were plotted on a graph (horizontal axis; temperature / vertical axis; reflection density). Then, the plotted points were connected to draw a concentration curve, and the temperature corresponding to the rising portion of this concentration curve was read from the graph and used as the "bleeding temperature".

Preparation of image receiving material 40g sodium hexametaphosphate aqueous solution 11g in 125g water
Was added, and 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were mixed and coarsely dispersed with a mixer. The liquid was dispersed with a Dynomill disperser, and 112 g of 8% polyvinyl alcohol was added to 200 g of the obtained liquid and mixed uniformly. A paper support having a basis weight of 55 g / m ² (as a fiber length distribution defined by JIS-P-8207, the sum of the weight% of 24 mesh residue and the weight% of 42 mesh residue is 30 to 60). % Of the fiber length distribution on a paper support [Japanese Patent Application Laid-Open No. 63-186239]), a uniform coating film having a wet film thickness of 30 .mu.m is formed, and then dried to obtain an image receiving material. It was created.

(2) Evaluation as a light-sensitive material Each light-sensitive material was imagewise exposed at 2000 lux for 1 second through a continuous filter (transmission density 0 to 3.0) using a tungsten bulb, and then placed on a hot plate at 150 ° C. It was heat-developed for 10 seconds. Then, each light-sensitive material was overlaid with the above image-receiving material, and in that state, it was passed through a pressure roller of 500 kg / cm ² . For each of the color densities (blue (D _B ), green (D _G ), and red (D _R )) of the image obtained on each image receiving material, the minimum density (Dmin) and the maximum density (Dmax) are determined by a Macbeth densitometer. Was measured using.

The above measurement results are summarized in Table 1.

From the results shown in Table 1, it can be seen that the photosensitive microcapsules according to the present invention have walls having a high "bleeding temperature", that is, a glass transition point. Further, by using the light-sensitive material having the capsule of the present invention,
It can be seen that a clear image having a low minimum density and a high maximum density can be obtained.

Claims (4)

[Claims] 1. A photosensitive microcapsule in which a shell made of a resin produced from a raw material containing an isocyanate having an isocyanurate ring structure is formed around a core substance containing a silver halide and a polymerizable compound. 2. A support having a photosensitive layer containing silver halide, a reducing agent and a polymerizable compound, wherein the silver halide and the polymerizable compound are contained in microcapsules. A light-sensitive material in which a shell is composed of a resin wall produced from a raw material containing an isocyanate having an isocyanurate ring structure. 3. A photosensitive material comprising a photopolymerizable composition or a core substance containing a photopolymerizable compound, and an outer shell made of a resin produced from a raw material containing an isocyanate having an isocyanurate ring structure, is formed around the core substance. Micro capsule. 4. A photopolymerizable composition or a photosensitive layer containing a photopolymerizable compound is provided on a support, and the photopolymerizable composition or photopolymerizable compound is contained in microcapsules. A photosensitive material in which the outer shell of the capsule is a resin wall produced from a raw material containing an isocyanate having an isocyanurate ring structure.