JPH023046A - Photosensitive microcapsule and photosensitive material - Google Patents

Abstract

PURPOSE:To obtain microcapsules having improved heat resistance and improved toughness of a photosensitive microcapsules having a compound wall consisting of an inside wall contg. an aromatic polyvalent isocyanate by specifying a weight ratio of the outside wall to the inside wall. CONSTITUTION:A weight ratio of an outside wall to an inside wall constituting a compound wall is regulated to 1:1 to 1:30, wherein said outside wall contains an amino aldehyde resin and said inside wall contains silver halide particles and consists of a polyurea resin and/or polyurethane resin obtd. from a material contg. aromatic polyvalent isocyanate, both being formed around a core material. Thus, distinct picture images can be obtd. by processing in a short time even if the material is heat-developed at high temp. Since the toughness of the capsules are improved simultaneously, the preservation stability of the capsules is also improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive microcapsule containing silver halide and a photosensitive material using the same. More specifically, the present invention relates to improvements in photosensitive microcapsules having composite walls and photosensitive materials using the same.

[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 Patent Publication No. 11149/1973.
No. 47-20741, No. 49-10697, JP-A-57-138632, and JP-A No. 58-16914
The image forming method is disclosed in various publications such as No. 3.

In addition, as an improvement on the above, a method has been proposed in which a polymer compound can be formed by dry processing (Japanese Patent Application Laid-Open No. 1983-1999-1).
69062 or 6173145), these methods require a photosensitive silver salt (silver halide), a reducing agent,
A recording material (photosensitive material) comprising a support supporting a photosensitive layer comprising a crosslinkable compound (polymerizable compound) and a binder or a color image forming substance is imagewise exposed to form a latent image. This is a method in which a polymerizable compound is polymerized in the area where the silver halide latent image is formed by heating after forming.

In addition, a patent application has already been filed for a method that can polymerize the polymerizable compound in the area where the silver halide latent image is not formed. This is a method in which a reducing agent is made to act on the area where the silver latent image is formed to suppress the polymerization of the polymerizable compound while at the same time promoting polymerization in other areas.

In addition, as a preferred embodiment of the above photosensitive material, a photosensitive material in which at least a polymerizable compound and a color image forming substance among the above components are housed in the same microcapsule, and an image forming method using the same have also been proposed. (Japanese Patent Application Laid-Open Nos. 61-275742 and 61-278849)
In this way, by introducing microencapsulation, good images can be obtained. For the purpose of forming images with higher sensitivity, lλ silver halide grains are usually accommodated in a capsule together with the polymerizable compound.

The photosensitive layer consists of several layers of microcapsules containing the above-mentioned main constituents on a support together with a binder, etc. Usually, capsules are required to have a certain degree of toughness and density in order to ensure storage stability and prevent scratches during handling. However, the polymerizable compounds contained in the capsules mentioned above have a relatively low boiling point, are easily volatile, and have a low molecular weight, and also because heat development treatment is performed in the image forming process. , storage stability, etc. tend to be poor, and therefore the capsules are required to have even higher density, etc. These factors will determine the quality of the image that is finally obtained.

The present applicant has proposed photosensitive microcapsules in which an outer shell made of polyurea resin and/or polyurethane resin is formed around a core material containing silver halide and a polymerizable compound, and photosensitive microcapsules made using these. A patent application has already been filed for the material (Japanese Unexamined Patent Publication No. 62-209438), and it is a photosensitive material in which an outer shell made of amino aldehyde resin is formed around a core material containing silver halide and a polymerizable compound. A patent application has already been filed for a photosensitive material using these microcapsules (Japanese Unexamined Patent Publication No. 62-209439).

Furthermore, the present applicant has proposed that an outer wall made of an amino aldehyde resin and an inner wall made of a polyurea and/or polyurethane resin containing silver halide particles are formed around a core material containing a polymerizable compound. A patent application has been filed for photosensitive microcapsules and photosensitive materials using the same (Japanese Patent Application No. 105099/1982). By using capsules with composite walls like this, the storage stability of photosensitive materials can be improved. It can be improved.

[Summary of the Invention] An object of the present invention is to provide photosensitive microcapsules that have even higher heat resistance and toughness.

Another object of the present invention is to provide a photosensitive material that provides images with good contrast by using the capsules as described above.

In particular, one object of the present invention is to provide a photosensitive material that can shorten the development time by improving the heat resistance and toughness of the capsule, and is also easy to handle.

In the present invention, an amino acid is added around a core material containing a polymerizable compound.
Photosensitivity in which a composite wall is formed consisting of an outer wall made of aldehyde resin and an inner wall made of polyurea and/or polyurethane resin obtained from raw materials containing silver halide particles and aromatic polyvalent isocyanate. An object of the present invention is to provide a photosensitive microcapsule characterized in that the weight ratio of the outer wall to the inner wall is in the range of 1:1 to 1:30.

Further, the present invention provides a photosensitive material having a photosensitive layer containing silver halide particles, a reducing agent, and a polymerizable compound on a support, and at least the polymerizable compound and the silver halide particles are accommodated in microcapsules. wherein the microcapsules are composed of an outer wall made of an amine-aldehyde resin and an inner wall made of a polyurea and/or polyurethane resin obtained from a raw material containing silver halide particles and containing an aromatic polyvalent isocyanate. It is an object of the present invention to provide a photosensitive material which is formed from a composite wall and has a weight ratio of the outer wall to the inner wall in the range of 1=1 to 1:30.

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

(1) The weight ratio of the outer wall and inner wall of the capsule is 1:
It ranges from 1 to 1:20.

(2) The aromatic polyvalent isocyanate is tolylene diisocyanate.

(3) The outer wall made of L amino aldehyde resin is melamine formaldehyde resin.

(4) 1-A reducing agent is contained in the core material.

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

(6) The photosensitive microcapsules have an average particle size of 0.5 to 50 lm.

[Effect of the invention] When a photosensitive material using a capsule having a composite wall as described above is developed at a higher temperature than usual after exposure, the polymerizable compound (monomer) contained in the capsule is It was found that bleed-out may be promoted and the contrast of the image may be reduced, which is thought to be due to this. It was also found that the strength of the capsule is still insufficient, and that when handling photosensitive materials, scratches (spotted color development) occur as the capsule breaks, which can lead to a decline in image quality. Ta.

As a result of the inventor's studies, the inner wall of the capsule is composed of aromatic polyvalent isocyanate, and the composition ratio (weight ratio) of the outer wall and the inner wall of the capsule is set at a specific ratio (weight ratio of the inner wall of the capsule to that of the inner wall). By creating capsules that increase the ratio of
It was found that the thermal properties and toughness of the capsule were further improved compared to the capsule having the above-mentioned structure (Japanese Patent Application No. 105099/1982). Therefore, by using capsules prepared in this way in photosensitive materials, even when thermal development is performed at high temperatures, the seepage of the monomer in the capsules is suppressed, and clear images can be obtained with short development processing. be able to. In addition, since the toughness of the capsule is improved at the same time, the storage stability of the photosensitive material is also improved and handling becomes easier.

[Detailed Description of the Invention] The wall material (outer shell material) constituting the outer shell of the photosensitive microcapsule of the present invention is made of aminoken aldehyde resin (outer wall) and polyurea and/or polyurethane containing silver halide particles. resin (inner wall), and the inner wall is produced from aromatic polyvalent isocyanate, and the IT ratio between the outer wall and the inner wall is in the range of 1:1 to 1:30. It is. Most of the silver halide grains exist near the interface between the core material and the inner wall, and all or part of the silver halide grains may be embedded in the inner wall. Particles may also be present within the core material.

As an example of the method for producing the photosensitive microcapsules of the present invention, the following interfacial polymerization method can be mentioned. In addition, as a method for forming the outer shell, for example, JP-A-56-10
The methods described in No. 2935 and No. 56-144739 can also be used.

Aromatic polyvalent isocyanate is dissolved in a hydrophobic liquid (hereinafter referred to as photosensitive composition) consisting of photosensitive silver halide and a polymerizable compound, or if necessary, a reducing agent and a core material such as a color image forming substance. Then, a dispersion liquid is prepared by dispersing this into fine droplets in an aqueous medium containing a polyamine and/or polyol and a dispersant. In addition, it is desirable to include in this dispersion a catalyst that promotes the polycondensation reaction between the aromatic polyvalent isocyanate and the polyamine and/or polyol. This will be discussed later.

When the dispersion prepared as described above is heated to a temperature in the range of 40 to 90°C, the polyurea resin and/or aromatic polyurethane resin, which is a reaction product of aromatic polyvalent isocyanate and polyamine (or water), appears at the interface of the microdroplets. An inner wall is formed consisting of a polyurethane resin which is the reaction product of a polyvalent isocyanate and a polyol.

In addition, in the present invention, the expressions polyurea resin and polyurethane resin do not necessarily mean resins having only bonding groups of urea bonds and urethane bonds. Resins that replace bonding are also included in polyurethane resins, and the same applies to polyurea resins.

In addition, there are already various methods for producing microcapsules using polyurea resin, polyurethane resin, or mixtures thereof as outer shell materials, and any of these methods can be used to produce the photosensitive microcapsules of the present invention. be able to.

In the present invention, the aromatic polyvalent isocyanate is used in an amount of 1.5 to 30% by weight (more preferably 3 to 20% by weight) based on the photosensitive composition.

Examples of aromatic polyvalent isocyanates, polyamines, and polyols used to form the outer shells of photosensitive microcapsules as described above are described below.

Examples of aromatic polyvalent isocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate)
, 2.6-) lylene diisocyanate, 2.4-) lylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-4,4゛-diisocyanate, 3,3゜-dimethoxy-4 , 4°-biphenyl diisocyanate, 3,3°-dimethyldiphenylmethane-
4,4°-diisocyanate, 4,4′-diphenylpropane diisocyanate, 4.4′,4″-triphenylmethane triisocyanate, toluene 2,4.6-
Triisocyanate, triisocyanate such as polymethylene polyphenylisocyanate, 4,4'-dimethyldiphenylmethane-2,2°, 5,5'-tetraisocyanate, 2,4-tolylene diisocyanate and prenz Examples include polyisocyanate prepolymers such as adducts with catechol, adducts with tolylene diisocyanate and hexanetriol, and adducts with tolylene diisocyanate and trimethylolpropane.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediaminepentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2-hydroxy Examples include trimethylenediamine, diethylenetriamine, triethylenetetraamine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds.

Examples of polyols include ethylene glycol 1.4-
Butanediol, catechol, resorcinol, hydroquinone, 1.2-dihydroxy-4-methylbenzene, 1.3-dihydroxy-5-methylbenzene, 3.4
-dihydroxy-1-methylbenzene, 3.5-dihydroxy-1-methylbenzene, 2.4-dihydroxyethylbenzene, l,3-naphthalenediol, l,5-
naphthalene diol, 2.7-naphthalene diol, 2
, 3-naphthalene diol and the like.

Next, an outer wall made of an amino aldehyde resin shell is formed around the inner wall of the polyurea resin and/or polyurethane resin described above.

That is, by adding separately prepared urea and formaldehyde or a melamine-formaldehyde initial condensate to the dispersion containing the microcapsules consisting of the inner wall formed above, and adjusting the pH 1 temperature, etc. External polymerization occurs to form an outer wall consisting of an amino aldehyde resin shell.

In the above shell-forming reaction, an anionic protective colloid is used. Due to the presence of anionic protective colloid,
A hydrophobic liquid (photosensitive composition) can be efficiently dispersed into microdroplets in an aqueous medium, and the microdroplets can be prevented from agglomerating or being stuck together.

Therefore, the anionic protective colloid is used by adding it to the aqueous medium in advance. Anionic protective colloid-forming substances suitable for such purposes are anionic polymeric compounds. Examples include polystyrene sulfonates and copolymers, polyvinyl sulfate ester salts, polyvinyl sulfonates, maleic anhydride/styrene copolymers, maleic anhydride/imbutylene copolymers, and maleic anhydride/ethylene copolymers. Coalescence, maleic anhydride/methyl vinyl ether copolymer, polyvinyl alcohol (saponified product) carboxyl-modified polyvinyl alcohol, gum arabic, polyacrylate and its derivatives and copolymers, carboxymethyl cellulose, gelatin pectin, pullulan, phthalated gelatin, succinated gelatin, other gelatin derivatives,
Examples include cellulose sulfate salts, alginate salts, and mixtures thereof.

In the present invention, the amount of the urea and formaldehyde or melamine formaldehyde initial condensate is in the range of 0.8 to 20% by weight (preferably 1.2% by weight) based on the photosensitive composition.
and 15% by weight).

In the above manner, microcapsules are obtained which have a double-layer outer shell, the outer wall of which is made of an amino aldehyde resin, and the inner wall of which is made of a polyurea resin and/or a polyurethane resin, which is made of an aromatic diisocyanate. The weight ratio of the outer wall and the inner wall constituting the microcapsule ranges from 1:1 to 1:30. In the present invention, the weight ratio of the outer wall and the inner wall ranges from 1:1 to 1:30. :20
It is preferable that there is a range of .

When photosensitive microcapsules are manufactured by the method described above to form a double-layered outer shell, silver halide particles are more reliably contained within the microcapsules without escaping into the aqueous phase. . In the present invention, melamine formaldehyde resin is more preferable for the outer wall.

When silver halide and a polymerizable compound, which will be described later, are introduced into a hydrophobic liquid as a core material, the silver halide is usually produced as an emulsion (silver halide emulsion) using water as a dispersion medium, and then this is made into a hydrophobic liquid. A method of mixing with a solvent is generally used. Since the aqueous medium of the silver halide emulsion is transferred to the aqueous phase of the dispersion medium during the preparation of the emulsified dispersion for microcapsule production, there is almost no water inside the core of the resulting photosensitive microcapsules. When a silver halide emulsion is transferred from an aqueous medium to an aqueous phase, the silver halide grains tend to move along with the water from the core material phase (oily phase) to the dispersion medium phase (aqueous phase). Because of this, silver halide tends to collect near the interface between the core material phase and the dispersion medium phase. Therefore, when silver halide is introduced into the core material using a silver halide emulsion, the silver halide grains are present at a high concentration near the inner wall or inside the inner wall. When the silver halide grains are at the above-mentioned position, exposure becomes easy and sensitivity is improved. Additionally, since the inner wall is made from aromatic polyvalent isocyanate, it is particularly more heat resistant than walls formed using aliphatic polyvalent isocyanate.

It becomes rich in toughness.

The silver halide grains may be introduced into the core material not as a silver halide emulsion as described above, but as a dispersion in which silver halide grains are dispersed in an organic solvent.
Alternatively, it is also possible to utilize a method in which silver halide grains obtained as a powder are simply mixed with a polymerizable compound.

From the aqueous liquid containing the photosensitive microcapsules obtained by the method described in L, the photosensitive microcapsules can be separated by evaporating the aqueous solvent or using a known separation method such as filtration or centrifugation. I can do it.

The average particle size of the microcapsules obtained as described above is preferably in the range of 0.5 to 50 pm, more preferably in the range of 3 to 20 pm. The particle size distribution of microcapsules is disclosed in Japanese Patent Application Laid-open No. 63-53.
As in the photosensitive material described in JP-A-63-81336, it is preferable that the microcapsules are uniformly distributed over a certain value, as in the photosensitive material described in JP-A-63-81336. It is preferable that the particle diameter is within a certain range of values.

When silver halide is contained in microcapsules, the average particle size of the silver halide grains is preferably one-fifth or less of the average size of the microcapsules, and more preferably one-tenth or less. A uniform and smooth image can be obtained by preferably setting the average grain size of the silver halide grains to one-fifth or less of the average size of the microcapsules.

The silver halide, reducing agent, polymerizable compound, and support constituting the photosensitive material will be sequentially explained below.

Light-sensitive materials contain silver chloride, silver bromide, silver halide,
Any grains of silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used.

The silver halide grains of the silver halide grains may be uniform or non-uniform on the surface and inside. Silver halide grains having a multilayer structure with different compositions on the surface and inside are disclosed in Japanese Patent Publication No. No. 57-154232, No. 58-108
No. 533, No. 59-48755, No. 59-52237
It is described in the Fongryong Publication, US Pat. Further, silver halide grains having a high proportion of silver iodide in the shell portion may be used as in the photosensitive material described in JP-A-62-183453.

There is no particular restriction on the crystal habit of the silver halide grains; for example, tabular grains having an aspect ratio of 3 or more may be used, as in the light-sensitive material described in Japanese Patent Application No. 55509/1982.

The above-mentioned silver halide grains are disclosed in Japanese Patent Application No. 61-2
It is preferable to use silver halide grains having a relatively low capri value, such as the light-sensitive material described in No. 14580.

For the silver halide used in the photosensitive material, two or more types of silver halide grains having different halogen compositions, crystal habits, grain sizes, etc. can be used in combination.

There is no particular restriction on the grain size distribution of silver halide grains6. For example, monodisperse silver halide grains having a substantially uniform grain size distribution are used as in the photosensitive material described in JP-A No. 62-210448. You can.

In the light-sensitive material, the average grain size of the silver halide grains is preferably 0.001 to 5 ILm,
More preferably, it is 0.001 to 2 ILm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to t in terms of silver, including organic silver salt, which is an optional component described below.
It is preferably in the range of Og/rn', and in terms of silver only for silver halide, it is preferably 1 g/m' or less, 1 mg to 500 mg/rn'
It is particularly preferable that

A reducing agent that can be used in a light-sensitive material has a function of reducing silver halide and/or a function of promoting (or inhibiting) polymerization of a polymerizable compound. There are various types of substances as reducing agents having the L function. The above reducing agents include hydroquinones, catechols, P-7 minophenols, p-phenylenediamines, 3-pyrazolidones, 3-7 minopyrazoles, 4-amino-5-
Pyrazolones, 5-aminouracils, 4゜5-dihydroxy-6-aminopyrimidines, reductones, amylreductones, 〇- or p-sulfonamidophenols, 0- or p-sulfonamidonaphthols,
2-sulfonamide indanones, 4-sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, hydrazines, etc. There is. By adjusting the type, amount, etc. of the reducing agent, it is possible to polymerize the polymerizable compound in either the area where the silver halide latent image is formed or the area where no latent image is formed. In addition, in a system in which a polymerizable compound is polymerized in a portion where a silver halide latent image is not formed, it is particularly preferable to use l-phenyl-3-pyrazolidones as the reducing agent.

Regarding various reducing agents having the above-mentioned a residue, please refer to JP-A No. 61-183640, JP-A No. 61-188535, and JP-A No. 61-188535.
Publications No. 1-228441 and JP-A-62-7
No. 0836, No. 62-86354, No. 62-8635
5, No. 60-227528, and No. 62-86355 (including those described as developing agents or hydrazine derivatives), and the above reducing agent is described in " The The
or2 of the Photographic Pr
4th edition, pp. 291-334 (1977)
, Research Disclosure Magazine Vol.1.170.1
No. 17029 (pages 9-15) of June 1978, and Vol. 1.176 of the same magazine, No. 17643 of December 1978
No. (pages 22-31). Also, JP-A-62
As in the photosensitive material described in Publication No. 210446, a reducing agent precursor capable of releasing a reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. The reducing agents and reducing agent precursors described in the above-mentioned specifications and literature can also be effectively used in photosensitive materials. Therefore, the r-reducing agent J in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, bibliography, and precepts. These reducing agents may be used alone, but as described in each 1 Jl specification of L, two or more types of reducing agents may be used in combination, or two or more types of reducing agents may be used. When these agents are used together, the interaction of the reducing agents is, firstly, to promote the reduction of silver halide (and/or organic silver salt) by so-called superadditivity, and secondly, to promote the reduction of silver halide (and/or organic silver salt). The oxidized form of the first reducing agent produced by the reduction of the first reducing agent (and/or organic silver salt) causes polymerization (or inhibits polymerization) of the polymerizable compound via a redox reaction with other reducing agents coexisting. ), etc. can be considered. However, in actual use, the reactions described above can occur simultaneously, so it is difficult to specify which effect is occurring.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p(N,N-diethylamino)phenol, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl -4-Methyl-4-heptadecylcarbonyloxymethyl-pyrazolidone, 2-phenylsulfonylamino 4-hexadecyloxy-5-t-octylphenol, 2-phenylsulfonylamino-4-1-butyl-5
-hexadecyloxyphenol, 2-(N-butylcarbamoyl)-4-phenylsulfonylaminonaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylami/naphthol, l-7cetyl-2-phenyl Hydrazine, l-acetyl-2-((p or 0)-7minophenyl)hydrazine, 1-formyl-2- ((p or 0)-aminophenyl) hydrazine, 1-acetyl-2-((p or 0) -methoxyphenyl)hydrazine, 1-lauroyl-2-((p
or 0)-aminophenyl) hydrazine, l-trityl-2-(2,6-dichloro-4-cyanophenyl)
hydrazine 1-) lythyl-2-phenylhydrazine, 1
-phenyl-2-(2,4.6-dolichlorophenyl)
Hydrazine, 1-(2-(2,5-di-1-pentylphenoxy)butyroyl)-2-((p or 0)
-aminophenyl)hydrazine, 1- +2- (2
, 5-di-t-pentylphenoxy)butyroyl)-2
-((p or o)-aminophenyl)hydrazine pentadecylfluorocaprylate, 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 0)-methoxyphenyl)hydrazine, 1-(methoxycarbonylbenzohydryl)-2-phenylhydrazine, l-formyl-2-[4-(2-(2,4-di-E-pentylphenoxy)butyramido)phenyl ]
Hydrazine, l-7 cetyl-2-[4(2-(2,4-
di-t-pentylphenoxy)butyramido)phenyl]hydrazine, 1-)lythyl-2-[(2,6-dichloro-4-(N.

N-di-2-ethylhexyl)carbamoyl)phenyl] hydrazine, 1-(methoxycarbonylbenzohydryl)-2-(2,4-dichlorophenyl)hydrazine, 1-1 lithium-2-[(2-(N-ethyl-N -octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, l-benzoyl-2-tritylhydrazine, 1-(4-butoxybenzoyl)-2-1lythylhydrazine, 1-(2,4-dimethoxybenzoyl)
-2-) lythylhydrazine, 1-(4dibutylcarbamoylbenzoyl)-2-)lythylhydrazine, and 1
-(1-naphthoyl)-2-tritylhydrazine and the like can be mentioned.

In the light-sensitive material, the reducing agent is preferably used in an amount of 0.1 to 1500 mol % based on 1 mol of silver (including the above-mentioned silver halide and optional organic 1M salt).

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and any known polymerizable compound can be used. In addition, when heat development treatment is planned as a method of using the photosensitive material, it is recommended to use a material with a high boiling point (for example, a boiling point of 80
It is preferable to use a compound having a temperature of at least 10°F (°C or higher), and in an embodiment in which the photosensitive layer contains a color image-forming substance as an optional component described below, the color image-forming substance is immobilized by polymerization and curing of a monopolymerizable compound. Therefore, it is preferable that the polymerizable compound is a crosslinkable compound having a plurality of polymerizable functional groups in the molecule.In addition, when forming a transferred image using an image-receiving material, Japanese Patent Application No. 61150079 Like the photosensitive materials mentioned.

It is preferable to use a highly viscous substance as the polymerizable compound.

Note that polymerizable compounds that can be used in photosensitive materials are described in the application specifications for the series of photosensitive materials described above and below.

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

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

Specific examples of polymerizable compounds that can be used in photosensitive materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, Dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate.

Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxydiethyleneated bisphenol A diacrylate, 2,2-dimethyl-3-
Diacrylate of hydroxypropionaldehyde and trimethylolpropane condensate, 2,2-dimethyl-3-
Examples include triacrylate of hydroxypropionaldehyde and pentaerythritol condensate, polyacrylate of hydroxypolyether, polyester acrylate, and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerynritol trimethacrylate, and pentaerynritol trimethacrylate. Examples include erythritol tetramethacrylate and polyoxyalkylenated bisphenol A dimethacrylate.

The polymerizable compound listed in L may be used alone or in combination of two types.For photosensitive materials using a combination of two or more types of polymerizable compounds, there is a description in JP-A-62-210445. be. It should be noted that a substance in which a polymerizable functional group such as a vinyl group or a vinyliso/group is introduced into the chemical structure of the color image forming substance, which is the above-mentioned reducing agent or an arbitrary component described later, can also be used as the polymerizable compound. Needless to say, the use of a reducing agent and a polymerizable compound, or a substance that serves both as a color image forming substance and a polymerizable compound, as described above, is also included in the embodiment of the photosensitive material.

In the light-sensitive material, the polymerizable compound is preferably used in an amount of 5 to 120,000 parts by weight, more preferably 12 to 120 parts by weight, per 1 part by weight of silver halide.
00 parts by weight.

Among the constituent components of the photosensitive layer described in 1-, at least a polymerizable compound and silver halide grains are contained in microcapsules. Preferably, the microcapsules contain a reducing agent, a color image forming substance, etc., which will be described later.

The microcapsules are as described above.

The photosensitive material is formed by providing a photosensitive layer containing the components described below on a support. There are no particular restrictions on this support, but if heat development is planned as a method of using the photosensitive material, it is preferable to use a material that can withstand the processing temperature of the development process. Materials that can be used include glass, paper, high-quality paper, coated paper, cast coated paper, synthetic paper, metals and their analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, and other films. Examples include paper laminated with a resin material or a polymer such as polyethylene.

In addition, when the support is made of a porous material such as paper, it is necessary to obtain a certain level of smoothness according to the waviness-based method, as in the case of the support used in the photosensitive material described in JP-A No. 62-209529. In addition, when a paper support is used, a paper support with low water absorption such as the photosensitive material described in Japanese Patent Application No. 61-183050, Japanese Patent Application No. 61-191273 Paper support having a certain Bekk smoothness like the photosensitive material described in the specification, Japanese Patent Application No. 1983-
A paper support with a low shrinkage rate such as the photosensitive material described in the specification of Japanese Patent Application No. 227766, a paper support with low air permeability such as the photosensitive material described in the specification of Japanese Patent Application No. 61-227768,
A paper support having a pH value of 5 to 9, such as the photosensitive material described in Japanese Patent No. 243552, can also be used.

In the following margins, various aspects of the photosensitive material, optional components that can be included in the photosensitive layer, auxiliary layers that can be optionally provided on the photosensitive material, etc. will be sequentially explained.

Optional components that can be included in the photosensitive layer of the photosensitive material include one-color image forming substances, sensitizing dyes, 41 silver salts, radical generators, various image formation accelerators, thermal polymerization inhibitors, and thermal polymerization initiators. , development stopper, fluorescent whitening agent, anti-fading agent, l
＼Relation or irradiation prevention dyes or pigments, pigments that decolorize when heated or exposed to light, matting agents, anti-smudge agents, plasticizers, water release agents, binders, photopolymerization initiators, polymerizable compounds Examples include solvents and water-soluble vinyl polymers.

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

The color image forming substance is preferably used in a proportion of 0.5 to 20 parts by weight per 100 parts by weight of the polymerizable compound,
More preferably, it is used in a proportion of 2 to 7 parts by weight.
Further, when 511 colorant is used, it is preferably used in a proportion of about 0.3 to 80 parts by weight per 1 part by weight of color former.

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

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and silver halide sensitizing dyes known in the photographic technology can be used.

The amount of sensitizing dye added is generally halogenated [1 mole]
The amount is about 0-8 to 10-2 mol.

The above-mentioned sensitizing dye is preferably added at the stage of preparing a silver halide emulsion, which will be described later.For light-sensitive materials obtained by adding the sensitizing dye at the stage of forming silver halide grains, JP-A-62- Japanese Patent Application No. 61-55510 describes light-sensitive materials obtained by adding a sensitizing dye at the stage of preparing a silver halide emulsion after the formation of silver halide grains in Japanese Patent Application No. 947. . Further, specific examples of sensitizing dyes that can be used in light-sensitive materials are also disclosed in the above-mentioned JP-A-62-947 and JP-A-62-947.
-55510. In addition, like the photosensitive material described in Japanese Patent Application No. 61-208786,
An infrared light-sensitive sensitizing dye may also be used.

Addition of organic silver salts to photosensitive materials is particularly effective in thermal development processing. That is, when heated to a temperature of 80° C. or higher, the organic silver salt is considered to participate in an oxidation-reduction 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 each other or in close proximity to each other.The organic silver salt is generally 0.0% per mole of silver halide. Ol to 10 mol, preferably 0.01 to 1 mol is used. Note that the same effect can be obtained by adding an organic compound constituting the organic silver salt (for example, benzotriazole) to the photosensitive layer instead of the organic silver salt. For photosensitive materials using organic silver salts, see 7th Patent Publication No. 1986-32.
There is a description in Publication No. 46. The organic silver salt as described above is preferably used in an amount of 0.1 to 10 mol per mol of silver halide, and 0.1 to 10 mol is used per mol of silver halide. It is more preferable to use it in a range of 1 mol to 1 mol.

The photosensitive layer may contain a radical generator that participates in the polymerization promotion (or polymerization inhibition) reaction of the reducing agent described above.
A photosensitive material using triazene silver as the radical generator is described in Japanese Patent Application Laid-Open No. 1988-62195639, and a photosensitive material using diazotar) II is described in Japanese Patent Application No. 1983-1989.
195640, and Japanese Patent Application Laid-Open No. 195641/1983, regarding photosensitive materials using azo compounds.

Various image formation accelerators can be used in the photosensitive material. 6 Image formation accelerators include promoting the redox reaction between silver halide (and/or organic silver salt) and a reducing agent; It has functions such as promoting the transfer of image-forming substances from the photosensitive material to the image-receiving material or image-receiving layer (these will be described later).

Image formation accelerators include bases, base precursors, oils, surfactants, compounds with capri-preventing mechanisms and/or development accelerating mechanisms, thermal solvents, and oxygen removal functions from the viewpoint of physicochemical opportunities. It is further classified into compounds with However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Therefore, the above classification is for convenience, and in reality, one compound often has multiple functions.

Examples of various image formation accelerators are shown below.

Preferable It! Examples of groups include, as inorganic bases, hydroxides of alkali metals or alkaline earth metals: tertiary phosphates, borates, carbonates, metaborates of alkali metals or alkaline earth metals; Combinations of zinc or zinc oxide with chelating agents such as sodium picolinate: ammonium hydroxide; hydroxides of quaternary alkyl ammonium: hydroxides of other metals, etc. Examples of organic bases include aliphatic Amines (trialkylamines, hydroxylamines, aliphatic polyamines): Aromatic amines (N-alkyl substituted aromatic amines, N-
Hydroxyalkyl-substituted aromatic amines and bis[
p-(dialkylamino)phenylcomethanes), heterocyclic amines.

Examples include amidines, cyclic amidines, guanidines, and cyclic guanidines, and those having a pKa of 7 or more are particularly preferred.

Base precursors include salts of organic acids and bases that are decarboxylated by heating, and intramolecular nucleophilic substitution reactions.

Preferably used are compounds that release bases by causing some kind of reaction when heated, such as compounds that release amines through reactions such as Rossen rearrangement and Beckmann rearrangement, and compounds that generate bases by electrolysis or the like. Specific examples of base precursors include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-
) luidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonylacetate, guanidine 4-chlorophenylsulfonylacetate, guanidine 4-methyl-sulfonylphenylsulfonylacetate, and guanidine 4-7cetylaminomethylbropiolate, etc. I can do it.

The base or base precursor can be used in the photosensitive material in a wide range of amounts. The base or base precursor is suitably used in an amount of 100% by weight or less, more preferably 0.1% by weight of the coating film of the photosensitive layer.
In the present invention, the base and/or base precursor may be used alone or as a mixture of two or more.

In addition, 11! Photosensitive materials using radical or base precursors are described in Japanese Patent Application No. 227528/1983. Further, for a photosensitive material using a tertiary amine as a base, see JP-A-62-170954, and for a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound with a melting point of 80 to 180°C. JP-A-62-209
No. 523 describes a photosensitive material using a guanidine derivative with a solubility of 0.1% or less in Japanese Patent Application No. 6l-2i56.
37, and Japanese Patent Application No. 61-96341 describes photosensitive materials using hydroxides or salts of alkali metals or alkaline earth metals.

Furthermore, regarding photosensitive materials using an acetylide compound as a base precursor, it is disclosed in Japanese Patent Application No. 167558/1983 that a propiolate is used as a base precursor, and silver, copper, a silver compound, or a copper compound is used as a catalyst for the base production reaction. Regarding the photosensitive materials included as
No. 191000, the above-mentioned propiolic acid salt and the above-mentioned silver.

Regarding a photosensitive material containing copper, a silver compound, or a copper compound in a mutually isolated state, Japanese Patent Application No. 61-227769 discloses that in addition to the above-mentioned propiolic acid salt and the above-mentioned silver, copper, a silver compound, or a copper compound in a free state, Regarding a photosensitive material containing a certain ligand, it is described in Japanese Patent Application No. 61-243555 that propiolic acid salt is used as a base precursor,
Furthermore, regarding a photosensitive material containing a heat-fusible compound as a reaction accelerator for the base-forming reaction, Japanese Patent Application No. 191001/1983 describes using a sulfonylacetate as a base precursor and further adding the heat-fusible compound to the base-forming reaction. Regarding photosensitive materials containing accelerators, patent application No. 61-1933
No. 75 describes a photosensitive material using a compound in which incyanate or inthiocyanate is bonded to an organic base as a base precursor in Japanese Patent Application No. 1675/1983.
Each of these is described in the specification of No. 58.

When using a base or base precursor in a photosensitive material,
It is preferable that the silver halide, the reducing agent, and the 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.
In addition to the above specification, photosensitive materials using microcapsules containing bases or base precursors, such as the photosensitive material described in Publication No. 21, may contain bases or base precursors in separate microcapsules. Alternatively, a photosensitive material in which a base precursor is dissolved or dispersed in an aqueous water retention agent solution and accommodated in microcapsules is disclosed in JP-A-62-209522, in which solid fine particles supporting a base or a base precursor are accommodated in microcapsules. A photosensitive material using microcapsules containing a basic compound with a melting point of 70°C to 210°C is described in Japanese Patent Application Laid-Open No. 62-209526,
212149, respectively. Furthermore, instead of the microcapsules containing the base or base precursor, particles containing a base or base precursor and a hydrophobic substance in a compatible state may be used, as in the photosensitive material described in Japanese Patent Application No. 61-243556. good.

In addition, the base or base precursor is #gansho 61-9
As described in the specification of No. 6340, it may be added to an auxiliary layer other than the photosensitive layer (a layer containing a base or a base precursor described later).
As described in US Pat. No. 6,417, the aforementioned supports may be porous and a base or base precursor may be included in the porous support.

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

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

A compound having an antifogging function and/or a development accelerating function can be used for the purpose of obtaining a clear image (an image with a high S/N ratio) having a high maximum density and a low minimum density. Note that a photosensitive material using an antifoggant as a compound having an antifogging function and/or a development accelerating function is described in JP-A-62-151838, and a photosensitive material using a compound having a cyclic amide structure is described in JP-A-62-151838. In Publication No. 151841/1983.

Regarding photosensitive materials using thioether compounds, see JP-A-62-151842, and about photosensitive materials using polyethylene glycol derivatives, see JP-A-62-151.
843, for photosensitive materials using thiol derivatives, see JP-A-62-151844, and for photosensitive materials using acetylene compounds, see JP-A-62-178.
232, for photosensitive materials using sulfonamide derivatives, see JP-A-62-183450, and for photosensitive materials using quaternary ammonium salts, see Japanese Patent Application No. 61.
Each of these is described in the specification of No.-238871.

Useful examples of the thermal solvent include compounds that can serve as solvents for reducing agents, and compounds with high dielectric constants that are known to accelerate the physical development of silver salts. A photosensitive material using a heat solvent is described in JP-A-62-86355.

A compound having an element remover 1@ can be used for the purpose of eliminating the shadow of oxygen (oxygen has a polymerization inhibiting effect) during development.

Thermal polymerization initiators that can be used in the following margin photosensitive materials are generally compounds that thermally decompose under heating to generate polymerization initiating species (particularly radicals), and are usually used as radical polymerization initiators. .

Thermal polymerization initiators are described in pages 6 to 18 of ``Addition Polymerization/Ring Opening Polymerization J'' edited by the Editorial Committee of Polymer Experiments, The Polymer Society of Japan, 1983, Kyoke Publishing).Thermal polymerization The initiator is 0.1 to 120% by weight based on the polymerizable compound.
It is preferable to use the polymerizable compound in the range of 1 to 10 i%, and it is more preferable to use it in the range of 1 to 10 i%. It is preferable to add a thermal polymerization initiator therein, and a photosensitive material using a thermal polymerization initiator is described in JP-A-62-70836.

Binders that can be used in photosensitive materials can be contained in the photosensitive layer alone or in combination. It is preferable to use a mainly hydrophilic binder.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing the unpolymerized normalizable compound after one image transfer. There is a description in JP-A-62-161149.

When using a solvent for a polymerizable compound in a photosensitive material, it is preferable to encapsulate it in a separate microcapsule from the microcapsule containing the polymerizable compound. For photosensitive materials using miscible organic solvents, see JP-A-62-2095.
There is a description in Publication No. 24.

A water-soluble vinyl polymer may be adsorbed onto the silver halide grains mentioned above, and a photographic material using a water-soluble vinyl polymer as described above is disclosed in Japanese Patent Application No. 61-2388.
It is described in the specification of No. 70.

In addition to those mentioned above, examples of optional components that can be included in the photosensitive layer and how they are used can also be found in the application specifications related to the series of photosensitive materials mentioned above and Research Disclosure Magazine Vol.

No. 17029, June 1978 (pages 9-15).

Layers that can be optionally provided on the photosensitive material include an image-receiving layer, a heating layer, an antistatic layer, an anti-curl layer, a peeling layer,
Examples include a cover sheet or protective layer, a layer containing a base or a base precursor, a base barrier layer, an antihalation layer (colored layer), and the like.

All 11 The method for manufacturing the photosensitive material will be described below.

Various methods can be used to produce photosensitive materials, but as mentioned above, the photosensitive material is produced by dissolving, emulsifying, or dispersing the constituent components of the photosensitive layer in an appropriate solvent. After preparing a composition, the composition is microencapsulated to prepare a coating solution containing a microcapsule dispersion, and the coating solution is coated on a support as described above and dried to obtain a photosensitive material. It is what it is.

Regarding the main components contained in the photosensitive layer, methods for preparing a liquid composition and a coating solution are shown below.

Preparation of the halogenated emulsion can be carried out using any known method such as an acid method, a neutral method or an ammonia method.

The reaction format between soluble silver salt and soluble halogen salt is 1
A back-mixing method in which zero particles are formed under conditions of excess silver ions and a Chondral double-jet method in which PAg is kept constant can also be employed, which may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. In addition, to accelerate particle growth,
The concentration, amount, or rate of addition of silver salts and halogen salts may be increased by 1 (Japanese Patent Laid-Open No. 55-158).
No. 124, No. 55-158124, and U.S. Pat. No. 3,650,757).

Silver halide emulsions used in the production of photosensitive materials are mainly of the surface latent image type, in which a latent image is formed on the surface of the grains, or the internal latent image type, in which the latent image is formed inside the grains. Direct inversion emulsions combining emulsions and nucleating agents can also be used. Internal latent image type emulsions suitable for this [1] are disclosed in U.S. Pat. No. 2,592,250, U.S. Pat.
It is described in No. 6641 in each public percentage. A preferred nucleating agent for combination with the above emulsion is U.S. Pat.
No. 2, No. 4245037, No. 4255511,
No. 4266013, No. 4276364 and OLS No. 2635316.

In the preparation of silver halide emulsions used in the production of light-sensitive materials, it is preferable to use a wood-philic colloid (eg, gelatin) as a protective colloid.

Silver halide emulsions are prepared by using ammonia, organic thioether derivatives (see Japanese Patent Publication No. 47-386), and sulfur-containing compounds (see Japanese Patent Application Laid-Open No. 144319-1987) as silver halide solvents in the stage of forming silver halide grains.
etc. can be used. In addition, in the process of particle formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, etc. may be allowed to coexist.Furthermore, for the purpose of improving high illumination failure and low illuminance failure, iridium chloride (■ or ■),
A water-soluble iridium salt such as ammonium hexachloroiridium salt or a water-soluble rhodium salt such as rhodium chloride may be used.

Soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening. In this case, this can be carried out according to the Tardel water washing method or the precipitation method. Silver halide emulsions may be used as they are unripe, but they are usually used after being chemically sensitized.For emulsions for conventional type sensitive materials, well-known sulfur sensitization methods, reduction sensitization methods, and noble metal sensitization methods are used. These can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (Japanese Patent Application Laid-open No. 58
-126526, No. 58-215644 Yongyong Publication Reference
! A).

In addition, when adding a sensitizing dye to a silver halide emulsion,
The aforementioned Japanese Patent Application Laid-Open No. 62-947 and Japanese Patent Application No. 1988-
Nitrogen-containing heterocyclic compounds are preferably added at the stage of preparing a silver halide emulsion as in the light-sensitive material described in No. When added, it is preferable to add the nitrogen-containing heterocyclic compound during the formation or ripening stage of silver halide grains in the preparation of a silver halide emulsion. Regarding the manufacturing method of photosensitive materials, please refer to JP-A-62-161144.
There is a description in the bulletin.

When the organic silver salt described above is included 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 described above.

In the production of photosensitive materials, polymerizable compounds can be used as a medium in preparing the composition of other components in the photosensitive layer. For example, silver halide (including silver halide emulsions), reduction A one-color image forming substance can be dissolved, emulsified or dispersed in a polymerizable compound and used in the production of a photosensitive material. Particularly when a color image forming substance is added, it is preferable to include a polymerizable compound therein.

A photosensitive composition containing silver halide in a polymerizable compound can be prepared using a silver halide emulsion. In addition to the /X silver halide emulsion, silver halide powder prepared by freeze-drying or the like can also be used to prepare the photosensitive composition.

Photosensitive compositions containing these silver halides can be prepared using a homogenizer, blender, mixer or other method.

It can be obtained by stirring with other commonly used stirrers.

In addition, it is preferable that a copolymer consisting of a woody repeating unit and a hydrophobic repeating unit is dissolved in the polymerizable compound used for preparing the photosensitive composition. is published in Japanese Unexamined Patent Application Publication No. 1986-
There is a description in No. 209449.

Furthermore, instead of using the above copolymer, a photosensitive composition may be prepared by dispersing microcapsules having a silver halogenide emulsion as a core material in a polymerizable compound.
Regarding photosensitive compositions containing microcapsules containing silver halide emulsions as core materials, JP-A-62-16404 discloses
There is a description in Publication No. 1.

[-The photosensitive composition obtained as described above is subjected to the above-described microencapsulation treatment to prepare a capsule dispersion. This dispersion can be used as it is as a coating solution for photosensitive materials. Alternatively, a coating liquid may be prepared by adding other optional components.

A photosensitive material is produced by applying the photosensitive layer coating solution prepared as described above onto a support and drying it. The coating liquid can be easily applied to the support according to known techniques.

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

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

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

The photosensitive material is developed at the same time as the above-mentioned imagewise exposure or after the imagewise exposure.
Development processing using a developer described in Publication No. 49 etc. may be performed. Furthermore, as mentioned above, since the method described in Japanese Patent Application Laid-open No. 61-69062, which involves heat development processing, is a dry process. , it has the advantage of being easy to operate and can be processed in a short time. Therefore, the development process for photosensitive materials is as follows:
The latter is especially good.

As the heating method in the above heat development treatment, various conventionally known methods can be used. In addition, like the photosensitive material described in JP-A No. 61-294434,
A heat generating layer may be provided on the photosensitive material and used as a heating means.Also, as in the image forming method described in JP-A-62-210461, the amount of oxygen present in the photosensitive layer must be suppressed. Heat development treatment may be carried out from
It is 0°C. The heating time is generally 1 second to 5 minutes, preferably 1 to 5 minutes, and more preferably 1 second to 1 minute.

Note that instead of including the base or base precursor in the photosensitive material as described above, a method of adding the base or base precursor may be performed, in which development processing may be performed while adding the base or base precursor to the photosensitive layer, or immediately after the addition. as a sheet containing a base or base precursor (
The method using a base sheet) is the easiest and preferable.
An image forming method using the above base sheet is described in Japanese Patent Application No. 176417/1983.

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

In the manner described above, a polymer image can be obtained on the photosensitive layer of the photosensitive material. It is also possible to obtain dye images by fixing dyes or pigments to the polymer.

When the photosensitive material is constructed like the photosensitive material described in JP-A No. 62-209444 mentioned above, there are two types of photosensitive materials in which the developed photosensitive material is pressurized to destroy the microcapsules and cause a color reaction. A color image can be formed on a photosensitive material by bringing the substances into contact with each other.

The image-receiving material can also be used to form an image on the image-receiving material.

Next, the image receiving material will be explained. A general image forming method using an image-receiving material or an image-receiving layer is described in JP-A-61-278849.

As a support for the image-receiving material, baryta paper can be used in addition to the supports that can be used for the photosensitive materials described above. In addition, when using a porous material such as paper as a support for the image-receiving material,
It is preferable that the image receiving material has a certain level of smoothness as in the image receiving material described in Japanese Patent Application No. 530, and an image receiving material using a transparent support is described in Japanese Patent Application Laid-Open No. 62-209531.

Image-receiving materials generally have an image-receiving layer provided on a support.

The image-receiving layer can be constructed in any desired form using various compounds according to the coloring system of the color image-forming substance described above. In addition, when forming a polymer image on an image-receiving material, when a dye or a pigment is used as a color image-forming substance, the image-receiving material may be composed only of the above-mentioned support.

For example, when using a coloring system consisting of a color former and a color developer, the image receiving layer can contain the color developer. Furthermore, the image-receiving layer can also be configured as a layer containing at least one mordant. The mordant can be selected from compounds known in the photographic technology, taking into consideration conditions such as the type of color image forming substance, and used. Note that, 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, binders that can be used in the photosensitive layer of the photosensitive material described above can be used. Furthermore, a polymer with low oxygen permeability may be used as the 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, the image-receiving layer itself is preferably constructed as an aggregate of fine particles of the thermoplastic compound. has the advantage that it is easy to form a transferred image, and that a glossy image can be obtained by heating after image formation. The above thermoplastic compound is not particularly limited and can be arbitrarily selected from known plastic resins (plastics), waxes, and the like. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200°C or less.For an image receiving material having an image receiving layer containing thermoplastic compound fine particles as described above, Japanese Patent Application No. 61-1249
No. 52 and No. 61-124953.

In image formation using an image-receiving material, the image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator,
The color image forming material is transferred together with the unpolymerized polymerizable compound as described below. For this reason, the smooth progress of the curing process (secondary process) of the unpolymerized polymerizable compound [first,
A photopolymerization initiator or a polymerization initiator can be added to the image-receiving layer. Further, regarding an image receiving material having an image receiving layer containing a photopolymerization initiator, see JP-A-62-161149, and regarding an image-receiving material having an image-receiving layer containing a thermal polymerization initiator, JP-A-67-210444 C3. There are descriptions for each.

The image-receiving layer may be of two or more types depending on the various functions described below.
The thickness of the image-receiving layer is:
It is preferable that the number is 1 or m.

It is extremely preferable that the thickness is from 2 to 20 μm.

Note that a protective layer may be further provided on the image-receiving layer.

The photosensitive material was developed as described above.

By pressurizing the above image-receiving materials in a state where they are pressed together,
The unpolymerized polymerizable compound can be transferred to an image-receiving material to obtain a polymer image on the image-receiving material. Regarding the pressurizing means described in 2., various conventionally known methods can be used.

Note that 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 No. 62-210459. The unpolymerized polymeric compound transferred onto the top becomes Togane,
There is also the advantage that the preservation of the obtained image is improved.

In addition, the applicant uses a photosensitive material to
Patent applications have already been filed for various image recording devices suitable for carrying out a series of image forming methods.
0-287492, etc.).

1986-289703) etc.

Photosensitive materials include black and white or color photosensitive materials for photographing and printing, printing photosensitive materials, printing plates, X-ray photosensitive materials, and medical photosensitive materials (for example, ultrasonic diagnostic CRT photosensitive materials).

It has many uses, such as computer graphic hard copy photosensitive materials and photocopying machine photosensitive materials.

The present invention will be explained in more detail with reference to Examples below. However, the present invention is not limited to this.

[Example 1] [Preparation of photosensitive microcapsules] Silver halide emulsion: A stirred aqueous gelatin solution (manufactured by JJ, containing 25 g of gelatin and 3 g of potassium bromide in lK1200mu and kept at 70°C) was added with bromide. Aqueous solution 6 containing 11.7 g of potassium
00mM and silver nitrate aqueous solution (silver nitrate 0 on ice 600m + J1
．． 74 mol dissolved) were simultaneously added at equal flow rates over 45 minutes.

5 minutes after this has finished, an additional 4.3 g of potassium iodide
200ml of an aqueous solution containing Q was added at equal flow rates over 5 minutes. After washing this emulsion with water and desalting it, 24 g of gelatin was added and stirred at 50°C for 15 minutes to obtain a yield of 10
00 g of silver halide emulsion was obtained.

To 100 g of W10 emulgin, add 0.4 g of the following copolymer and 10 g of Burger Script Red l-6-B (manufactured by Ciba Geigy).
I made you understand. In 18 g of this solution M, 0.36 g of Ssan Nonion NS 208.5 (manufactured by NOF) was dissolved in 1M surfactant, and 1.2 g of the following hydrazine derivative (reducing agent) was dissolved.
A solution of 9 g and 1.22 g of the following developer (reducing agent) dissolved in 4 g of methylene chloride was added to form an oil phase (0).

On the other hand, silver halide emulsion 2. obtained above. Og, 0.45 g of 10% aqueous solution of potassium bromide, 0 benzotriazole
．． 022 g was added to form an aqueous phase (W).

Next, add the water phase (W) to the above oil phase (0),
Using a homogenizer, the mixture was stirred at 15,000 revolutions per minute for 5 minutes to obtain a W10 emulsion.

Below Margin Trimethylolpropane triacrylate (copolymer) C0zCH201bOH 002C2H5 (Hydrazine derivative) (Developer) Partial sodium salt of polyvinylbenzenesulfonic acid (V
ERS^, Tl2O3, manufactured by National Starch) 5%
The aqueous solution was adjusted to pH 2.5 with a 20% aqueous phosphoric acid solution. Into 40 g of this aqueous solution, add 4.95 g of a 75% ethyl acetate solution of tolylene diisocyanate (aromatic polyvalent isocyanate compound) (trade name: Burnock D750, manufactured by Takeda Pharmaceutical Company Ltd.) to the above W10 emulsion and mix well. The mixture was stirred at 9000 revolutions per minute for 30 minutes using a homogenizer at 25°C. A thin shell of polyurea resin was formed around the oil phase of the W10/W emulsion produced here.

Separately, 13.2 g of melamine, 21.6 g of a 37% formaldehyde aqueous solution, and 70.8 g of water were heated and stirred at 60° C., and after 30 minutes, a transparent melamine/formaldehyde initial condensate was obtained.

3 g of the initial condensate L was added to the above W10/W emulsion (P
! The outer shell of the polyurea membrane A microcapsule liquid (A) in which melamine/formaldehyde resin was deposited was prepared (outer wall/inner wall (weight ratio) = 1/6).

Furthermore, in order to remove formaldehyde remaining in the capsule liquid, 5.4 g of a 40% urea aqueous solution was added, the pH was adjusted to 3.5 with a 20% phosphoric acid aqueous solution, and stirring was continued for 40 minutes. The capsule liquid was adjusted to pH 7.0 with a % aqueous sodium hydroxide solution and cooled.

[Comparative Example 1] In Example 1, when a W10 emulsion containing a silver halide emulsion was prepared and a capsule dispersion was further prepared using this W10 emulsion, xylylene diisocyanate was used instead of tolylene diisocyanate. Example 1 except that the same amount of a 75% ethyl acetate solution of an adduct of trimethylolpropane (aliphatic polyisocyanate compound) (trade name: Takenate DIION, manufactured by Takeda Pharmaceutical Company Ltd.) was used. Capsule dispersion (X) was prepared in the same manner as above (outer wall/inner wall (weight ratio) = 1/6).

[Comparative Example 2] In Example 1, a W10 emulsion containing a silver halide emulsion was prepared, and when a capsule dispersion was further prepared using this W10 emulsion, 4.95 g of tolylene diisocyanate was changed to 0.27 g. A capsule dispersion (Y) was prepared by the same procedure as in Example 1, except that 3 g of the melamine formaldehyde initial condensate was changed to 20.4 g (outer wall/inner wall (weight) ratio)=20/1).

[Comparative Example 3] In Example 1, a W10 emulsion containing a silver halide emulsion was prepared, and when a capsule dispersion was further prepared using this W10 emulsion, 4.95 g of tolylene diisocyanate was changed to 5.6 g. A capsule dispersion (Z) was prepared by the same procedure as in Example 1, except that 3 g of the melamine/formaldehyde initial condensate was changed to 0.51 g (outer wall/inner wall (weight) ratio)=40/1).

[Preparation of photosensitive material and evaluation thereof] Preparation of photosensitive material (A) Microcapsule dispersion (A) prepared in Example 1 above
) 30.0 g of solid dispersion of base precursor 6.8
g, 9 g of a 20% aqueous solution of Vine Hitol, 20 liters of corn starch dispersion io.

g and surfactant (trade name; 'n-71/ ・
, 4.0 g of a 5% aqueous solution of Cus NP8, ■ Hon Emuljo/# manufactured by IJ were added. Furthermore, add A comparison to this, Z,
T: A coating solution made of J4 was prepared at 75° C., and then the coating solution was coated with 100 W ttt thick poly 1-y.
-y, 7te1.・Lid・-to・-to I: To? The fabric was dried at 63° C./'m' for 30 minutes to prepare a photosensitive material (A) according to the present invention.

Preparation of solid dispersion of base precursor 40 g of the above base precursor was dispersed in 160 g of a 3% polyvinyl alcohol aqueous solution using a Daitsuno Mill dispersion machine (.C) to prepare a 20% solid dispersion of base breaker.

F Margin base breaker leaf - C-NH(CH2)-2NH-C \ \ HN
In the preparation of the photosensitive material (A), in place of the solution (A), I. -F, , >', photosensitive material 1 (A
) A comparative photosensitive material (X) was prepared in the same manner as in the preparation of (X).

Preparation of photosensitive material (Y) In the preparation of photosensitive material (A), the above Comparative Example 2 was used instead of the microcapsule liquid (A) prepared in Example 1 above.
A comparative photosensitive material (Y) was prepared in the same manner as in the preparation of the above photosensitive material (A, ), except that the microcapsule liquid (Y) prepared in (2) was used.

Preparation of photosensitive material (Z) In the preparation of the photosensitive material (A), the microcapsule liquid (2) prepared in Comparative Example 3 above was used instead of the microcapsule liquid (A) prepared in Example 1 in 1-. Other than using 1. A comparison photosensitive material (Z) was prepared by performing the same operations as in the preparation of the photosensitive material (A).

Next, each photosensitive material (A, X,
Y and Z) were evaluated using an image receiving material prepared as follows.

Preparation of image-receiving material 11 g of 40% sodium hexametaphosphate aqueous solution was added to 125 g of water, and further mixed with 34 g of zinc 3,5-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry, and coarsely dispersed with a mixer. did. The liquid was dispersed using a Dynamyl disperser, and 200% of the resulting liquid
6 g of 50% SXR latex and 55 g of 8% polyvinyl alcohol aqueous solution were added to the mixture and mixed uniformly.

Pour the mixed liquid into n5t80g/rrr' paper-L for 30
After uniform coating to a wet film thickness of gm, an image receiving material was prepared by drying.

(1) Use a tungsten light bulb to measure each photosensitive material from 0 to 3.
Pass through a continuous filter with a transmission density of up to 20
After exposing for 1 second at 00 lux each, this was
It was heated for 10 seconds using a heat roller heated to 5°C.

Next, each photosensitive material is overlapped with the above image-receiving material,
In that state, it was passed through a pressure roller of 500 kg/c rn'. A magenta positive color image was obtained on each image-receiving material -1-. Using a reflection densitometer for the obtained color image, the lowest density (I + in) and the highest density (Dx)
was measured.

(2) In addition, after scratching the surface of each of the above photosensitive materials with a telescope (2 cm x 2 cm) on which a 150 g weight was placed, the material was exposed to light at 200 lux for 1 second, and at 155°C for 10 min.
0, developed with a second heat roller type developing machine,
This photosensitive material was layered with the above image receiving material and weighed at 500 kg.
/ crn' pressure roller, and visually check the density of the scratched area (density of the scratched area caused by capsule destruction), r large (dark), medium (intermediate density), small (thin) J. It was evaluated on a three-level scale.

The above measurement results are shown in Table 1.

Table 1 Exposure Minimum density Maximum density Density of scratched part material (D layer in) (D intestine ax) (A) 0.131.05 Small (X) 0.481.10 Large (Y) 0.121.08 Large (Z) 0.291.07 As is clear from the results in Table 1, the image obtained from the photosensitive material (A) constructed using the microcapsules according to the present invention is It showed good contrast even when In addition, scratches caused by capsule destruction were less likely to occur.

Claims (1)

[Scope of Claims] 1. A polyurea obtained from a raw material containing an aromatic polyvalent isocyanate, containing an outer wall made of an amino aldehyde resin, silver halide particles, and a core material containing a polymerizable compound; and/or an inner wall made of polyurethane resin, and the weight ratio of the outer wall and the inner wall is in the range of 1:1 to 1:30. A photosensitive microcapsule characterized by: 2. A photosensitive material having a photosensitive layer containing silver halide grains, a reducing agent, and a polymerizable compound on a support, and at least the polymerizable compound and silver halide grains are housed in microcapsules, The capsule is
A composite wall is formed of an outer wall made of an amino aldehyde resin and an inner wall made of a polyurea and/or polyurethane resin obtained from a raw material containing silver halide particles and containing an aromatic polyvalent isocyanate. . A photosensitive material, characterized in that the weight ratio of the outer wall to the inner wall is in the range of 1:1 to 1:30.