JPS63173041A - Photosensitive material and production thereof - Google Patents

Abstract

PURPOSE:To shorten development time in an image forming stage by incorporating a neutral binder into a photosensitive layer. CONSTITUTION:When a photosensitive layer contg. microcapsules each made of a polycondensed aldehyde resin wall and holding silver halide, a reducing agent and a polymerizable compd. is formed on a support to obtain a photosensitive material, a neutral binder is incorporated into the photosensitive layer in place of anionic protective colloid. A pH value necessary for development is attained at an increased rate and an image can be acceleratedly formed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive material having a photosensitive layer on a support containing a photosensitive composition comprising silver halide, a reducing agent, and a polymerizable compound, and a method for producing the same. . More specifically, the present invention relates to a photosensitive material having microcapsules made of an aldehyde polycondensed resin wall and containing the above-mentioned photosensitive composition, and a method for producing the same.

[Background of the Invention] A photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support forms a latent image of silver halide and polymerizes the polymerizable compound by the action of the reducing agent. It can be used in image forming methods.

Examples of image forming methods include methods described in Japanese Patent Publications Nos. 45-11149, 47-20741, 49-10697, and 57-138632 and 58-169143. In these methods, when exposed silver halide is developed using a developer, the reducing agent is oxidized and at the same time the coexisting polymerizable compounds (e.g.
(vinyl compound) starts polymerization to form an image-like polymer compound. Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

Further, as an improvement on the above, JP-A-61-69062 discloses a method in which a polymer compound can be formed by dry treatment. This method uses a recording material (photosensitive material) in which a photosensitive layer consisting of a photosensitive silver salt (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound), and a binder is supported on a support.

In this method, a polymer compound is formed in the area where the latent image of the photosensitive silver salt has been formed by exposing one image of the photosensitive silver salt to form a latent image and then heating it. That is, this method is a method of polymerizing the polymerizable compound in the area where the silver halide latent image is formed.

A patent application has already been filed for a method for polymerizing the polymerizable compound in the area where the silver halide latent image is not formed (Japanese Patent Application No. 210657/1982).

By the way, as another aspect of the image forming method described in JP-A-61-69062, an image-forming method is known in which a color image-forming substance is further added to the constituent elements (JP-A-61-73145). Publication No.).

Additionally, the applicant has already filed a patent application for a photosensitive material in which at least a polymerizable compound and a color image-forming substance (coloring component) are housed in the same microcapsules for the purpose of improving sensitivity and storage stability over time. , Ru (Special application 1986-
117089), among which methods already known as microcapsule manufacturing techniques are used, such as the core cell page method, interfacial polymerization method, or in-situ method. Various polymeric substances have been mentioned as microcapsule wall forming materials suitably used in these methods.

As an example of using the above-mentioned wall-forming material, there is a photosensitive material created by the present applicant that uses microcapsules made of amino aldehyde resin around a core substance containing silver halide and a polymerizable compound (Patent Application No. 61). -53873 specification).

Various microencapsulation methods are already known, and any method can be selected from these methods and used in the production of microcapsules made of the above-mentioned amino aldehyde resin wall. A commonly used method for forming an outer shell is to emulsify a hydrophobic liquid (photosensitive composition) containing a core substance in an aqueous medium to form microdroplets, and then form an outer shell around the microdroplets. method (external polymerization method).

Usually, during the formation of the shell, an anionic protective colloid is added to the aqueous medium to prevent agglomeration and integration of the capsules and to obtain a stable emulsified state. Therefore, it is common that a considerable amount of anionic protective colloid is contained in the final photosensitive material having the above structure.

When a photosensitive material having microcapsules made of an aldehyde polycondensation resin wall as described above is used to form an image, it takes a relatively long development time to obtain a certain level of sensitivity (image density). It was a trend.

[Summary of the Invention] An object of the present invention is to provide a photosensitive material that can quickly form an image by shortening the development processing time, and a method for producing the same.

Another object of the present invention is to provide a photosensitive material that is free from scratches and provides good images, and a method for producing the same.

That is, the present invention provides a photosensitive material having, on a support, a photosensitive layer containing microcapsules made of an aldehyde polycondensation resin wall containing silver halogenide, a reducing agent, and a polymerizable compound. A photosensitive material characterized by containing a neutral binder.

The present invention also provides a microcapsule dispersion solution by forming an aldehyde polycondensation resin wall around a photosensitive composition containing silver halide, a reducing agent, and a polymerizable compound in an aqueous medium containing an anionic protective colloid. After preparing, the 7-ionic protective colloid is removed from the dispersion, a neutral binder is then added to prepare a coating solution for forming a photosensitive layer, and this coating solution is coated on a support. There is a method for manufacturing a photosensitive material.

[Effects of the Invention] The photosensitive material of the present invention has a structure in which a neutral binder is added instead of an anionic protective colloid to the photosensitive layer, so that the speed at which the pH value required during development is reached (increase) is increased. image formation speed). Therefore, by using the photosensitive material of the present invention, it is possible to shorten the development time in the image forming process.

Usually, when forming an image using a photosensitive material, a compound (such as a base) that makes the reaction system basic is used for the purpose of accelerating development. However, the photosensitive material formed according to the conventional method has a structure in which the photosensitive layer contains a 7-ionic protective colloid (contained in the form of a salt), which exhibits a kind of buffering effect during image formation. In addition, the pH rise time until reaching a certain atmosphere (generally pH in the range of 8 to 9) suitable for image formation was delayed, resulting in a relatively long development process. A photosensitive material constructed according to the manufacturing method of the invention is manufactured during its manufacturing process. Preparation stage of coating solution for photosensitive layer formation: Most of the anionic protective colloid contained in the coating solution is removed and a neutral binder is added instead, so when forming an image using this, , the above-mentioned bases, etc. are hardly affected by anionic protective colloids. Therefore, the photosensitive layer is smoothly transferred to an appropriate basic atmosphere, so it is more stable than photosensitive materials obtained by conventional manufacturing methods. Image formation can be performed quickly.

Furthermore, since a highly dispersible neutral binder can be used in the photosensitive material constructed by the above method, it is possible to suppress the occurrence of scratches, etc., which are thought to be mainly caused by agglomeration of capsules. Therefore, by using the photosensitive material according to the method of the present invention, good images without scratches can be obtained.

[Detailed Description of the Invention] The photosensitive material of the present invention has a photosensitive layer containing microcapsules made of an aldehyde polycondensation resin wall containing silver halogenide, a transition agent, and a polymerizable compound on a support. , and the photosensitive layer contains a neutral polymer.

As the silver halide in the light-sensitive material of the present invention, silver halides known in the photographic technology can be used. In the present invention, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, Any grains of silver, silver iodobromide, or silver chloroiodobromide can be used.

The halogen composition of silver halide grains may be uniform or non-uniform on the surface and inside. For silver halide grains having a multiple structure with different compositions on the surface and inside, Japanese Patent Laid-Open No. 57 -154232, 58-10853
No. 3, No. 59-48755, No. 59-52237, US Pat. No. 4,433,048, and European Patent No. 100.984. Also, like the photosensitive material described in Japanese Patent Application No. 61-25576,
Silver halide grains having a high proportion of silver iodide in the shell portion may also be used.

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.

In the silver halide used in the light-sensitive material of the present invention, two or more types of silver halide grains different in halogen composition, crystal habit, grain size, etc. may be used in combination.

There are no particular restrictions on the grain size distribution of silver halide grains1.For example, monodisperse silver halide grains with a substantially uniform grain size distribution, such as the photosensitive material described in Japanese Patent Application No. 61-55508, are used. May be used.

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

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 1 in terms of silver, including organic silver salt, which is an optional component described below.
It is preferable to set it in the range of Og/rrf.

The reducing agent that can be used in the light-sensitive material of the present invention has a function of reducing silver halide and/or a function of promoting (or suppressing) polymerization of a polymerizable compound. There are various types of reducing agents having the above functions.

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, amyl reductones, O- or p-sulfonamidophenols, O- or p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamide-5- Examples include pyrazolones, 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines. By adjusting the type, amount, etc. of the reducing agent, it is possible to polymerize the polymerizable compound in either the area where the silver halide latent image is formed or the area where no latent image is formed. In addition, in a system in which a polymerizable compound is polymerized in a portion where a silver halide latent image is not formed, l is used as a reducing agent.
It is particularly preferred to use -phenyl-3-pyrazolidones.

Regarding various reducing agents having the above functions, see Japanese Patent Application No. 60-22980, No. 60-29894, and No. 60-298.
No. 68874, No. 60-210657, No. 60-22
No. 6084, No. 60-227527, No. 60-227
528, and 61-42746, etc.! (including those described as developing agents or hydrazine derivatives); and regarding the above reducing agents, T.

“The Theory of the” by James
PhotographicP r a c e s s
"Fourth Edition, pp. 291-334 (1977), Research Volume Disclosure Magazine, Vol.

170. It is also described in No. 17029 (pages 9 to 15) of June 1978, No. 17643 of December 1978 (pages 22 to 31). Furthermore, as in the photosensitive material described in Japanese Patent Application No. 61-55505, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. good.

In the light-sensitive material of the present invention, the reducing agents and reducing agent precursors described in the above-mentioned specifications and literatures can be effectively used.

Therefore, the r-reducing agent J in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned specifications and literatures.

These reducing agents may be used alone, but as described in the above specifications, two or more reducing agents may be used in combination, or two or more reducing agents may be used. When used together, the interaction of 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).
8 and/or organic silver salt)
It is conceivable that the oxidized form of the reducing agent causes polymerization of the polymerizable compound (or suppresses the polymerization) via an oxidation-reduction reaction with another reducing agent coexisting. 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 pentadecyl/\hydroquinone, 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-hexa Decyloxy-5-t-octylphenol, 2-phenylsulfonylamine-4-t-butyl-5-hexadecyloxyphenol, 2-(N-
butylcarbamoyl)-4-phenylsulfonylaminonaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol, l-acetyl-2-phenylhydrazine, 1-7cetyl-2-
((p or 0)-7minophenyl)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-)
Lythyl-2-(2,6-dichloro-4-cyanophenyl)hydrazine, 1-trityl-2-phenylhydrazine, 1-phenyl-2-(2,4,6-)dichlorophenyl)hydrazine, l-(2-( 2,5-di-t-pentylphenoxy)butyroyl) -2-((p or 0)
-7minophenyl)hydrazine, 1-(2-(2,5-
di-t-pentylphenoxy)butyroyl)-2-((
p or o)-7minophenyl)hydrazine pentadecylfluorocaprylate, 3-indazolinone, 1-
(3,5-dichlorobenzoyl)-2-phenylhydrazine, l-)richyl-2-[(2-N-butyl-N-octylsulfamoyl)-4-methanesulfonyl)phenylhydrazine, 1-(4-( 2,5-di-t-pentylphenoxy)butyroyl)-2-((p or O)-
methoxyphenyl)hydrazine, l-(methoxycarbonylbenzohydryl)-2-phenylhydrazine, 1-
formyl-2-[4-(2-(2,4-di-t-pentylphenoxy)butyramido)phenyl]hydrazine,
l-7 Cetyl-2-, [4-(2-(2,4-di-t-
pentylphenoxy)butyramido)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, l-benzoyl-2-tritylhydrazine, 1-(4-butoxybenzoyl)- 2-1 Lythylhydrazine, 1-(2,4-dimethoxybenzoyl)-2
-tritylhydrazine, 1-(4-dibutylcarbamoylbenzoyl)-2-)lythylhydrazine, and 1-
(1-naphthoyl)-2-tritylhydrazine and the like can be mentioned.

In the light-sensitive material of the present invention, 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 silver salt). .

The polymerizable compound that can be used in the photosensitive material of the present invention is not particularly limited, and known polymerizable compounds can be used.

Note that when heat development treatment is planned as a method of using the photosensitive material, it is preferable to use a compound with a high boiling point (for example, a boiling point of 80° C. or higher) that is difficult to volatilize during heating.
Furthermore, in the embodiment that includes a color image-forming substance as an optional component described below, the color image-forming substance is immobilized by polymerization and curing of the polymerizable compound. A crosslinkable compound having a group is preferable.

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 having an ethylenically unsaturated group that can be used in the photosensitive material of the present invention include acrylic acid and its salts;
Acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, f# water mamalate maleate,
Examples include itaconic acid 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 the present invention include acrylic esters such as 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, to dipentaerythritol Examples include hexaacrylate, diacrylate of polyoxyethylated bisphenol A, polyacrylate of hydroxypolyether, polyester acrylate, and polyurethane acrylate.

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

The above-mentioned polymerizable compounds may be used alone or in combination of two or more types.A photosensitive material using a combination of two or more types of polymerizable compounds is described in Japanese Patent Application No. 1983-55504. . Note that a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the above-mentioned reducing agent can also be used as the polymerizable compound of the present invention. It goes without saying that the use of a substance that functions both as a reducing agent and a polymerizable compound as described above is also included in the embodiment of the present invention.

In the light-sensitive material of the present invention, the polymerizable compound is preferably used in an amount of 5 to 120,000 parts by weight, more preferably 10 to 10,000 parts by weight, per 1 part by weight of silver halide. .

In the photosensitive material of the present invention, a polymer image can be obtained by polymerizing a polymerizable compound with the above-described structure, but a color image can be formed by including a color image forming substance in the photosensitive layer as an optional component described below. You can also do that.

In the photosensitive material of the present invention, silver halide, a reducing agent, and a polymerizable compound are contained in a photosensitive layer in a state in which they are housed in microcapsules made of an aldehyde polycondensation resin wall.

As for the microencapsulation method using the aldehyde polycondensation resin wall material (shell material), various known methods can be used without any particular limitations.

Specifically, Japanese Patent Publication Nos. 53-84881 and 53-84
No. 882, No. 53-84883, JP-A-52-668
No. 78, JP-A-51-144383, JP-A-51-9
No. 079, JP-A No. 47-42383, JP-A No. 52-1
Publications such as No. 8671 and U.S. Patent No. 3,993,83
Examples include the method described in Specification No. 1 and the like.

Examples of materials that can be advantageously used as the wall material (shell material) of the microcapsules of the present invention include urea resins and melamine resins. As a method for forming these outer shells, for example, the following method can be used.

A hydrophobic liquid (photosensitive composition) consisting of a core substance such as a polymerizable compound, silver halide, a reducing agent, and an optional component such as an image forming substance (for example, a dye) is mixed with a 7-ionic protective colloid described below. It is emulsified and dispersed in an aqueous medium containing at least one type.

Next, a reactive compound (for example, urea and formaldehyde) is added to this emulsion.

By adjusting the PI3 temperature, etc., external polymerization occurs around the oil droplet-shaped core material and the aldehyde polycondensation resin wall (
In the above case, a capsule shell consisting of a urea resin wall is formed.

As described above, the anionic protective colloid is used to disperse a hydrophobic liquid into microdroplets in an aqueous medium and to prevent the microdroplets from agglomerating or becoming one body. Anionic protective colloid-forming substances suitable for such purposes are anionic polymeric compounds. Such examples include polystyrene sulfonates and copolymers, polyvinyl sulfate ester salts, polyvinyl sulfonates, maleic anhydride/styrene copolymers, maleic anhydride/imbutylene copolymers, maleic anhydride/ethylene Copolymers, maleic anhydride/methyl vinyl ether copolymers, polyvinyl alcohol (saponified products), carboxyl-modified polyvinyl alcohol, gum arabic, polyacrylates and their derivatives and copolymers, carboxymethyl cellulose, pectin, pullulan, cellulose sulfate Examples include ester salts and alginates.

The photosensitive layer, which is a feature of the present invention, contains a neutral binder instead of an anionic protective colloid.

That is, in order to produce the photosensitive material of the present invention, the anionic protective colloid is removed from the dispersion containing microcapsules containing the photosensitive ffi composition obtained by the method described above, and instead, the medium is added. The purpose is to add a binder to form a coating solution for forming a photosensitive layer.

As a method for removing the anionic protective colloid, a known physical treatment method can be used.

Specifically, the microcapsules are separated by centrifugation that also serves as washing of the dispersion: 'The pH of the dispersion is adjusted to a constant condition, and then the microcapsules are removed by steam distillation (Japanese Patent Laid-Open No. 55 -47138 publication); the above dispersion is subjected to membrane permeation treatment (dialysis, filtration) (see Publication No. 56-21639). By using these methods, most of the anionic protective colloid contained in the capsule dispersion is removed, and only the microcapsules can be separated from the dispersion and taken out. Note that the above removal methods have different processing times depending on the method adopted.

The treatment temperature and number of treatments can be determined as appropriate.

In particular, in the present invention, it is preferable to remove the anionic protective colloid by centrifugation from the viewpoint of simplicity in the manufacturing process, and in this case, after dispersing the capsule liquid by adding water as appropriate, It is a good idea to repeat the centrifugation several times.

Next, an aqueous solution containing a neutral binder is added to the microcapsules separated from the dispersion to prepare a coating solution for forming a photosensitive layer.

The above-mentioned neutral Paigoo is not particularly limited and can be appropriately selected from known binders used in photographic technology and the like. However, the binder that can be used in the present invention is preferably a polymer compound with a molecular weight in the range of about 10 million to 10 million.
Such examples include cellulose derivatives such as methylcellulose, hydroxyethylcellulose, and hydroxypropylcellulose, water-soluble polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and starch. Among these, cellulose derivatives are particularly preferred.

By performing the above series of operations.

The anionic protective colloid is almost completely removed from the photosensitive layer forming coating solution. however.

There is no particular problem with the anionic protective colloid as long as its amount is 50% or less (preferably 10% or less) of the neutral binder.

A photosensitive material constructed using a coating solution for forming a photosensitive layer from which the anionic protective colloid has been removed can be prevented from becoming basic by a basic compound used during development during the image formation process. Since there is no problem, the development processing time can be shortened as described above.

The photosensitive material of the present invention comprises a support and a photosensitive layer containing microcapsules made of aldehyde polycondensation resin walls containing a core material such as silver halide. There are no particular restrictions on the material used for this support. However, when thermal development processing 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 processing.

Materials that can be used for the support include glass, paper, wood-free paper, coated paper, cast coated paper, synthetic paper, metals and their analogs, polyesters, acetylcellulose, and cellulose esters.

Examples include films such as polyvinyl acetal, polystyrene, polycarbonate, and polyethylene terephthalate, and papers laminated with resin materials and polymers such as polyethylene. In addition, when the support is made of porous material such as paper, Japanese Patent Application No. 61-529
It is preferable that the support has a certain level of smoothness like the support used in the photosensitive material described in No. 96.

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

In the photosensitive material of the present invention, a polymerizable compound is contained in microcapsules having walls of aldehyde polycondensation resin. Inside the microcapsules, the above-mentioned silver halide and reducing agent are contained, or will be described later. Any component that can be included in a photosensitive material can also be included.

When silver halide is contained in microcapsules, it is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsules.For photosensitive materials containing silver halide in the wall material of the microcapsules, Special request 1986
It is described in the specification of No.-11556.

Also, silver halide, reducing agents, and polymerizable compounds.

Two or more microcapsules in which at least one component is different among the components accommodated in the microcapsules, such as a color image forming substance, which is an optional component described below, may be used together, especially when forming a full-color image. It is preferable to use three or more types of microcapsules in which the colored image-forming substances contained therein have different color hues, and for photosensitive materials that use two or more types of microcapsules in combination, it is disclosed in Japanese Patent Application No. 6
It is described in the specification of No. 1-42747.

The average particle size of the microcapsules is preferably 3 to 20 ILm. The particle size distribution of the microcapsules is uniformly distributed over a certain value, as in the photosensitive material described in Japanese Patent Application No. 81-150080. It is preferable that the film thickness of the microcapsules is
As in the photosensitive material described in No. 227767, the particle size is preferably within a certain range.

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

Optional components that can be included in the photosensitive layer of the photosensitive material include a one-color image forming substance, a #1 sensitive dye, an organic silver salt, a radical generator, and various image formation accelerators.

Thermal polymerization inhibitors, thermal polymerization initiators, development stoppers, fluorescent whitening agents, antifading agents, anti-irradiation dyes or pigments, pigments that can be decolored by heating or light irradiation, matting agents, Examples include anti-smudge agents, plasticizers, water release agents, binders, photopolymerization initiators, solvents for polymerizable compounds, and water-soluble vinyl polymers.

In the photosensitive material of the present invention, a polymer image can be obtained by the above-described structure of the photosensitive layer, but a color image can also be formed by including a color image forming substance as an optional component in the photosensitive layer.

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. General photosensitive materials using one-color image forming substances are described in the above-mentioned Japanese Patent Application Laid-open No. 73145/1983. Regarding photosensitive materials using dyes or pigments as color image forming substances, see Japanese Patent Application No. 61-29987, and about photosensitive materials using leuco dyes, see Japanese Patent Application No. 61-53876. For photosensitive materials using leuco dyes, see Japanese Patent Application No. 61-96339, and for photosensitive materials using yellow coloring leuco dyes, see Japanese Patent Application Nos. 133091 and 1983.
No. 092 describes a photosensitive material using a cyan color-forming leuco dye in patent application No. 1'li! (61-19796
Specification No. 3 contains the respective descriptions.

Dyes and pigments, which are substances that color themselves, are available commercially as well as in various literature (for example, "Dye Handbook" edited by the Organic Synthetic Chemistry Association, published in 1970; "Latest Pigment Handbook" edited by the Japan Pigment Technology Association; The publicly known one described in ``Published in 1972'' can be used. These dyes or pigments are used after being dissolved or dispersed.

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

Examples of substances that develop color upon contact with another component include various systems that develop color due to acid-base reactions, redox reactions, coupling reactions, chelate formation reactions, etc. between two or more components. For example, pressure-sensitive copying paper (pages 29-58) and Azography (pages 87-58) described in Hiroyuki Moriga's Introduction to Special Paper Chemistry J (published in 1975)
95 pages), known coloring systems such as heat-sensitive coloring by chemical changes (pages 118-120), or a preview of the seminar sponsored by the Kinki Chemical Industry Association - Latest Pigment Chemistry - Attractive Uses and New Developments as Functional Dyes - 1 Collection, pp. 26-32, (198
It is possible to use the coloring system described in June 19, 2013).

Specifically, the coloring system consists of coloring agents with partial structures such as lactones, lactams, and spiropyrans used in pressure-sensitive paper, and acidic substances (coloring agents) such as acid clay and phenols; aromatic diazonium salts and Systems that utilize azo coupling reactions between diazotate, diazosulfonates, naphthols, anilines, active methylenes, etc.; reactions between hexamethylenetetramine and ferric ions and gallic acid; and reactions between phenolphthalein and combreculanes. Chelate-forming reactions such as reactions with alkaline earth metal ions, redox reactions such as reactions between ferric nistearate and pyrogallol, and reactions between silver behenate and 4-methoxy-1-naphthol can be used.

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

In addition, when using two types of substances that cause a coloring reaction when brought into contact with each other as the above-mentioned solid color image forming substances, one of the substances that cause a coloring reaction and a polymerizable compound are placed in microcapsules. A color image can be formed on the photosensitive layer by accommodating the microcapsules containing the polymerizable compound and allowing other substances among the substances that cause the color-forming reaction to exist outside the microcapsules containing the polymerizable compound. A photosensitive material capable of producing a color image without using an image-receiving material as described above is described in Japanese Patent Application No. 53881/1981.

What are the sensitizing dyes that can be used in photosensitive materials?

There are no particular limitations, and silver halide sensitizing dyes known in the photographic technology can be used. The sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, and the like. These sensitizing dyes may be used alone or in combination. Especially when the purpose is supersensitization, it is common to use a combination of sensitizing dyes. be. In addition, along with the sensitizing dye, a dye that itself does not have a spectral sensitizing effect, or a substance that does not substantially absorb visible light but exhibits supersensitization may be used in combination.The amount of the sensitizing dye added is as follows: Generally 10-8 per mole of halogenated fi
The amount is about 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. k! Regarding a light-sensitive material obtained by adding a tJ-sensitizing dye at the stage of forming silver halide grains, Japanese Patent Application No. 139746/1984 describes that the sensitizing dye is added to silver halide grains after the formation of silver halide grains. The light-sensitive materials obtained by adding these at the stage of emulsion preparation are described in Japanese Patent Application No. 55510/1983. Further, specific examples of sensitizing dyes that can be used in light-sensitive materials are also disclosed in the above-mentioned patent application No. 13974/1986.
No. 6 and No. 61-55510. Further, as in the photosensitive material described in Japanese Patent Application No. 61-208786, a sensitizing dye sensitive to infrared light may be used in combination.

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 catalyzed by a latent image of silver halide. 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 compounds constituting the organic silver salt include aliphatic or aromatic carboxylic acids, mercapto groups, or α-hydrogen. Examples thereof include thiocarbonyl group-containing compounds and imi-7 group-containing compounds. Among them.

The organic silver salts are particularly preferably benzotriazole,
Generally 0.01 to 10 mol per mol of silver halide,
Preferably it is used in an amount of 0.01 to 1 mol. Note that 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. For photosensitive materials using organic silver salts, a patent application was filed in 1986.
It is preferable to use 0 or more of the organic silver salts described in Japanese Patent No. 141,799 in an amount of 0.1 to 10 mol per mol of silver halide.

It is more preferable to use it in a range of 0.01 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 No. 38510/1983, and a photosensitive material using silver diazotate is described in Japanese Patent Application No. 61-38510.
No. 38511 describes a photosensitive material using an azo compound, and Japanese Patent Application No. 38512/1983 describes a photosensitive material using an azo compound.

Various image formation accelerators can be used in the photosensitive material. The image formation accelerator includes silver halide (and/or an organic FF1F!) and a reducing agent, an oxidation-reduction agent, and an oxidation amount photoreaction. 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).

From the viewpoint of physicochemical functions, image formation accelerators include bases,
Base precursors, oils, surfactants.

It is further classified into compounds having a capri-preventing function and/or a development accelerating function, a heat solvent, a compound having an oxygen removing function, and the like. 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.

Examples of preferred bases include inorganic bases such as alkali metal or alkaline earth metal hydroxides; 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 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-hydroxylalkyl-substituted aromatic amines and bis[p
-(dialkylamino)phenyl]methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, etc., and those having a pKa of 7 or more are particularly preferred.

Examples of base precursors include salts of organic acids and bases that decarboxylate when heated, compounds that release amines through reactions such as intramolecular nucleophilic substitution, Rossen rearrangement, and Beckmann rearrangement. Compounds that emit bases and compounds that generate bases by electrolysis or the like are preferably used. Specific examples of base precursors include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, p-1 luidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonylacetate, 4-chlorophenylsulfonylacetate guanidine, and 4-chlorophenylsulfonylacetate. Examples include guanidine methyl-sulfonylphenylsulfonylacetate and guanidine 4-7cetylaminomethylpropiolate.

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 0.61% 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.

Incidentally, a photosensitive material using a base or a base precursor is described in Japanese Patent Application No. 60-227528. Regarding photosensitive materials using a tertiary amine as a base, Japanese Patent Application No. 13181/1981 describes a photosensitive material using a fine particle dispersion of a hydrophobic a-basic compound having a melting point of 80 to 180°C. For the patent application No. 61-52992
The patent application No. 61-215637 describes a photosensitive material using a guanidine derivative with a solubility of 0.1% or less.
In the specification of the patent application No. 1987, for photosensitive materials using hydroxides or salts of alkali metals or alkaline earth metals,
Each of these is described in the specification of No.-96341.

Furthermore, regarding a photosensitive material using an acetylide compound as a base precursor, Japanese Patent Application No. 167558/1984 describes using a propiolate as a base precursor and further using silver, copper, a silver compound, or a copper compound as a catalyst for the base production reaction. Regarding the photosensitive materials included as
Japanese Patent Application No. 191000 describes a photosensitive material containing the propiolic acid salt and the silver, copper, silver compound, or copper compound separated from each other in Japanese Patent Application No. 1982-227769. Regarding photosensitive materials containing copper, a silver compound, or a ligand in a free state in addition to a copper compound, Japanese Patent Application No. 61-243555 spec. Regarding photosensitive materials containing chemical compounds as reaction accelerators for base-forming reactions, Japanese Patent Application No. 1986-19100
In the specification of No. 1, a photosensitive material using a sulfonylacetate as a base precursor and containing a heat-melting compound as a reaction accelerator for the base production reaction is disclosed in Japanese Patent Application No. 1983-1983.
No. 3375 describes a photosensitive material using a compound in which inocyanate or isothiocyanate is bonded to an organic base as a base precursor in Japanese Patent Application No. 61-16.
Each of these is described in the specification of No. 7558.

When a base or a base precursor is used in the photosensitive material of the present invention, silver halide,
It is preferable to adopt a mode in which a reducing agent and a polymerizable compound are accommodated, and a base or a base precursor is present in the photosensitive layer outside the microcapsules.
In addition to the above specification, there are photosensitive materials that use microcapsules containing bases or base precursors, such as the photosensitive material described in No. 52988, which may contain a base or a base precursor in another microcapsule. Japanese Patent Application No. 61-52989 describes a photosensitive material in which a base or a base precursor is dissolved or dispersed in an aqueous solution of a water retention agent and housed in a microcapsule. The photosensitive material housed in the patent application No. 61-5299
5 and Japanese Patent Application No. 61-212149 describes a photosensitive material using microcapsules containing a basic compound having a melting point of 70 DEG C. to 210 DEG C., 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.

Note that the base or base precursor is
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. Regarding photosensitive materials using antifoggants as compounds having antifogging and/or development accelerating functions, see Japanese Patent Application No. 60-294337, and about photosensitive materials using compounds having a cyclic amide structure. is described in Japanese Patent Application No. 60-294338, and the photographic material using a 1,000-oneythyl compound is described in Japanese Patent Application No. 60-294338.
No. 0-294339 describes a photosensitive material using a polyethylene glycol derivative in Japanese Patent Application No. 60-294.
340, Japanese Patent Application No. 60-294341 for photosensitive materials using thiol derivatives, and Japanese Patent Application No. 61-2 for photosensitive materials using acetylene compounds.
For photosensitive materials using sulfonamide derivatives, see Japanese Patent Application No. 61-25578.
Photosensitive materials using quaternary ammonium salts are described in Japanese Patent Application No. 61-238871.

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. Useful thermal solvents include:
Polyethylene glycols described in U.S. Patent No. 3,347,675, derivatives such as oleic acid esters of polyethylene oxide, beeswax, monostearin, -S
Compounds with high dielectric constant having O2- and/or -CO- groups, polar substances described in U.S. Pat. No. 3,667,959, t,io-decanediol described in Research Disclosure magazine, December 1976 issue, pages 26-28 , methyl anisate, biphenyl perate and the like are preferably used. Note that a photosensitive material using a hot solvent is described in Japanese Patent Application No. 1983-227527.

A compound having the ability to remove oxygen can be used for the purpose of eliminating the influence of oxygen (oxygen has a polymerization inhibiting effect) during development. Examples of compounds having an oxygen removing function include compounds having two or more mercapto groups. Note that a photosensitive material using a compound having two or more mercapto groups is described in Japanese Patent Application No. 53880/1980.

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

Thermal polymerization initiators are described in pages 6 to 18 of "Addition Polymerization/Ring-Opening Polymerization J, 1983, Kyoritsu Shuppan," edited by the Editorial Committee of Polymer Experiments, The Polymer Society of Japan.Initiation of thermal polymerization Specific examples of agents include azobisisobutyronitrile,
1.1'-azobis(l-cyclohexanecarbonitrile), dimethyl-2,2'-azobisisobutyrate,
Azo compounds such as 2,2-azobis(2-methylbutyronitrile) and azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydro Examples include organic peroxides such as peroxide, inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, and sodium p-toluenesulfinate.

The amount of S polymerization initiator is 0.1 to 12 per polymerizable compound.
It is preferable to use it in the range of 0% by weight, and 1 to 10% by weight.
It is more preferable to use a thermal polymerization initiator in the range of % by weight.In a system in which the polymerizable compound is polymerized in the area where a silver halide latent image is not formed, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Further, a photosensitive material using a thermal polymerization initiator is described in Japanese Patent Application No. 1983-210657.

The development stopper that can be used in the present invention is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and silver salts, and that quickly neutralizes the base or reacts with the base to reduce the base concentration in the film and stop the development. It is a compound that suppresses development. Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include
Oxime esters described in JP-A No. 08837 and JP-A No. 60-192939, and compounds that release an acid by Rossen rearrangement described in JP-A-60-230133 can be mentioned. In addition, as an example of an electrophilic compound that causes a substitution reaction with a base when heated, JP-A-60-230
Examples include the compounds described in Publication No. 134.

A dye or pigment may be added to the photosensitive layer of a photosensitive material for the purpose of preventing halation or irradiation. The material is described in Japanese Patent Application No. 174402/1982.

In addition, the microcapsules may contain a dye having the property of decolorizing by heating or light irradiation.
It can function as a yellow filter in conventional silver halide photography. Regarding photosensitive materials using dyes that have the property of being decolored by heating or light irradiation as mentioned above, Japanese Patent Application No. 61-24
It is described in the specification of No. 3551.

The anti-smudge agent used in photosensitive materials is preferably a particulate material that is solid at room temperature.
Starch particles described in US Pat. No. 2,322,347, fine polymer powders as described in US Pat. No. 3,625,736, etc., microcapsule particles not containing a color former as described in UK Pat. No. 1,235,991, etc., US Pat. No. 2,711,375 Examples include inorganic particles such as cellulose fine powder, talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina. The average particle size of the above particles is 3 to 50 JL per volume average diameter.
m is preferably in the range of 5 to 40. A range of Bm is more preferable, and the particles are more effective if they are larger than microcapsules. Regarding photosensitive materials using a binder together with microcapsules, Japanese Patent Application No. 1986-
It is described in the specification of No. 52994.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing unpolymerized polymerizable compounds after image transfer. It is described in the specification of No. 1983-3025.

When a solvent for a polymerizable compound is used in the photosensitive material of the present invention, it is preferable to encapsulate the solvent in a microcapsule separate from the microcapsule containing one polymerizable compound. Regarding photosensitive materials using organic solvents that are miscible with compounds, patent application No. 1986-
It is described in the specification of No. 52993.

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 above-mentioned series of photosensitive materials and Research Disclosure Magazine Vol.

No. 17029, June 1978 (pages 9-15). - The photosensitive layer of the photosensitive material comprising the above-mentioned components preferably has a pH value of 7 or less, as in the photosensitive material described in Japanese Patent Application No. 104226/1982.

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

As a method of using the photosensitive material of the present invention, instead of using the image-receiving material described later, the above 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 include:
The structure can be similar to that of the image-receiving layer provided on the image-receiving material. Details of the image receiving layer will be described later.

Regarding photosensitive materials using one heating layer, a patent application filed in 1986
For photosensitive materials provided with a cover sheet or a protective layer, see Japanese Patent Application No. 61-55507, and for photosensitive materials provided with a layer containing a base or base precursor, see Japanese Patent Application No. 61-96340. A photosensitive material provided with a colored layer as an antihalation layer is described in Japanese Patent Application No. 1983-246901. Furthermore, a photosensitive material provided with a single base barrier layer is also described in the above-mentioned Japanese Patent Application No. 61-96340. Furthermore, examples of other auxiliary layers and their usage are also described in the applications relating to the above-mentioned series of light-sensitive materials.

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

Although various methods can be used to produce the photosensitive material of the present invention, the general production method includes the step of preparing a photosensitive composition consisting of a core material containing a polymerizable compound, as described above. A step of microencapsulating the composition in an aqueous medium, further removing the 7-ionic protective colloid from the microcapsule dispersion and adding a neutral binder instead, to prepare a coating solution for forming a photosensitive layer, and the coating solution. The process consists of applying the above-mentioned material to a support and drying it.

Generally, the above-mentioned photosensitive composition is prepared by preparing a liquid composition containing each component and then mixing the respective liquid compositions. Some of the constituent components of the photosensitive layer can also be added during the preparation of the photosensitive composition or coating solution or after production. Furthermore, a method of preparing a secondary composition by further emulsifying an oil-based (or aqueous) composition containing one or more components in an aqueous (or oil-based) solvent can also be used.

Regarding the main components contained in the photosensitive layer, methods for preparing the photosensitive composition and coating liquid 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 silver ion excess conditions, which may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof, and a Chondral double-jet method in which pAg is kept constant can also be employed. In addition, to accelerate particle growth,
The concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Application Laid-Open No. 1581-1581).
24, 55-158124 and US Pat. No. 3,650,757).

Silver halide emulsions used in the production of photosensitive materials may be of the surface latent image type, in which the latent image is mainly formed on the surface of the grains, or the internal latent image type, in which the latent image is formed inside the grains. It is also possible to use direct inversion emulsions in combination with type emulsions and nucleating agents. Internal latent image emulsions suitable for this purpose are described in U.S. Pat. No. 2,592,250 and U.S. Pat. No. 3,761,276;
No. 6641, various publications, etc. are described. A preferred nucleating agent for combination with the above emulsion is US Pat. No. 3,227,552
No. 4245037, No. 4255511, No. 4266013, No. 4276364, and OLS No. 2635316.

In the preparation of silver halide emulsions used in the production of photosensitive materials, it is preferable to use woody colloids as protective colloids. Examples of woody colloids include gelatin, gelatin derivatives, gelatin and other polymers. Graft polymers with proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfate esters, sugar derivatives such as alginic soda, starch derivatives; and polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl A wide variety of synthetic wood-philic polymeric materials can be mentioned, such as single or copolymers of imidazole, polyvinylpyrazole, and the like. Among these, gelatin is preferred.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

[Silver halide emulsion is prepared by using ammonia, organic onythyl derivatives (see Japanese Patent Publication No. 47-386), and sulfur-containing compounds (see Japanese Patent Application Laid-Open No. 144319-1988) 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 coexist, and in addition, iridium chloride (■ or ■) may be used to improve high illuminance failure and low illuminance failure.
, water-soluble iridium salts such as ammonium hexachloroiridium salt, or water-soluble rhodium salts such as rhodium chloride.

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 unheated, 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, Publication No. 58-215644).

In addition, when adding a sensitizing dye to a silver halide emulsion,
The above-mentioned patent applications No. 80-139746 and No. 61-5
It is preferable to add the nitrogen-containing heterocyclic compound in the preparation stage of the silver halide emulsion as in the light-sensitive material described in No. In the case of silver halide emulsion preparation, the nitrogen-containing heterocyclic compound is preferably added at the stage of forming or ripening silver halide grains. The manufacturing method is described in Japanese Patent Application No. 3024/1983.

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, such as silver halide (including silver halide emulsions), reducing agents, A color image-forming substance or the like can be dissolved, emulsified or dispersed in a polymerizable compound and used in the production of a photosensitive material. In particular, when adding a color image forming substance, it is preferable to include it in a polymerizable compound, and when microcapsulating oil droplets of a monopolymerizable compound as described later, microencapsulation The polymerizable compound may contain components such as wall materials necessary for this purpose.

Photosensitive JIIi containing silver halide in a polymerizable compound
Some can be prepared using silver halide emulsions. In addition to the 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 obtained by stirring with a homogenizer, blender, mixer, or other commonly used stirrers.

In addition, it is preferable that a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit is dissolved in the polymerizable compound used for preparing the photosensitive composition.For photosensitive compositions containing the above-mentioned copolymer, , special application 1986-
It is described in the specification of No. 261887.

Alternatively, instead of using the above copolymer, a photosensitive composition may be prepared by dispersing microcapsules having a silver halide emulsion as a core material in a polymerizable compound. A photosensitive composition containing microcapsules is described in Japanese Patent Application No. 5750/1983.

It is preferable to use the polymerizable compound (including those containing other constituent components like the above-mentioned photosensitive composition) as an emulsion in an aqueous solvent.
When oil droplets of a polymerizable compound are microencapsulated, as in the photosensitive material described in No. 117089, a wall material necessary for microencapsulation is added to the emulsion, and the outside of the microcapsules is A shell-forming treatment can also be carried out at this emulsion stage. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

The photosensitive composition obtained above is first microencapsulated (microcapsules having an aldehyde polycondensation resin wall) according to the shell forming method described above to prepare a capsule dispersion. Furthermore, the 7-ionic protective colloid is removed from this capsule dispersion using the above-mentioned method, and then a neutral binder is added to prepare a coating solution for forming a photosensitive layer.

Other components can also be added at this stage of coating blood in the same manner as in the case of the emulsion described above.

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

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

The light-sensitive material of the present invention is used after being subjected to development treatment simultaneously with imagewise exposure or after imagewise fogging.

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

The photosensitive material of the present invention can be subjected to imagewise exposure at the same time as described above.

Alternatively, after imagewise exposure, a photosensitive material may be subjected to a development process using a developer described in Japanese Patent Publication No. 11149/1983.In addition, as mentioned above, a heat development process may be carried out. The method described in Japanese Unexamined Patent Publication No. 61-69062 is a dry treatment, so it has the advantage of being simple to operate and capable of being processed in a short time. Therefore, the latter method is particularly excellent for developing photosensitive materials.

As the heating method in the above heat development treatment, various conventionally known methods can be used. Furthermore, as in the photosensitive material described in Japanese Patent Application No. 60-135568, a heat generating layer may be provided on the photosensitive material and used as a heating means. As in the image forming method described above, heat development may be carried out while suppressing the amount of oxygen present in the photosensitive layer, and the heating temperature is generally 80°C to 200°C, preferably 100°C to 100°C.
The temperature is 60°C. The heating time is generally 1 second to 5 minutes.
Preferably it is 5 seconds 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. 178417/1983.

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 photosensitive material described in No. 210657, by adjusting the type, amount, etc. of the reducing agent, it is also possible to polymerize the polymerizable compound in the area where the silver halide latent image is not formed.

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 the above-mentioned Japanese Patent Application No. 61-53881, the developed photosensitive material is pressurized to destroy the microcapsules and cause a coloring reaction. Color images can be formed on photosensitive materials by bringing different types of substances into contact.

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

The image-receiving material will be explained below. The general image forming method using an image-receiving material or an image-receiving layer is described in Japanese Patent Application No. 121284/1984.

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. Note that when a porous material such as paper is used as the support for the image-receiving material, it is preferable that it has a certain level of smoothness as in the image-receiving material described in Japanese Patent Application No. 61-52990. Further, an image receiving material using a transparent support is described in Japanese Patent Application No. 52991/1983.

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.

It is preferable that the image-receiving layer contains a polymer as a binder. In addition to the binder that can be used in the photosensitive layer of the photosensitive material described above, natural substances such as gelatin, gelatin derivatives, and gum arabic can be used as the binder. Alternatively, synthetic polymeric materials such as acrylamide polymers can also be used. Further, as in the image-receiving material described in Japanese Patent Application No. 61-53879, a polymer with low oxygen permeability may be used as the binder.

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 forming the image. There are no particular restrictions on the thermoplastic compound mentioned above, and known plastic resins (
It can be arbitrarily selected from among (plastic), wax, etc. However, it is preferable that the glass transition point of the thermoplastic resin and the melting point of the wax be 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. 1986-124
No. 952 and 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, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of smoothly proceeding with the curing treatment (fixing treatment) of the unpolymerized polymerizable compound. Further, regarding an image receiving material having an image receiving layer containing a photopolymerization initiator, see Japanese Patent Application No. 61-3025, and regarding an image receiving material having an image receiving layer containing a thermal polymerization initiator, see Japanese Patent Application No. 61-55502. There are descriptions for each.

A dye or pigment can be included 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 an image a specific color. In addition, for the purpose of easily distinguishing between the front and back sides of the image-receiving material, a dye or a pigment may be included in the image-receiving layer. Various substances known in the art can be used, but if the dye or pigment may impair the image formed in the image-receiving layer, the dye density of the dye or pigment may be lowered (e.g., reflection density 1 or less), or it is preferable to use a dye or pigment that has the property of decolorizing by heating or light irradiation.
An image-receiving material having an image-receiving layer containing a dye or pigment that has the property of being decolored by heating or light irradiation is described in Japanese Patent Application No. 1983-96339.

Furthermore, 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 amount of white pigment is 10 g per 1 g of the thermoplastic compound.
It is preferable to use the amount in the range of 100 g to 100 g.

When the dye or pigment mentioned above is contained in the image-receiving layer, it may be contained uniformly or unevenly distributed in some areas.For example, the support described below may be made of a light-transmitting material. However, by including the white pigment in a part of the image-receiving layer, a part of the reflected image can be made into a projected image.

By doing so, image information that is unnecessary in the projected image can also be written as a reflected image in the image-receiving layer portion containing the white pigment.

The image-receiving layer may be configured as two or more layers depending on the functions described above, and the thickness of the image-receiving layer may range from 1 to 1.
00 gm is preferable.

More preferably, it is 1 to 20 #Lm.

Note that a protective layer may be further provided on the image-receiving layer, or a layer made of aggregates of fine particles of a thermoplastic compound may be provided on the image-receiving layer. An image receiving material provided with a layer made of aggregates of fine particles of a compound is described in Japanese Patent Application No. 55503/1983.

Furthermore, an adhesive or a layer containing an adhesive and a release paper may be sequentially laminated on the surface of the support opposite to the side on which the image-receiving layer is provided, the sticker-like image-receiving material having the above structure. 1 Patent application filed by the applicant 1986-16926
It is stated in the Specification No. 4.

The photosensitive material of the present invention is developed as described above,
By pressing the above image-receiving materials in a stacked state,
The unpolymerized polymerizable compound can be transferred to an image-receiving material to obtain a polymer image on the image-receiving material. Regarding the above-mentioned pressurizing means, various conventionally known methods can be used.

Further, in an embodiment in which the photosensitive layer contains a color image forming substance,
By performing a similar development treatment, the polymerizable compound is polymerized and cured, thereby immobilizing the color image forming substance in the cured portion. Then, by pressing the photosensitive material and the image-receiving material in a superimposed state, the uncured portion of the color-image forming substance 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 Japanese Patent Application No. 61-55501. There is also the advantage that unpolymerized polymerizable compounds transferred to the image are polymerized and the storage stability of the obtained image is improved.

The photosensitive material of the present invention includes a photosensitive material for monochrome or color photography and printing, a printing photosensitive material, a printing plate, an X-ray photosensitive material, a medical photosensitive material (for example, a CRT photosensitive material for an ultrasound diagnostic machine), and a computer graphic hard copy. It has many uses such as photosensitive materials and photosensitive materials for copying machines.

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

[Example 1] [Creation of photosensitive material] A photosensitive material was prepared as follows.

Preparation of silver halide milk Dissolve 40 g of gelatin and potassium bromide in 3000 mu of water, heat to 50°C, and add 1R3 nitric acid while stirring.
4g dissolved in 200mM water was added over 10 minutes. Thereafter, 3.3 g of potassium iodide dissolved in 100 mM of water was added over 2 minutes. The pH of the silver iodobromide emulsion thus obtained was adjusted, and after removing excess salt by sedimentation, the pH was adjusted to 6.0 to obtain a silver iodobromide emulsion with a yield of 400 g.

Preparation of benzotriazole silver emulsion 28 g of gelatin and 13.2 g of benzotriazole are mixed with 3 ml of water.
000 mJL. This solution was stirred while being maintained at 40°C, and a solution of 17 g of silver nitrate dissolved in 100 mJl of water was added over 2 minutes.

Excess salt was precipitated and removed by adjusting the pH of the resulting emulsion. Thereafter, the pH was adjusted to 6.30 to obtain a benzotriazole silver emulsion. The yield of emulsion was 400 g.

Preparation of sensitive composition Add 100 g of trimethylolpropane triacrylate to Nocobo! J-2-0, 40g, Pargus Script Red l-6-B (manufactured by Ciba Geigy)6. OOg was dissolved. A solution prepared by dissolving 0.61 g of the following hydrazine derivative and 1.22 g of the following developer in 1.8 g of methylene chloride was added to 18.00 g of the above solution. 4.06 g of the above silver halide emulsion, 3.35 g of benzotriazole silver emulsion
Add 15 g of mixture per minute using a homogenizer.
The mixture was stirred at 000 rpm for 5 minutes to obtain a photosensitive composition.

Below Margin (Copolymer) CH3-+cH2-C←2゜GG20aHq (Hydrazine derivative) (Developer) Preparation of microcapsule liquid Isopan (manufactured by Kuraray ■) [Inbutylene maleic anhydride copolymer, anionic protective colloid 5 10.51 g of a 18.6% aqueous solution of pectin [anionic protective colloid] and 48.56 g of a 2.89% aqueous solution of pectin [anionic protective colloid] were added, and the above photosensitive composition was added to the aqueous solution, which was adjusted to pH 4.0 using a 10% aqueous sulfuric acid solution. 700 using a homogenizer.
The photosensitive composition was stirred at 0 rotation for 2 minutes to emulsify it in the aqueous solvent.

To 72.5 g of this aqueous emulsion, 8.32 g of urea 40% aqueous solution was added.
g, resorcinol 11.3% aqueous solution 2°82g, formalin 37% aqueous solution 8.56g, ammonium sulfate 8.76g
% aqueous solution and continued heating at 60° C. for 2 hours while stirring to prepare a microcapsule dispersion having a urea resin wall (first preparation step).

The microcapsule dispersion obtained above was centrifuged (25
00 rpm, 20 minutes), then add 100 g of water,
Ultrasonic dispersion. After that, centrifugation was performed again. This operation was repeated six times to separate the microcapsules as solid matter.

Next, 50.23% of a 5.7% aqueous solution (pH 7.0) of methyl cellulose (Metrose 65-3R1 manufactured by Shin-Etsu Chemical) [neutral binder] was added to the solid content of the microcapsules.
After adding g, the pH was readjusted to 7.0 using a 10% aqueous sulfuric acid solution to remove the anionic protective colloid to prepare a microcapsule dispersion (first preparation step).

Preparation of photosensitive material To 10.0 g of the microcapsule dispersion prepared as described above (Preparation No.
A coating solution for forming a photosensitive layer was prepared by adding 1.0 g of a solution (water/ethanol = 5:150 volume ratio).

(Anionic surfactant) CH2COOCH2-CHCC2Hs)CaHqNa0
3S-(H-COOCH2-C:H(C2Hs)C4H
q Next, the above coating solution was applied onto a 100 gm thick polyethylene terephthalate using a #40 coating rod and dried at about 40°C to remove the anionic protective colloid and replace it with a neutral binder. A photosensitive material (A) according to the present invention was prepared.

[Comparative Example 1] In Example 1, instead of the microcapsule dispersion after preparation No. 2 in which the anionic protective colloid was removed,
A photosensitive material (B) for comparison was prepared in the same manner as in Example 1 except for using the microcapsule dispersion after the first preparation.

[Evaluation of Photosensitive Materials] The photosensitive materials (A) and (B) obtained in Example 1 and Comparative Example 1 were evaluated by the methods shown in (1) and (2) below. The image-receiving material used was prepared as follows.

Preparation of image-receiving material 11 g of a 40% sodium hexametaphosphate aqueous solution was added to 125 g of water, and 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were combined and coarsely dispersed using a mixer. The liquid was dispersed using a Dynamyl disperser, and 6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added to 200 g of the obtained liquid and mixed uniformly. This mixed solution was uniformly applied onto art paper weighing 43 g/m'' to a wet film thickness of 30 gm, and then dried to prepare an image-receiving material.

(1) The photosensitive materials (A and B) were exposed for 1 second each at 200 lux using a tungsten bulb, then placed on a hot plate heated to 125°C and heated for 20 seconds at 10°C. Each of the materials was layered with the above image-receiving material and passed through a pressure roller of 350 kg/cm", and the density of each magenta color image obtained on the image-receiving material was measured using a Macbeth reflection densitometer.

(2) The photosensitive materials (A and B) were placed on a hot plate heated to 125°C without being exposed to light, and heated for 10 to 20 seconds.Then, the blue photosensitive materials were layered on each of the above image-receiving materials at a density of 350 kg/cm''. The density of each magenta color image obtained on the image-receiving material was measured using a Macbeth reflection densitometer.

The above results are summarized in Table 1.

Table 1 Heating time: 10 seconds Heating time: 20 seconds Exposure □ □ Material Exposure Unexposed Exposure Unexposed A
O,151,32-- B 1.31 1.30 0.20 1.
31%As is clear from the results in Table 1, the photosensitive material (A) of the present invention contains a neutral binder instead of anionic protective colloid.

A photosensitive material containing an anionic protective colloid (B
) showed a good positive image with a short development (heating) process.

Claims (1)

[Scope of Claims] 1. A photosensitive material having, on a support, a photosensitive layer containing microcapsules made of aldehyde polycondensation resin walls containing silver halide, a reducing agent, and a polymerizable compound,
A photosensitive material characterized in that a neutral binder is added to the photosensitive layer. 2. The photosensitive material according to claim 1, wherein the neutral binder is made of a polymeric substance having a molecular weight of 10 million to 10 million. 3. The photosensitive material according to claim 1, wherein the neutral binder is a cellulose derivative. 4. The photosensitive material according to claim 1, wherein the aldehyde polycondensation resin wall is made of urea resin or melamine resin. 5. A microcapsule dispersion was prepared by forming an aldehyde polycondensation resin wall around a photosensitive composition containing silver halide, a reducing agent, and a polymerizable compound in an aqueous medium containing an anionic protective colloid. A photosensitive material characterized in that the anionic protective colloid is then removed from the dispersion, a neutral binder is then added to prepare a coating solution for forming a photosensitive layer, and this coating solution is coated on a support. manufacturing method. 6. The method for producing a photosensitive material according to claim 5, wherein the neutral binder is made of a polymeric substance having a molecular weight of 10 million to 10 million. 7. The method for producing a photosensitive material according to claim 5, wherein the neutral binder is a cellulose derivative. 8. The method for producing a photosensitive material according to claim 5, wherein the aldehyde polycondensation resin wall is a urea resin or a melamine resin.