JPS6332535A - Photosensitive material - Google Patents

Abstract

PURPOSE:To improve the shelf stability of a photosensitive material before development by prescribing the amount of residual aldehyde in the polycondensed aldehyde resin walls of microcapsules forming the photosensitive layer. CONSTITUTION:A photosensitive material is composed of a support and a photosensitive layer contg. microcapsules having polycondensed aldehyde resin walls formed with aldehyde as one component on the support. The microcapsules contain silver halide, a reducing agent and a polymerizable compound. When the microcapsules are produced, residual free aldehyde is removed to <=5mol per 1mol reducing agent so as to inhibit the action of aldehyde deteriorating the function of the reducing agent. Thus, the shelf stability of the photographic sensitive material before development is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support. More specifically, the present invention relates to a photosensitive material having microcapsules made of aldehyde polycondensation resin walls.

[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 Japanese Patent Publications Nos. 11149/1980, 20741/1980, 10697/1987, 138632/1980, and 169143/1980.
There are methods described in various publications such as No. In these methods, when exposed silver halide is developed using a developer, the reducing agent is incubated, and at the same time, the coexisting polymerizable compounds (e.g., vinyl compounds) start polymerizing, creating an image-like image. It forms a high molecular compound. Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

The present inventors attempted to improve the above method and invented a method capable of forming a polymer compound by dry treatment, and a patent application for this invention has already been filed (Japanese Patent Laid-Open No. 60-6906).
No.), this method uses a photosensitive silver salt (halogenated ff1)
, a recording material comprising a support supporting a photosensitive layer comprising a reducing agent, a crosslinkable compound (polymerizable compound), and a binder (
A photosensitive material) is exposed for one image to form a latent image, and then heated to form a polymer compound in the area where the latent image of the four-photosensitive silver salt has been formed. That is, this method is a method of polymerizing the polymerizable compound in the area where the silver halide latent image is formed.

Furthermore, the present inventors have further invented a method for polymerizing the polymerizable compound in the area where the silver halide latent image is not formed, and this invention has also already been patented (Japanese Patent Application No. 210-657-1988). issue).

By the way, as a photosensitive material that can be used in the above image forming method, one in which a polymerizable compound, which is one of its constituent elements, is housed in microcapsules is known (
JP-A No. 61-73145).

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. (Tokugan Sho 6)
0-117089), among which methods already known as microcapsule manufacturing techniques such as coacervation method, interfacial polymerization method, or in-situ method are used. There is. Furthermore, various polymeric substances have been mentioned as microcapsule wall forming materials suitably used in these methods.

An example using the above-mentioned wall-forming material is provided by the present applicant. There is a photosensitive material using microcapsules made of amino aldehyde resin around a core material containing silver halide and a polymerizable compound (Japanese Patent Application No. 53873/1982).

The present invention relates to a photosensitive material having microcapsules made of an aldehyde polycondensation resin wall using an aldehyde substance such as formaldehyde as one component as described above.
Research was conducted with the aim of improving its characteristics. As a result, it was found that the storage stability of photosensitive materials using microcapsules as described above is reduced. Further research was conducted to find out the cause, and the following facts were revealed.

That is, when forming the capsule wall as described above,
In order to obtain a capsule wall in good condition during the preparation of a capsule dispersion, an excess amount of aldehyde substance is usually added. Therefore, among the added aldehyde substances, excess aldehyde substances that do not contribute to wall formation remain in the capsule dispersion in a free state. Furthermore, in the production of conventional photosensitive materials, the above-mentioned capsule dispersion was used as a coating liquid and directly coated onto a support to form a photosensitive layer. Therefore, the photosensitive materials proposed so far contain a considerable amount of aldehyde substances.

As a result of the studies conducted by the present inventors, the above-mentioned decrease in storage stability of the photosensitive material is caused by the presence of a considerable amount of the residual aldehyde substance in the manufacturing stage of microcapsules or in the photosensitive layer of the photosensitive material finally formed. However, it has been found that these problems occur because they act on the reducing agent in the coexisting photosensitive composition, impairing its function as a reducing agent.

[Summary of the Invention] An object of the present invention is to provide a photosensitive material that is highly stable during storage (raw storage stability) before being subjected to development processing.

That is, the above object is to provide a photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support, in which the photosensitive layer contains at least an aldehyde substance containing the polymerizable compound as one component. The present invention is characterized in that it has a microcapsule consisting of an aldehyde polycondensation resin wall, and the amount of residual aldehyde substance present is 5 moles or less (preferably 1 mole or less) per mole of ρ stimulant. This can be achieved by the photosensitive material of the invention.

[Effects of the Invention] In the photosensitive material of the present invention, the amount of residual aldehyde substance present in the photosensitive layer is 5 mol or less per 1 mol of reducing agent (preferably,
1 mole or less).

As mentioned above, by removing the aldehyde substance remaining in the photosensitive layer so that it is below a certain ratio with respect to the amount of the reducing agent, the influence of the remaining aldehyde substance on the reducing agent g (promotion of reaction) can be reduced. ) can be effectively suppressed. That is, according to the photosensitive material of the present invention, the amount of aldehyde substances present in the photosensitive layer is maintained in an extremely small amount compared to photosensitive materials formed by conventional methods, so that the movement of the reducing agent is reduced. Therefore, the virgin photosensitive material thus formed has excellent storage stability (raw storage stability).

In addition, the above means that the reducing agent is effectively used.

This means that the polymerization promoting reaction of the polymerizable compound in the area where the silver halide latent image is formed also proceeds smoothly. Therefore, sensitivity is improved, and as a result, clear images can be obtained.

[Detailed Description of the Invention] The photosensitive material of the present invention comprises an aldehyde f formed as one component of an aldehyde substance containing at least a polymerizable compound among silver halide, a reducing agent, and a polymerizable compound, on a support.
f [having a photosensitive layer containing microcapsules made of a synthetic resin wall, and the amount of residual aldehyde substance present is 5 mol or less (preferably 3 mol or less, more preferably 1 mol or less) per 1 mol of the reducing agent; ).

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.0 For silver halide grains having a multiple structure with different compositions on the surface and inside, Japanese Patent Laid-Open No. 57 -154232, l'1lf158-
No. 108533, No. 59-48755, No. 59-52
No. 237, US Pat. No. 4,433.048, and European Patent No. 1°O,984.

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 Japanese Patent Application No. 61-25576.

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 grains.6 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 present invention, the average grain size of the silver halide grains is preferably 0.001 to 5 gm, more preferably 0.001 to 2 gm.

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 preferable to set it in the range of Og/m'.

The reducing agent that can be used in the light-sensitive material of the present invention has a behavior based on silver halide and/or a behavior that promotes (or suppresses) the polymerization of a polymerizable compound. There are various types of reducing agents having the above-mentioned properties.

The above reducing agents include hydroquinones, catechols, p
-aminophenols, p-fuynylenediamines, 3
-Pyrazolidones, 3-7 minopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4.5
-dihydroxy-6-aminopyrimidines, reductones, amylreductones, 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, 1M base material is used.
It is particularly preferred to use -phenyl-3-pyrazolidones.

Regarding various reducing agents having the above-mentioned machine 11, please refer to Japanese Patent Application No. 60-22980, No. 60-29894, and No. 60-2989.
-68874, 60-210657, 60-2
No. 26084, No. 60-227527, No. 60-22
No. 7528 and No. 61-42746, etc., include description a (including those described as developing agents or hydrazine derivatives), and regarding the above-mentioned reducing agent, T.

“The Theory of
the Photographic Process”
4th edition, pp. 291-334 (1977), Research.
Disclosure Magazine, Vat.

170. It is also described in No. 17029 (pages 9-15) of June 1978, and No. 17643 (pages 22-31) of the same magazine Vol. 1.176, December 1978. 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 1 in this specification includes the reducing agents and reducing agent precursors described in each of the above specifications and literature.

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 in combination, the interaction of the reducing agents is, firstly, to promote the reduction of halide (and/or organic silver salt) by so-called superadditivity, and secondly, to promote the reduction of silver halide (and/or organic silver salt).
and/or an oxidized form of the first reducing agent produced by the reduction of silver salts) 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 pentadecylnohydroquinone, 5-t-butylcatechol, p-(N,N-diethylamino)phenol, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l- Phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenylsulfonylamino-4-t-butyl-5- Hexadecyloxyphenol, 2-(N-butylcarbamoyl)-4-7enylsulfonylaminonaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol, l-acetyl-2-7enyl Hydrazine, l-7 cetyl-2-(
(p or O)-aminophenyl)hydrazine, 1-formyl-2-((p or 0)-7minophenyl)hydrazine, l-acetyl-2-((p or 0)-methoxyphenyl)hydrazine, 1-lauroyl −2−((p
or 0)-aminophenyl) hydrazine, 1-trityl-2-(2,6-dichloro-4-cyanophenyl)
hydrazine, 1-trityl-2-phenylhydrazine,
l-Phenyl-2-(2,4,6-drichlorophenyl)hydrazine, 1-(2-(2,5-di-t-hentylphenoxy)butyroyl)-2-((p or 0)-
7minophenyl)hydrazine, 1- (2-(2,5-
(pentylphenoxy)butyroyl) -2-(
(p or o)-aminophenyl)hydrazine pentadecylfluorocaprylate, 3-indazolinone, 1
-(3,5-dichlorobenzoyl)-2-phenylhydrazine, l-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-t-pentylphenoxy)butyramido)phenylhydrazine, 1-acetyl-2-[4-<2-C2,4-di1-
pentylphenoxy)butyramido)phenyl] hydrazine, 1-trityl-2-[(2,6-dichloro-4
-(N.

N-di-2-ethylhexyl)carbamoyl)phenyl] hydrazine, l-(methoxycarbonylbenzohydryl)-2-(2,4-dichlorophenyl)hydrazine, 1-trityl-2-[(2-(N-ethyl-N -octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, 1-benzoyl-2-tritylhydrazine, 1-(4-butoxybenzoyl)-2-1lythylhydrazine, 1-(2,4-dimethoxybenzoyl) −
2-tritylhydrazine, 1-(4-dibutylcarhemoylbenzoyl)-2-tritylhydrazine, and 1
-(1-naphthoyl)=2-tritylhydrazine, etc. can be mentioned.

In the light-sensitive material of the present invention, the reducing agent may be used in an amount of 0.1 to 1,500 mol % based on 1 mol of silver (including the aforementioned silver halide and optional silver salt). preferable.

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, which will be described later, the color image forming substance is immobilized by polymerization and curing of the polymerizable compound. It is preferable that it is a crosslinkable compound having the following.

Note that polymerizable compounds that can be used in photosensitive materials are described in the application specifications for a 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 esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, maleic anhydride, maleic esters, itaconic esters, styrenes, vinyl ethers,
Examples include 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.

n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, hydroxyethoxyethyl acrylate, dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol Diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetra7 acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexa7
Examples include acrylate, diacrylate of polyoxyethylenated bisphenol A, polyacrylate of hydroxypolyether, polyester acrylate, and polyurethane 7-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. . In addition, a substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical compound of the reducing agent described above 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.

The monopolymerizable compound in the photosensitive material of the present invention is:

It is preferably used in a range of 0.05 to 1200% by weight based on silver halide, and a more preferred range is 5 to 950% by weight.

In the photosensitive material of the present invention, a polymer image can be obtained by polymerizing a polymerizable compound according to one or more configurations, but a color image can be obtained by including a color image forming substance in the photosensitive layer as an optional component mentioned in 1. It can also be formed.

In the photosensitive material of the present invention, at least the above-mentioned polymerizable compound is contained in the photosensitive layer in a state of being housed in microcapsules having an aldehyde polycondensation resin wall formed of an aldehyde substance as one component.

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. 53-8'4883, JP-A-52-66
No. 878, JP-A-51-144383, JP-A-51-
No. 9079, JP-A No. 47-42383, JP-A No. 52-
Publications such as No. 18671 and U.S. Patent No. 3,993,8
Examples include the method described in Specification No. 31 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 polymerizable compound or, if necessary, a core substance such as silver rogenide, a reducing agent, an image forming substance (e.g., a dye), is converted into a 7-anionic composition as described below. It is emulsified and dispersed in an aqueous medium containing at least one type of protective colloid.

Next, a monoreactive 7mer (e.g., urea and formaldehyde) is added to this emulsion, and the pH and temperature are adjusted to cause external polymerization to occur around the oil droplet-shaped core substance. Aldehyde polycondensation resin wall (in the above case,
A capsule shell consisting of a urea resin wall) is formed.

The anionic protective colloid is used to disperse the iA aqueous liquid into microdroplets in an aqueous medium and to prevent the microdroplets from coagulating or staying together.

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, polyacrylic 1% i salt and its derivatives and copolymers, carboxymethyl cellulose, gelatin, pectin, pullulan, Examples include phthalated gelatin, succinated gelatin, other gelatin derivatives, cellulose sulfate ester salts, and alginates.

In the method for forming a microcapsule shell as described above,
In order that the resulting capsules are formed in good condition, the aldehyde substance (formaldehyde in the above case) is added in excess relative to the amount of monomer added. For example, when the outer shell is formed from a urea resin, Generally, 1.6 to 1.8 moles of formaldehyde are added per mole of urea.

Therefore, in the microcapsule dispersion, along with the formed microcapsules, excess aldehyde substances in a free state (
residual aldehyde substances) will coexist.

Excess aldehyde substances are then removed from the dispersion containing microcapsules containing at least a polymerizable compound obtained by the method described above. As a removal method, a method (physical treatment method) already known as a method for removing aldehyde substances 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 Unexamined Patent Application Publication No. 1983-1982). 47138 Publication); The above dispersion is subjected to membrane permeation treatment (dialysis, ultrafiltration) through a thin film formed from a semi-synthetic membrane made of cellulose acetate or the like, a synthetic membrane made of polyacrylate, or an electrolyte composite membrane. (Japanese Unexamined Patent Publication No. 56-21639). By these methods, residual aldehyde substances contained in the capsule dispersion can be contained in the photosensitive layer of the obtained photosensitive material in an amount of 5 mol or less (
Preferably, the amount is 3 mol or less, more preferably 1 mol or less). That is, depending on the method employed, the processing time, processing temperature, number of processing times, etc. are determined as appropriate. In the present invention, it is preferable to remove residual aldehyde substances 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, centrifugation It is a good idea to repeat the steps several times.

By the method described above, only the microcapsules can be separated (removed) at the stage of manufacturing the photosensitive material, and the influence on the coexisting reducing agent (reaction with the reducing agent) can be prevented. This is particularly effective when a hydrazine compound, which is highly reactive with aldehyde substances, is used as the reducing agent. Therefore, the photosensitive material in which the amount of residual aldehyde substance is kept to a certain level as described above has improved shelf life.

As described above, the photosensitive material of the present invention comprises a support 1- provided with a photosensitive layer containing microcapsules made of aldehyde polycondensation resin walls containing at least a polymerizable compound. There are no particular limitations on the material used for this support, however, 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 for the support include glass, paper, wood-free paper, coated paper, cast coated paper, synthetic paper, metals and their analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal carbonate, polyethylene terephthalate, etc. film,
Examples include paper 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. 1986-
It is preferable that the support has a certain level of smoothness, like the support used in the photosensitive material described in the specifications for No. 52996.

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 on the photosensitive material, etc. will be sequentially described below.

The photosensitive material of the present invention is one in which a monopolymerizable compound is contained in microcapsules each having a wall of an 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 the photosensitive layer can also be included. An example of a photosensitive material in which oil droplets of a polymerizable compound are in the form of microcapsules is described in Japanese Patent Application No. 117089/1989.

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

In addition, 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.A photosensitive material containing silver halide in the wall material of the microcapsules This is described in Japanese Patent Application No. 11556/1983.

Note that at least one of the components contained in microcapsules, such as a polymerizable compound, silver halide, and reducing agent, may be contained in two or more different microcapsules, and these may be used in combination. In particular, when forming a full-color image using a color image-forming substance as an optional component, it is preferable to use three or more types of microcapsules containing colorants with different color hues, or two or more types of microcapsules. A photosensitive material using a capsule in combination is described in Japanese Patent Application No. 42747/1983.

Optional components that can be included in the photosensitive layer of the photosensitive material of the present invention include color image forming substances, sensitizing dyes, organic silver salts, various image formation accelerators (e.g., bases or base precursors, oils, surfactants, etc.). agent.

compounds with anti-fogging and/or development accelerating functions, thermal solvents, compounds with oxygen removal functions, etc.), thermal polymerization inhibitors, thermal polymerization initiators, development stoppers, fluorescent whitening agents, anti-fading agents, Examples include antihalation or irradiation dyes, merging agents, antismudge agents, plasticizers, water release agents, binders, photopolymerization initiators, and solvents for polymerizable compounds.

There are no particular restrictions on the color image forming substance that can be used in the photosensitive material of the present invention, and various types can be used.
For example, substances that are themselves colored (pigments and dyes),
Or, it itself is uncolored or light-colored, but it is exposed to external energy (heating, pressure, light irradiation, etc.) or another component CIt.
Color image-forming substances also include substances that develop color upon contact with coloring agents (coloring agents). Incidentally, as mentioned above, a photosensitive material using a color image forming substance is described in detail in Japanese Patent Application Laid-open No. 73145/1983. In addition, for photosensitive materials using dyes or pigments as color image-forming substances, a patent application was filed in 1983.
1-29987, Japanese Patent Application No. 1983-53876 and Japanese Patent Application No. 1982-
No. 133091 and Japanese Patent Application No. 133092/1987 each have descriptions thereof.

Sensitizing dyes that can be used in the light-sensitive material of the present invention are:
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, 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 with the sensitizing dye. I? I-sensitivity color-sensitivity plate loading is generally 10-1 mole of silver halide.
The amount is about 8 to 10-2 moles. The sensitizing dye is preferably added at the stage of preparing the silver halide emulsion, as will be described later.For light-sensitive materials obtained by adding the sensitizing dye at the stage of forming silver halide grains, Japanese Patent Application No. 1983
Japanese Patent Application No. 139746 describes a photographic material obtained by adding a sensitizing dye after the formation of silver halide grains/at the stage of preparing a silver halide emulsion.
Each is described in the specification of No. 510. Further, regarding specific examples of sensitizing dyes that can be used in light-sensitive materials, the above-mentioned Japanese Patent Application No. 60-139746 and No. 61-5551
No. 0 is described in each specification.

Addition of an organic silver salt to the light-sensitive material of the present invention is particularly effective in thermal development processing. That is, when heated to a temperature of 80° C. or higher, the Ja-containing 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 include thiocarbonyl group-containing compounds and imino group-containing compounds. Among them, benzotriazole is particularly preferred. The above organic silver salt is generally used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of silver halide. 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. Regarding photosensitive materials using organic silver salts, patent application No. 141/1986
It is described in the specification of No. 799.

Various image formation accelerators can be used in the photosensitive material of the present invention. The image formation accelerator includes a redox reaction between silver halide (and/or organic silver salt) and a reducing agent. promotion of photosensitive material to image receiving material or receiving material
0 Imaging promoters that have features such as promoting the migration of imaging substances into layers (these will be discussed below) have a! It is further classified into compounds having group or base precursors, oils, surfactants, antifoggant and/or development accelerator moieties, thermal solvents, compounds having oxygen removal properties, 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 mechanical moats.

Examples of the image forming accelerator include a base, a base precursor, an oil, a surfactant, a compound having an anti-fogging machine moat and/or a development accelerator 7E, a thermal solvent, and a compound having an oxygen removing machine 1. show.

Examples of preferred bases include, as inorganic bases, 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; hydroxide of quaternary alkylammonium; hydroxide 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-
(Sialamino)phenylcomethanes), 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 Ti acids and bases that undergo de-'rXWA upon heating, compounds that release amines through reactions such as intramolecular nucleophilic exchange reactions, Loaf heptan rearrangement, and Beckmann rearrangement, and compounds that release amines when heated. Compounds that generate a base by causing a reaction, and compounds that generate a base by electrolysis or the like are preferably used. Specific examples of base precursors include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid fa, p-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid,
Examples include guanidine phenylsulfonylbutyrate, guanidine 4-lylorphenylsulfonylacetate, guanidine 4-methyl-sulfonylphenylsulfonylacetate, and guanidine 4-acetylaminomethylpropiolate.

The base or base precursor can be used in the light-sensitive material of the present invention 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 0.5% by weight or less, calculated as the weight of the coating film of the photosensitive layer.
A range of 1% to 40% by weight is useful. 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. In addition, regarding photosensitive materials using tertiary amines as bases or base precursors, patent application No. 131-1988
No. 81 specifies that a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound with a melting point of 80 to 180°C is described in Japanese Patent Application No. 61-52992. Photosensitive materials using oxides or salts are described in Japanese Patent Application No. 61-96341.

When a base or a base precursor is used in the photosensitive material of the present invention, silver halide, a reducing agent, and a polymerizable compound are contained in the microcapsules described above, and the base or base precursor is contained in the photosensitive layer outside the microcapsules. Preferably, it is present. Or, patent application 1986-52
In addition to the above-mentioned specification, photosensitive materials using microcapsules containing bases or base precursors, such as the photosensitive material described in No. 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 is disclosed in Japanese Patent Application No. 61-52989. The photosensitive materials accommodated are described in the specification of Japanese Patent Application No. 61-52995. The base or base precursor may be added to an auxiliary layer other than the photosensitive layer (a layer containing a base or base precursor described later) as described in Japanese Patent Application No. 81-96341.

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.

The anti-fogging compound 3 and/or the compound having a development acceleration mechanism 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. In addition, fog prevention 1j1. fi and/or development acceleration* As a compound having iF,
For photosensitive materials using antifoggants, a patent application was filed in 1980-
No. 294337 describes a photosensitive material using a compound having a cyclic amide structure in Japanese Patent Application No. 60-29433.
8, for photosensitive materials using thioether compounds, see Japanese Patent Application No. 60-294339, and for photosensitive materials using polyethylene glycol derivatives, see Japanese Patent Application No. 60-294340. Regarding photosensitive materials using derivatives, patent application No. 60-294341
For photosensitive materials using acetylene compounds, see Japanese Patent Application No. 61-20438, and for photosensitive materials using sulfonamide derivatives, see Japanese Patent Application No. 61-25.
Each is described in the specification of No. 578.

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 -C〇- groups, polar substances described in U.S. Pat. No. 3,667,959, 1,10-decane described in Research Disclosure magazine, December 1976 issue, pages 26-28 Diol, methyl anisate, biphenyl perate, etc. are preferably used.

A compound having an oxygen remover 18 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. Regarding photosensitive materials using compounds having two or more mercapto groups, there is a description in Japanese Patent Application No. 61-53880. Thermal polymerization initiators that can be used in the photosensitive materials of the present invention include: Generally, it is a compound that thermally decomposes under heating to generate polymerization initiating species (particularly radicals), and is usually used as an initiator for radical polymerization. Regarding thermal polymerization initiators, please refer to “Addition Polymerization and
"Ring-Opening Polymerization" (1983, Yame Publishing), pages 6 to 18, etc. Specific examples of thermal polymerization initiators include:
Azobisisobutyronitrile, 1,1゛-Ambis(1
-cyclohexa7carponitrile), dimethyl-2,2
゛-7zobisisobutyrate, 2,2-ambis(2-
methylbutyronitrile), azo compounds such as atbisdimethyl/hereronitrile, organic peroxides such as henzoyl peroxide, dihydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, Examples include inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, and sodium p-)luenesulfinate. The thermal polymerization initiator is preferably used in an amount of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound. In addition, in a system in which a polymerizable compound is polymerized in areas where a silver halide latent image is not formed, it is preferable to add a thermal polymerization initiator to the photosensitive layer. is described in Japanese Patent Application No. 60-210657.

The development stopper that can be used in the photosensitive material of 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 the development immediately after proper development, or silver and silver salts. It is a compound that interacts to inhibit development. Specifically, an acid precursor that releases an acid when heated, and an electrophilic compound that causes a substitution reaction with a coexisting base when heated.

Alternatively, nitrogen-containing heterocyclic compounds, mercapto compounds, etc. may be mentioned. Examples of acid precursors are:

Japanese Patent Publication No. 60-108837 and No. 60-19293
Oxime esters described in each publication No. 9, patent application No. 1986-8
Examples include compounds that release acid through Rossen rearrangement as described in No. 5834. Examples of electrophilic compounds that undergo a substitution reaction with a base upon heating include compounds described in JP-A-60-230134.

The anti-smudge agent used in the photosensitive material of the present invention is preferably a particulate material that is solid at room temperature. Specific examples include starch particles described in British Patent No. 12,322,347;
Fine polymer powder of U.S. Patent No. 3,625,736, color former-free microcapsule particles of British Patent Section 1.235,991, U.S. Pat. No. 2,711 Examples include the fine cellulose powder described in No. 375, and inorganic particles such as talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina. The unrestricted particle size of the above particles is preferably in the range of 3 to 50 gm in volume average diameter, and 5 to 4 gm.
A range of 0 pm is more preferred. As mentioned above, when the polymerizable compound is in the form of microcapsules, it is more effective if the particles are larger than the microcapsules.

The binders that can be used in the photosensitive material of the present invention and the image-receiving material described below can be contained in the photosensitive layer or the image-receiving layer alone or in combination. It is preferable to use a mainly hydrophilic binder. Hydrophilic binders are typically transparent III or semi-rPLIJJ, and include natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylic Other synthetic polymeric materials include synthetic polymeric materials such as water-soluble polyvinyl compounds such as raremid polymers, particularly in the form of latexes, dispersed vinyl compounds which increase the dimensional stability of photographic materials. Regarding photosensitive materials using binders, Japanese Patent Application Laid-open No. 6
There is a description in Publication No. 1-69062. Further, a photosensitive material using a binder together with microcapsules is described in Japanese Patent Application No. 1983-52994.

In the photosensitive layer of the photosensitive material of the present invention, after image transfer.

A photosensitive material using a photopolymerization initiator to which a photopolymerization initiator may be added for the purpose of polymerizing an unpolymerized polymerizable compound is described in Japanese Patent Application No. 3025/1983.

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 the 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.

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).

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 release layer, a cover sheet or a protective layer, a layer containing a base or a base precursor, and a base barrier. One layer, etc. can be mentioned.

Instead of using the image-receiving material described above, the image-receiving layer may be provided on the photo-sensitive material and an image may be formed on this layer. It can be configured similarly to. Details of the image receiving layer will be described later.

For photosensitive materials using a 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. 135568, and for photosensitive materials provided with a layer containing a base or base breaker, see Japanese Patent Application No. 61-55507. 96341, respectively. Further, the base barrier layer is also described in the above-mentioned Japanese Patent Application No. 61-96341. 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 of the present invention will be described below.

Various methods can be used to produce photosensitive materials, but the numerical method involves preparing a coating solution in which the components of the photosensitive layer are dissolved, emulsified, or dispersed in an appropriate solvent; This process consists of applying a coating liquid to a support and drying it to obtain a photosensitive material.

Generally, the above-mentioned coating liquid is prepared by preparing a liquid composition containing each component and then mixing the respective liquid compositions. The above liquid composition may be prepared individually for each component or may be prepared to contain a plurality of components. It can also be used by adding during or after preparation. Furthermore, a method of preparing a secondary composition by further emulsifying an oily (or aqueous) composition containing one or more components in an aqueous (or oily) solvent can also be used.

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

In producing the light-sensitive material of the present invention, silver halide is preferably prepared as a silver halide emulsion. There are various methods for preparing silver halide emulsions known in photographic technology, etc., but there are no particular restrictions on the production of the light-sensitive material of the present invention. It can be prepared using any of the following methods. The reaction method between the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A back-mixing method in which particles are mixed under conditions of excess silver ion and a Chondral double-jet method in which PAg is kept constant can also be employed.

Further, the silver halide emulsion may be of a surface latent image type in which a latent image is mainly formed on the surface of the grains, or may be of an internal latent image type in which a latent image is formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used.

In the silver halide emulsion used in the production of the light-sensitive material of the present invention, it is preferable to use a lignophilic colloid as the protective colloid. As a woody colloid,
For example, gelatin, gelatin derivatives, graft polymers of gelatin and other polymeric substances, proteins such as albumin and casein, derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sodium alginate, starch derivatives, etc. derivatives; and polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic wood-philic polymeric materials can be mentioned, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like. Among these, gelatin is preferred. As for gelatin, 1. In addition to lime-treated gelatin,
Acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzyme-treated decomposition products may also be used.

By preparing a silver halide emulsion using a wood-philic colloid, the sensitivity of the light-sensitive material of the present invention produced using this emulsion is improved. Silver halide emulsions are prepared using ammonia, organic thioether derivatives (Japanese Patent Publication No. 47-38
(see Publication No. 6) and sulfur-containing compounds (Japanese Patent Application Laid-open No. 53-14)
4319) etc. can be used. In addition, in the process of particle formation or physical ripening, cadmium salt,
Zinc salt, lead salt, thallium salt, etc. may be present together. Furthermore, for the purpose of improving high illuminance discomfort and low illuminance failure, water-soluble iridium salts such as iridium chloride (monovalent or ■valent), ammonium chloroiridium salt, or water-soluble rhodium salts such as rhodium chloride may be used. can.

The soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening. In this case, it can be carried out according to the Tardel water washing method or the sedimentation method. Although the silver halide emulsion may be used without post-ripening, it is usually used after being chemically sensitized.

In emulsions for conventional sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination.

In addition, when adding a sensitizing dye to a silver halide emulsion,
Patent Application No. 60-139746 and No. 61-55510
Nitrogen-containing compounds are preferably added in the preparation stage of silver halide emulsions as in the light-sensitive material described in the specification of the above-mentioned patent. When a heterocyclic compound is added, it is preferably added at the stage of forming or ripening silver halide grains in the preparation of a silver halide emulsion. A method for producing a photosensitive material in which a nitrogen-containing heterocyclic compound is added at the stage of forming or ripening silver halide grains 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 the photosensitive material of the present invention, the polymerizable compound can be used as a medium for preparing the composition of other components in the photosensitive layer.For example, silver halide (including silver halide emulsions) ), reducing agent etc. are dissolved in a polymerizable compound,
It can be emulsified or dispersed and used in the production of photosensitive materials.

A photosensitive composition containing silver halide in a polymerizable compound can be prepared using a silver hexahalide emulsion. 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.

The photosensitive composition is prepared by mixing the above-mentioned silver halide, the above-mentioned polymerizable compound and reducing agent, and other optional components with a commonly used stirring a (homogenizer, blender, mixer, etc.).
It can be obtained by adding it to the water and stirring it.

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 as a substance is described in Japanese Patent Application No. 1983-5750.

The photosensitive composition obtained above is then encapsulated (microcapsules consisting of an aldehyde polycondensation resin wall) according to the shell forming method described above to prepare a capsule dispersion. Further, this capsule dispersion liquid is subjected to a treatment for removing residual aldehyde substances according to the present invention to prepare a coating liquid for forming a photosensitive layer. As mentioned above, it is preferable that the microcapsules formed in this manner also contain a color image forming substance.

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

An image forming method using the photosensitive material of the present invention 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 exposure.

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. Also.

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, the light-sensitive material of the present invention which is subjected to development treatment after imagewise exposure may be subjected to development treatment using a developer described in Japanese Patent Publication No. 45-11149.

In addition, as mentioned above, the method of JP-A-61-2003, which performs heat development processing,
Since the method described in Publication No. 69062 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 the photosensitive material of the present invention 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. Further, as in the photosensitive material described in the above-mentioned Japanese Patent Application No. 135568/1980, a heat generating layer may be provided on the photosensitive material and used as a heating means. Further, as in the image forming method described in Japanese Patent Application No. 61-55506, heat development may be carried out while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 80°C to 200°C, preferably 100°C to 1
The temperature is 60°C. The heating time is generally 1 second to 5 minutes.
Preferably it is 5 seconds to 1 minute.

The photosensitive material of the present invention 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. can. In the photosensitive material of the present invention, the polymerizable compound in the area where the latent image of silver halide is generally polymerized in the heat development process, but the photosensitive material described in the above-mentioned Japanese Patent Application No. 60-210657 It is also possible to polymerize the polymerizable compound in the area where the silver halide latent image is not formed by adjusting the type and amount of the reducing agent like the material.

By polymerizing and curing the polymerizable compound as described above, it is possible to immobilize the color image forming substance in the cured portion.

For example, the above-mentioned patent application No. 61-53 describes the photosensitive material of the present invention.
When the photosensitive material is constructed like the photosensitive material described in the specification of No. 881, the developed photosensitive material is pressurized and
A color image is formed on a photosensitive material by destroying microcapsules containing a color image-forming substance (e.g., leuco dye) and bringing this color image-forming substance into contact with another color-forming component (e.g., an acidic color developer). can be formed.

However, as described above, in the image forming method using the photosensitive material of the present invention, it is preferable to use an image-receiving material 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 supports that can be used for photosensitive materials described below. 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. . Furthermore, an image-receiving material using a transparent support is described in Japanese Patent Application No. 61-52991.

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

Note that when using a color image-forming substance using a system that develops color by utilizing a reaction between two or more components, for example, a system consisting of the above-mentioned leuco dye and an acidic color developer, the photosensitive material of the present invention may be Even if one of the color-forming components (in the above case, the leuco dye) is allowed to coexist in the layer with the other component separated from the other, the color can be developed before or at the same time as the transfer to the image-receiving material. In that case, the image-receiving material may consist only of the support.

However, as described above, it is more preferable that the image-receiving layer contains one of the color forming components (in the above case, an acidic color developer).

The image-receiving layer preferably contains a polymer as a binder. As the binder, a hainder that can be used in the photosensitive layer of the photosensitive material described above can 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 be constructed as an aggregate of fine particles of thermoplastic material, as in the image-receiving material described in Japanese Patent Application No. 61-55503. In addition, a white pigment such as titanium dioxide may be added to the image-receiving layer so that the image-receiving layer functions as a white reflective layer. An initiator or thermal polymerization initiator may also be added. Regarding an image receiving material having an image receiving layer containing a photopolymerization initiator, see the specifications for Japanese Patent Application No. 61-3025, and regarding an image receiving material having an image receiving layer containing a thermal polymerization initiator,
Each of these is described in the specification of Japanese Patent Application No. 61-55502.

Note that when the image-receiving layer is located on the surface of the image-receiving material, it is preferable to further provide a protective layer.

The photosensitive material of the present invention is developed as described above,
By pressing the image-receiving materials in a stacked state j9, the color image-forming substance in the uncured portion can be transferred to the image-receiving material, and a color image can be obtained on the image-receiving material. Regarding the above-mentioned pressurizing means, various conventionally known methods can be used.

As mentioned above, in order to obtain a color image using the color reaction between a leuco dye and an acidic color developer, this color development system is promoted under heating conditions, so it is necessary to heat the image-receiving material after transfer. preferable.

When the image-receiving material after transfer is heated as described above, as in the image forming method described in Japanese Patent Application No. 61-55501, the unpolymerized polymerizable material transferred together with the image-forming substance (leuco dye) Another advantage is that the compound is polymerized and the storage stability of the obtained image is improved.

The photosensitive material of the present invention includes a photosensitive material for black and white 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), a computer graph ink/ ＼-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 Examples below, but the present invention is not limited thereto.

[Example 1] Preparation of silver halide emulsion 40 g of gelatin and potassium bromide were dissolved in 3 g of water.
Heat to 0℃, continue stirring, and add 34g of silver nitrate to 22g of water.
00 ml 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 the emulsion was precipitated. After removing excess salt, 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 were mixed with 3000 + n! of water. ;Dissolved in L. This solution was stirred while being maintained at 40° C., and a solution of 17 g of silver nitrate dissolved in 100 mM 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 photosensitive composition 100 g of trimethylolpropane triacrylate, 0.40 g of the following copolymer, Pargus Script Red 1-6-B (manufactured by Ciba Geigy)6. OOg was dissolved. Add 0.00 g of the following hydrazine derivative to 18.00 g of the above solution.
61g and 1.22g of the following developer in methylene chloride 1
．． A solution of 8 g was added. A mixture of 4.06 g of the silver halide emulsion and 3.35 g of benzotriazole silver emulsion was added, and the mixture was heated at 1,500 g/min using a homogenizer.
The mixture was stirred at 0 rotation for 5 minutes to obtain a photosensitive composition.

Below Margin (copolymer) OH3CH3 CO2CH2CH2N GH3\
l CH3-+CH2-C:←2゜C02Ca)19 (Hydrazine derivative) (Developer) Preparation of microcapsule liquid 18.6% aqueous solution of isohene (manufactured by Kuraray ■) 10.51
g, add 48.56 g of a 2.89% aqueous solution of pectin,
The photosensitive composition was added to an aqueous solution adjusted to pH 4.0 using a 10% aqueous sulfuric acid solution, and stirred for 2 minutes at 7000 rpm using a homogenizer to emulsify the photosensitive composition in an aqueous solvent.

To 72.5 g of this aqueous emulsion, 8.32 g of urea 40% aqueous solution was added.
g, resorcinol 1163% aqueous solution 2°82g, formalin 37% aqueous solution 8.56g, ammonium sulfate 8.76g
% aqueous solution was added thereto, and heating was continued at 60° C. for 2 hours while stirring to prepare a microcapsule dispersion having a urea resin wall.

The microcapsule dispersion obtained above was centrifuged @ (2
500 rpm, 20 minutes), 100 g of wood was added and ultrasonically dispersed. After that, centrifugation was performed again. This operation was repeated six times to separate the microcapsules as solid matter.

Next, 8.94 g of an 18.6% aqueous solution of In/Kun (manufactured by Kuraray Kaga) and 41.29 g of a 2.89% aqueous solution of pectin were added to the solid content of the microcapsules, and the pH was adjusted to 6.0 using a 10% aqueous sulfuric acid solution. A microcapsule dispersion liquid from which formaldehyde had been removed was prepared.

Preparation of photosensitive material Microcapsule dispersion prepared as above 10.
0g, 1% aqueous solution of the following 7-ion surfactant 1.0g
and coated on 100 gm thick polyethylene terephthalate using a #40 coating rod, approximately 40 gm thick.
A photosensitive material (A) according to No. 4 was prepared by drying at a temperature of 0.degree. C. and having a dry film thickness of 23 pm from which formaldehyde had been removed.

(Anionic surfactant) CH2COOCH2-OH(C2Hs)CaH9Na0
3S-OH-C: 00CH2-CH(CzHs)C4H
q [Comparative Example 1] The photosensitive material (B) was prepared in the same manner as in Example 1 except that the dispersion was not centrifuged when preparing the microcapsule dispersion. Created.

Preparation of base sheet Add 3 g of a 10% aqueous solution of gelatin and 1.4-
Diazabicyclo[2,2,2]octane (DABCO)
Add 0.69 g of a 30% aqueous solution of DA
B CO) dispersion was prepared.

Next, polyethylene terephthalate film (support,
The above base dispersion was applied onto a 10,100p surface using a coating rod and dried at 25° C. for 1 hour to obtain a base sheet having a base on the surface layer.

Preparation of image-receiving material 11 g of 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 mixed and coarsely dispersed with a mixer. . The liquid was dispersed with Dynamyl content %R, 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 liquid mixture was uniformly applied onto art paper weighing 43 g/m' to a wet film thickness of 30 tiles, and then dried to prepare an image-receiving material.

[Evaluation of Photosensitive Materials] The photosensitive materials (A) and CB) obtained in Example 1 and Comparative Example 1 were subjected to the following free formaldehyde test (
Acetylaceto method; JIS, L 1041-1983
) was carried out.

Acetylacetone method: Cut a photosensitive material of 100 crn' into thin pieces.
Soak in distilled water, heat to 40°C, and extract for 1 hour.

Next, centrifugation! (4000 rpm, 10 minutes) to remove impurities, and to 5 ml of the supernatant liquid obtained, 5 ml of the acetylacetone test solution described below was added and mixed. Next, this mixed solution was heated at 4° C. for 30 minutes, left to stand for 30 minutes, and the absorbance of the obtained sample at 415 nm was measured.

Acetylacetone test solution: Dissolve 150 g of special grade ammonium acetate [JIS K 8359 ammonium acetate (reagent)] in 800 m of water, add 3 ml of special grade acetic acid [JIS K 8355 acetic acid (reagent)] and acetylacetone [JIS K 8
Add 2 ml of special grade 027 acetylacetone (reagent)], shake well, and then add water to bring the temperature to 10100O.

The concentration of formaldehyde was measured from a calibration curve created using the absorbance measured above and an aqueous formaldehyde solution with a known concentration.

The above results are shown in Table 1, where the amount of residual formaldehyde is a value converted to the amount per 1 mole of reducing agent.

Table 1: Photosensitive materials: Amount of residual formaldehyde (moh) A
O, 2B
5.2 Next, the photosensitive materials (A) and (B) above were subjected to the raw storage test shown below, and the resulting images were evaluated.

In the raw storage test, each photosensitive material was placed in a constant temperature bath (temperature;
50° C.) for 10 days.

(1) After leaving the photosensitive materials (A and B) exposed for 1 second each at 200 lux using a tungsten bulb, the photosensitive surfaces of each were brought into close contact with the surface side of the base sheet and heated to 125°C. 40 on a heated hot plate
The base sheet was heated for 0 seconds, then the base sheet was peeled off, and both photosensitive materials were stacked on top of the above image receiving material at a weight of 350 kg/
The density of the magenta color obtained on the image-receiving material was measured using a Macbeth reflection densitometer.

(2) After exposure, the photosensitive materials (A and B) were brought into close contact with the surface side of the base sheet without being exposed, and heated for 40 seconds on a hot plate heated to 125°C. Next, the base sheet was peeled off, and both photosensitive materials were stacked on the image-receiving material and passed through a pressure roller of 350 kg/cm'', and the density of the magenta color on the image-receiving material was measured using a Macbeth reflection densitometer.

The above results are summarized in Table 2. The table below also includes evaluations of each photosensitive material before storage (0 days).

All white Table 2 below Before storage Exposure after 10 days □ □ Material Exposure Unexposed Exposure Unexposed A
O, 0B 1.30 0.0B
1.30B O,081,290,601,2
9 As is clear from the results in Table 2, the photosensitive material (A) of the present invention from which residual formaldehyde was removed had a higher shelf life than the conventional photosensitive material (B).

In addition, the maximum concentration is high and the minimum concentration is low (
A positive image with a high S/N ratio was provided.

Claims (1)

[Scope of Claims] 1. A photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support, wherein the photosensitive layer contains at least an aldehyde substance containing the polymerizable compound as a component. 1. A photosensitive material having microcapsules made of an aldehyde polycondensation resin wall formed as a polycondensate, and having a residual aldehyde substance present in an amount of 5 mol or less per 1 mol of a reducing agent. 2. The photosensitive material according to claim 1, wherein the amount of residual aldehyde substance present is 1 mol or less per 1 mol of reducing agent. 3. The photosensitive material according to claim 1, wherein the reducing agent contains a hydrazine compound. 4. The photosensitive material according to claim 1 or 2, wherein the residual aldehyde substance is formaldehyde. 5. The photosensitive material according to claim 1, wherein the aldehyde polycondensation resin wall is made of urea resin or melamine resin.