JPH02240648A - Photosensitive material - Google Patents

Abstract

PURPOSE:To accelerate development and polymn. and to obtain an image having high image quality under milder development conditions by incorporating a borate compd. into a photosensitive layer. CONSTITUTION:A borate compd. represented by formula I (where each of R1-R4 is alkyl, cycloalkyl, etc., and M is an alkali metal or prim. to quat. ammonium) is incorporated into a photosensitive layer. The borate compd. in the photosensitive layer is subjected to direct or indirect one-electron oxidation with silver halide to generate radical species and free radicals having polymn. initiating ability are generated from the radical species to accelerate development and polymn. A photosensitive material giving an image having superior discrimination under development conditions of low temp. and short time can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention provides a method for disposing on a support at least silver halide, a reducing agent,
The present invention relates to a photosensitive material having a photosensitive layer containing a polymerizable compound and a borate compound.

``Prior Art'' A photosensitive material has a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support. When exposed to light, a latent image of silver halide is formed, and the polymerizable compound is removed by the action of the reducing agent. It can be used in image forming methods that involve polymerization.

Examples of image forming methods include methods described in Japanese Patent Publication Nos. 11149/1982, 20741/1982, 10697/1987, 138632/1980, and 169143/1980. . 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.

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 Application Laid-Open No. 61-6906).
No. 2), this method is a recording material (photosensitive material) in which a photosensitive layer consisting of a photosensitive silver salt (silver halide), a reducing agent, a crosslinking compound (polymerizable compound), and a binder is supported on a support. is imagewise exposed to form a latent image, and then heated to form a polymer compound in the area where the latent image of the photosensitive root salt has been formed.

The above image forming method is a method of polymerizing the polymerizable compound in the area where the latent image of silver halide is formed. He invented a method that can polymerize , and a patent application for this invention has already been filed (Japanese Patent Laid-Open No. 62-7
No. 0836).

In this method, a reducing agent is applied to the area where the latent image of silver halide has been formed by heating to suppress the polymerization of the polymerizable compound and at the same time promote the polymerization of other areas.

As one embodiment of the image forming method as described above, a photosensitive material having a photosensitive layer containing silver halide, a reducing agent, a polymerizable compound, and a color image forming substance on a support is imagewise exposed at the same time. Alternatively, after imagewise exposure, a development process is performed to polymerize and harden the polymerizable compound, thereby immobilizing the color image-forming substance in the cured area, and then receiving the photosensitive material in which the color image-forming substance in the cured area has been immobilized. There is a method of transferring an uncured color image forming material to an image-receiving material by applying pressure while overlapping the material (Japanese Patent Laid-Open No. 61-278849).

``Problem to be solved by the invention'' However, these methods have the disadvantage that the process from development to polymerization is slow or inefficient, requiring high temperatures or long periods of time for development. there were.

The present inventor has intensively studied techniques for accelerating the process of development polymerization, and has arrived at the present invention. That is, an object of the present invention is to provide a photosensitive material that can produce images with excellent discrimination under lower temperature and shorter development conditions.

``Means for solving rtjRB'' The present invention provides a photosensitive material having a photosensitive layer containing silver halide, a reducing agent, a polymerizable compound and a borate compound on a support.

The photosensitive material of the present invention is characterized in that it contains a borate compound as an accelerator for development polymerization.According to research by the present inventors, adding a borate compound to the photosensitive layer significantly accelerates development polymerization. This makes it possible to obtain high-quality images under milder developing conditions.

The borate compound used in the photosensitive material of the present invention can be represented by the following general formula (I).

General formula (I) In the above formula, R1-R4 are an alkyl group, a cycloalkyl group,
8M representing a substituent selected from an aralkyl group, an alkenyl group, an aryl group, and a heterocyclic group represents an alkali metal or a primary to quaternary ammonium group, and the above group is further substituted with another substituent. The borate compounds will be explained in more detail below.

Examples of alkyl groups applicable to substituents R1 to R4 include unsubstituted or substituted alkyl groups having 1 to 18 carbon atoms (ethyl group,
butyl group, octyl group, etc.). Examples of the cycloalkyl group include a cyclohexyl group, a cyclopentyl group, and a 4-methylcyclohexyl group. Examples of aralkyl groups include benzyl group, p-methoxybenzyl group, and 2-phenethyl group. Examples of alkenyl groups include vinyl, crotyl, and styryl groups. Examples of aryl groups include phenyl Lp
-tolyl group, P-methoxyphenyl L p-chlorophenyl group, and the like. ? 3[Examples of the cyclic group include 2-thienyl group, 2-furyl group, 4-pyridyl group, etc. Among the above substituents, alkyl groups and aryl groups are preferred, and particularly preferred are those in which 1 to 3 of R1 to R4 are alkyl groups and the remainder are aryl groups.

M represents an alkali metal or a primary to quaternary ammonium group. Preferred alkali metals include Na and KSCs. Among the primary to quaternary ammonium groups, quaternary ammonium groups are particularly preferred, and tetraalkylammonium groups, aryltrialkylammonium groups, and aralkyltrialkylammonium groups are most preferred.

Specific examples of borate compounds useful in the present invention are shown below, but the present invention is not limited thereto.

CHs O8, / CF z B-36 B-37 The borate compound used in the present invention can be synthesized according to a known method.
Various borate compounds can be synthesized according to the method described in No. 044.

The present inventor conducted a detailed study on the action mechanism of the borate compound in the present invention, and found that the borate compound is directly or indirectly oxidized with one electron by silver halide to generate radical species, from which free radical species having the ability to initiate polymerization are generated. It was assumed that radicals were generated.

In the photosensitive material of the present invention, the borate compound is preferably used in an amount of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the polymerizable compound.

The borate compound of the present invention can be added to the photosensitive material in various ways6.For example, it can be added by dissolving it in a water-miscible organic solvent, it can be added as a solid dispersion in the form of fine particles, or it can be added by dissolving it in a water-insoluble non-volatile oil. The most preferable method is to dissolve the compound in a liquid polymerizable compound and use it.

The photosensitive material of the present invention will be explained below. A photosensitive material has a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support.

11. for photosensitive materials. As the silver halide, any grains of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used.

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having a multilayer structure with different compositions on the surface and inside, Japanese Patent Application Laid-open Nos. 57-154232 and 5B-10853 disclose
No. 3, No. 59-48755, No. 59-52237, U.S. Patent No. 4433048 and European Patent No. 1
There are descriptions in each specification of No. 00984. Also, JP-A-62
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 No. 183453.

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

In addition, as the silver halide grains mentioned above, Japanese Patent Application Laid-Open No. 63-6
It is preferable to use silver halide grains having a relatively low fog value, such as the light-sensitive material described in Japanese Patent No. 8830.

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

There are no particular restrictions on the grain size distribution of silver halide grains. For example, monodisperse silver halide grains with a substantially uniform grain size distribution are used, as in the photosensitive material described in JP-A No. 62-210448. It's okay.

In the photosensitive material, the average grain size of the silver halide grains is preferably 0.001 to 5 μm, o,
More preferably, the thickness is from ooi to 2 μm.

(■) of silver halide contained in the photosensitive layer is Q, 1 mg to 1
It is preferable to set it in the range of 0 g/m'', and in terms of silver only for silver halide, it is preferable to set it in the range of 1 g/rr? or less, from 1 rr+g to 500 mg/rn.
” is particularly preferable.

The reducing agent used in the photosensitive material has a function of reducing tin halide and a function of promoting (or suppressing) polymerization of a polymerizable compound. However, two or more types of reducing agents each having the above functions may be used in combination. There are various types of reducing agents having the above functions. The reducing agents include hydroquinones, catechols, p-aminophenols, p-ph, I-nylene diamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracil. 4,5-dihydroxy-6-aminopyrimidines, reductones,
Amyl reductones, 0- or P-sulfonamidophenols, 0- or p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamido-5-pyrazolones, 3-sulfonamidoindoles, sulfonamides Pyrazolobenzimidazoles,
Examples include sulfonamide pyrazolotriazoles, α-sulfonamide ketones, and hydrazines. By adjusting the type, amount, etc. of the reduction M, 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 latent image of silver halide is formed, it is particularly preferable to use hydrazines as a reducing agent. In systems for polymerizing chemical compounds, it is particularly preferable to use 1-phenyl-3-pyrazolidones as the reducing agent.

Regarding various reducing agents having the above functions, please refer to JP-A-61-183640, JP-A No. 61-188535, and JP-A-61-188535.
No. 1-228441, No. 62-70836, No. 62-
No. 86354, No. 62-86355, No. 62-264
There are descriptions in various publications such as No. 041 and No. 62-198849 (including those described as a developer or a hydrazine rust conductor). Regarding the above reducing agent, T, JaL
The Theory of th by Iles
e Photographic Process”
4th board, pp. 291-334 (I977), Reser f-Disclosure Magazine Vol. , 170.1978
No. 17029 (pages 9-15) of June, and the same magazine V
o1.176, No. 17643 of December 1978 (2
There is also a description on pages 2-31). Also, JP-A-62-21
As in the photosensitive material described in Publication No. 0446, a reducing agent precursor capable of releasing a reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. As the material, the reducing agents and reducing agent precursors described in the above-mentioned publications and literature can be effectively used. Therefore, "reducing agent j" in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications and literature.

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

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p-(N,N-diethylamino)phenol, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 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-phenylsulfonylaminonaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol,!
-acetyl-2-phenylhydrazine, 1-acetyl-
2-((p or 0)-aminophenyl)hydrazine,
1-formyl-2-((p or O)-aminophenyl)hydrazine, 1-acetyl-2-((p or 0)-
methoxyphenyl)hydrazine, 1-lauroyl-2-
((p or 0)-aminophenyl)hydrazine, 1-
Trityl-2-(2,6-dichloro-4-cyanophenyl) and drazine, 1-trityl-2-phenylhydrazine, 1-phenyl-2-(2,4,6-dolichlorophenyl)hydrazine, 1-( 2-(2,5-di-t-pentylphenoxy)butyroyl)-2=((p or 0
)-aminophenyl)hydrazine, 1-(2-(2,
5-di-t-pentylphenoxy)butyroyl)-2-
((p or.)-aminophenyl)hydrazine pentadecylfluorocaprylate, 3-indazolinone,
1-(3,5-dichlorophenyl)-2-phenylhydrazine, 1-trityl-2-[((2-N-butyl-N
-octylsulfamoyl)-4-methanesulfonyl)
Phenylhydrazine, 1-(4-(2,5-di-t-pentylphenoxy)butyroyl)-2-((p or 0
)-methoxyphenyl)hydrazine,! -(methoxycarbonylbenzohydryl)-2-phenylhydrazine,
l-Formyl-2-[4-(2-(2,4-di-t-pentylphenoxy)butyramido)phenyl]hydrazine, 1-acetyl-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] and drazine, 1-(methoxycarbonylbenzohydryl)-2-(2,4-dichlorophenyl)hydrazine,
1-) Richyl-2-[(2-(N-ethyl-N-octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, 1-benzoyl-2-tritylhydrazine, 1-(4-butoxybenzoyl)- 2-Tritylhydrazine, 1-(2,4-dimethoxybenzoyl)-2
-tritylhydrazine, 1-(4-dibutylcarbazoylbenzoyl')-2-tritylhydrazine, and 1
-(I-naphthoyl)-2-tritylhydrazine and the like can be mentioned.

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

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and any known polymerizable compound can be used. In addition, when heat development treatment is planned as a method of using the photosensitive material, it should be noted that materials with a high boiling point (for example, a boiling point of 8
It is preferable to use a compound with a temperature of 0°C or higher, and in an embodiment in which the photosensitive layer contains a color image forming substance as an optional component described below, a polymer compound is produced by polymerization and curing of a polymerizable compound. The polymerizable compound is preferably a crosslinking compound having a plurality of polymerizable functional groups in the molecule.

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

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

Specific examples of polymer compounds that can be used in photosensitive materials include acrylic esters, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, Toshikiethoxyethyl acrylate, synchhexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythryl hexaacrylate, polyoxoethylenated bisphenol A diacrylate, 22-dimethyl-3-hydroxy Examples include diacrylates of propionaldehyde and trimethylolbromone rods, triacrylates of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol condensates, polyacrylates of hydroxypolyethers, polyester acrylates, and polyurethane acrylates. .

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, 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 kinds. A photographic material using a combination of two or more kinds of polymerizable compounds is described in JP-A-62-210445. In addition, a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of the above-mentioned ring original agent can also be used as a polymerizable compound.

In photosensitive materials, the polymerizable compound is halogenated 111
It is preferable to use it in the range of 50,000 to 120,000 parts by weight, and the more preferable range is 12 to 120,000 parts by weight.
000 parts by weight.

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

In addition, when the support is made of a porous material such as paper, it is necessary to obtain a certain level of smoothness according to the waviness-based method, as in the case of the support used in the photosensitive material described in JP-A No. 62-209529. It is preferable to have. In addition, when using a paper support, a paper support with low water absorption such as the photosensitive material described in JP-A No. 63-38934, and a paper support with a constant water absorption rate such as the photosensitive material described in JP-A No. 63-47754 can be used. Paper support having Bekk smoothness of JP-A-63-8133
A paper support with a low shrinkage rate such as the photosensitive material described in JP-A No. 9, a paper support with low air permeability such as the photosensitive material described in JP-A-63-81340, and a paper support as described in JP-A-63-97941. A paper support having a pH value of 5 to 9, such as the photosensitive material described above, can also be used.

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

In the photosensitive material, it is preferable that the polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets! An example of a photosensitive material in which a monomer compound is dispersed in the form of oil droplets in a photosensitive layer is described in JP-A-62-78552. The above-mentioned oil droplets may contain other components in the photosensitive layer such as silver halide, a reducing agent, a color image forming substance, etc. Regarding a photosensitive material containing silver halide in the oil droplets. is JP-A-62-2
No. 09450 and No. 62-164040,
For photosensitive materials that further contain a reducing agent within the oil droplets,
Each is described in JP-A-62-183453. In addition, when silver halide is contained in the oil droplets, as described in JP-A-63-15239,
It is preferable that the number of silver halide grains contained in the oil droplet is 5 or more.

More preferably, the oil droplets of the polymerizable compound are in the form of microcapsules. Regarding the microcapsules, various known techniques can be used without particular limitations. An example of a photosensitive material in which oil droplets of a polymerizable compound are in the form of microcapsules is disclosed in Japanese Patent Laid-Open No. 61-27.
There is a description in Publication No. 8441.

There are no particular restrictions on the wall material that constitutes the outer shell of the microcapsules. In the present invention, the wall material constituting the outer shell of the microcapsule is preferably impermeable to the liquid contained in the photosensitive layer during image formation, and is preferably made of polyamide resin and/or polyester. Regarding a photosensitive material using microcapsules having an outer shell made of resin, see Japanese Patent Application Laid-Open No. 62-209437.
Regarding a photosensitive material using microcapsules having an outer shell made of polyurea resin and/or polyurethane resin, see JP-A-62-209438, and about a photosensitive material using microcapsules having an outer shell made of amino aldehyde resin. JP-A-62-209439 describes a photosensitive material using microcapsules having an outer shell made of gelatin, and JP-A No. 62-209440 describes a photosensitive material using microcapsules having an outer shell made of epoxy resin. For photosensitive materials, see JP-A-62-209.
No. 441 discloses a photosensitive material using microcapsules having a composite resin shell containing a polyamide resin and a polyurea resin, and Japanese Patent Application Laid-open No. 62-209447 describes a photosensitive material having a composite resin shell containing a polyurethane resin and a polyester resin. Photosensitive materials using microcapsules are described in JP-A-62-209442.

When using aldehyde-based microcapsules, as in the photosensitive material described in JP-A No. 63-32535,
It is preferable to keep the amount of residual aldehyde below a certain value.

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

In addition, microcapsules containing at least one of the components contained in the microcapsules, such as silver halide, a reducing agent, a polymerizable compound, and a color image-forming substance, which is an optional component described below, can be used. Two or more types of microcapsules may be used in combination, and in particular, when forming a full-color image, it is preferable to use three or more types of microcapsules containing different coloring hues of the color image forming substances contained therein. For photosensitive materials that use JP-A-62-1
There is a description in Publication No. 98850.

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

In addition, when storing silver halide in microcapsules, the average particle size of the tin halide particles 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.

The following optional components that can be included in the photosensitive layer of the margin photosensitive material include color image forming substances, sensitizing dyes, mui salts, radical generators, various image formation accelerators, thermal polymerization inhibitors, and thermal polymerization initiators. development stopper, fluorescent whitening agent, anti-fading agent, anti-halation or irradiation dye or pigment, pigment that decolors when heated or exposed to light, matting agent, anti-smudge agent, plasticizer, water Examples include a releasing agent, a binder, a photopolymerization initiator, a solvent for a polymerizable compound, a water-soluble vinyl bomber, and a hardening agent.

Although a Bommer image can be obtained from the photosensitive material by the above-described structure of the photosensitive layer, 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 (R colorants). Substances that develop color upon contact (color formers) are also included in color image forming substances. Incidentally, general photosensitive materials using color image-forming substances are described in the above-mentioned Japanese Patent Laid-Open No. 73145/1983. Regarding photosensitive materials using dyes or pigments as color image forming substances, see JP-A-62-187346, and about photosensitive materials using leuco dyes, see JP-A-62-209436. For photosensitive materials using leuco dyes, see JP-A No. 62-251741, and for photosensitive materials using yellow coloring leuco dyes, see JP-A Nos. 62-288827 and 62-288.
No. 828 describes a photosensitive material using a cyan color-forming leuco dye, and Japanese Patent Application Laid-Open No. 63-53542 discloses a photosensitive material using a cyan color-forming leuco dye. 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 1972, "
Latest Pigments Handbook” edited by Japan Pigment Technology Association, published in 1972)
The known ones described in 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 materials develop color upon heating, pressurization, light irradiation, or air oxidation.

Examples of substances that develop color when they come into 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 components6. For example, pressure-sensitive copying paper (pages 29-58), Azography (87
~95 pages), heat-sensitive color development by chemical change (I18~120
Pages 26-32 of the Proceedings of the seminar rIjC New Pigment Chemistry - Attractive Utilization and New Developments as Functional Pigments - 1 sponsored by the Kinki Chemical Industry Association, pages 26-32.
It is possible to use the coloring system described in J. I. June 19, 1980).

Specifically, lactones and colorants used in pressure-sensitive paper)
A coloring system consisting of aromatic diazonium salts, diazotates, diazosulfonates and azo coupling reactions such as naphthols, anilines, and activated methylenes; hexamethylenetetramine, ferric ion kudzu, and gallic acid. Chelate-forming reactions such as the reaction of phenolphthalein-complecranes with alkaline earth metal ions; reactions of ferric stearate with pyrogallol and reactions of silver behenate with 4-methoxy-1-naphthol, etc. Oxidation-reduction reactions, etc. can be used.

More preferably, when a color developer is used, it is about 0.3 to 8031ff for the color developer t and mt parts.
It is preferable to use i parts.

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

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and silver halide sensitizing dyes known in the photographic technology can be used. The above-mentioned sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Includes styryl dyes and hemioxonol dyes. Kowara's 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. It is. 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 from 10-8 to 10-1 per mole of silver halide.
It is about 2 moles.

The above-mentioned sensitizing dye is preferably added at the stage of preparing a silver halide emulsion, which will be described later. A photographic material obtained by adding a sensitizing dye at the stage of forming silver halide grains is described in JP-A-62-947, f&! Regarding light-sensitive materials obtained by adding a sensitive dye at the stage of preparing a silver halide emulsion after the formation of silver halide grains,
Each is described in JP-A-62-216449. Further, specific examples of sensitizing dyes that can be used in light-sensitive materials are also described in the above-mentioned JP-A-62-947 and JP-A-62-210449. Further, as in the photosensitive material described in JP-A-63-184738, a sensitizing dye sensitive to infrared light may be used in combination.

Addition of organic silver salts to light-sensitive materials is particularly effective in thermal development processing. That is, when heated to a temperature of 80° C. or higher, the above organic silver salt 28 is considered to participate in an oxidation-reduction reaction catalyzed by the 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 0.01 to 10 mol, preferably 0.0 mol per mol of silver halide.
Use 1 to 1 mole. In addition, instead of the organic silver salt, an organic compound (for example, benzotriazole) constituting it may be used.
A similar effect can be obtained by adding to the photosensitive layer. A photosensitive material using an organic silver salt is described in JP-A-62-3246. The organic silver salt as described above is preferably used in an amount of 0.1 to 10 mol, more preferably 0.017y to 1 mol, per 1 mol of silver halide.

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

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

Various image formation accelerators can be used in the photosensitive material. Image formation accelerators include those that promote the redox reaction between silver halide (and/or a silver salt) and a reducing agent; , promoting the movement 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.

They are further classified into compounds having an antifogging function and/or a development accelerating function, heat solvents, compounds 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, 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;
Examples include ammonium hydroxide; hydroxide of quaternary alkylammonium; hydroxide of other metals, etc. Existing bases include aliphatic amines (trialkylamines,
Hydroxylamines, aliphatic polyamines): Aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis[P-
(dialkylamino)phenylcomethanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, etc., and those in which p has a 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-toluidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonylacetate, 4-chlorophenylsulfonylacetate guanidine, and 4-methyl- Examples include guanidine sulfonylphenylsulfonylacetate and guanidine 4-acetylaminomethylpropiolate.

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 10011% by weight or less, more preferably from 0.1% to 40% 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 JP-A-62-264041. Regarding photosensitive materials using tertiary amines as bases, JP-A-82-170954 discloses that the melting point is 8.
Regarding a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound at a temperature of 0 to 180°C, Japanese Patent Application Laid-Open No. 62-209523
No. 62 215 G37 describes a photosensitive material using a guanidine rust conductor with a solubility of 0.1% or less.
JP-A No. 1983-1999 describes photosensitive materials using hydroxides or salts of alkali metals or alkaline earth metals.
Each of these is described in JP-A No. 209448.

Furthermore, regarding a photosensitive material using an acetylide compound as a base precursor, JP-A-63-24242 discloses a photosensitive material using a propiolate as a base precursor.
Furthermore, regarding photosensitive materials containing silver, steel, silver compounds, or copper compounds as catalysts for base generation reactions, JP-A-63-46
446, and JP-A-63-81338 describes a photosensitive material containing the above-mentioned propiolic acid salt and silver, copper, a silver compound, or a copper compound separated from each other.
Regarding photosensitive materials containing the above-mentioned propiolate and the above-mentioned silver, copper, a silver compound, or a ligand in a free state in addition to the copper compound, JP-A No. 63-97942 describes a propiolate as a base precursor. JP-A-63-46447 discloses a photosensitive material that uses a sulfonylacetate as a base precursor and further contains a heat-fusible compound as a reaction accelerator for the base-forming reaction. JP-A No. 63-48543 discloses a photosensitive material containing a compound containing an isocyanate or an isothiocyanate as a base precursor, and JP-A No. 63-24242 contains a compound containing an isocyanate or an isothiocyanate as a base precursor. There are descriptions for each.

When using a base or base precursor in a photosensitive material,
It is preferable that silver halide, a reducing agent, and a polymerizable compound are contained in the microcapsules described above, and a base or a base precursor is present in the photosensitive layer outside the microcapsules. Or, JP-A-62-2095
As in the photosensitive material described in Japanese Patent No. 21, the base or base precursor may be contained in separate microcapsules. In addition to the above publication, there is a photosensitive material using 72F microcapsules containing a base or a base precursor. Japanese Patent Application Laid-Open No. 62-209522 discloses a photosensitive material in which solid fine particles carrying a base or a base precursor are housed in microcapsules, and JP-A-62-209526 discloses microcapsules containing a basic compound with a melting point of 70°C to 210°C. Regarding photosensitive materials using JP-A-63
-65437 publication, respectively. Alternatively, 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 disclosed in JP-A No. 63-97943. good.

In addition, the base or base precursor
As described in Japanese Patent No. 253140, it may be added to an auxiliary layer other than the photosensitive layer (a layer containing a base or a base precursor, which will be described later). Furthermore, JP-A-63-3
As described in Japanese Patent No. 2546, the above-mentioned support may be made porous, and a base or a base precursor may be contained 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 viridinicum salts, ammonium salts, and phosphonium salts disclosed in JP-A-59-74547, polyalkylene oxides described in JP-A-59-57231, and the like.

A compound having an antifogging function and/or a development accelerating function can be used for the purpose of obtaining a clear image (an image with a high S/N ratio) having a high maximum density and a low minimum density. Note that the photosensitive material using an antifoggant as a compound having an antifogging function and/or the development accelerating function is described in JP-A-62-151838, and the photosensitive material using a compound having a cyclic amide structure is described in the special publication. For photosensitive materials using 5-thio-ester compounds, see JP-A No. 62-151841.
No. 151842 describes a photosensitive material using a polyethylene glycol conductor, and Japanese Patent Application Laid-open No. 151843/1983
No. 62-1511344 for a photosensitive material using a thiol conductor, and No. C for a photosensitive material using an acetylene compound in JP-A No. 62-178.
232, for photosensitive materials using sulfonamide derivatives, see JP-A-62-183450, and for photosensitive materials using quaternary ammonium salts, see JP-A-63.
Publication No. 91653 has their own statements.

Useful examples of the thermal solvent include compounds that can serve as solvents for reducing agents, and compounds that are known to have a high conductivity and promote physical development of silver salts. Useful thermal solvents include:
Polyethylene glycols described in U.S. Patent No. 3,347,675, derivatives such as oleic esters of polyethylene oxide, beeswax, monostearin, -50
Compounds with high phoneticity having 2- and/or 100- groups, polar substances described in U.S. Pat. Diol, methyl anisate, biphenyl shaleate, etc. are preferably used. Incidentally, a photosensitive material using a heat solvent is described in JP-A-62-86355.

A compound having an oxygen removing function can be used for the purpose of eliminating oxygen shadow 1 (oxygen has a polymerization inhibiting effect) during development. Examples of compounds having an oxygen removing function include compounds having two or more mercapto groups. Incidentally, a photosensitive material using a compound having two or more mercapto groups is described in JP-A-62-209443.

A development stopper that can be used in photosensitive materials 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 the daughter and silver salt to stop the development after proper 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 JP-A-6010
Examples thereof include oxyesters described in JP-A-8837 and JP-A-60-192939, and compounds that release an acid by Rossen rearrangement as described in JP-A-60-230133.

Examples of electrophilic compounds that undergo a substitution reaction with a base upon heating include compounds disclosed in Japanese Patent Application Laid-open No. 60-230134.

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

When the photosensitive layer of the photosensitive material uses the above-mentioned microcapsules, the microcapsules may contain a dye that can be decolored by heating or light irradiation. The dye having the property of being decolored by heating or light irradiation can function as a yellow filter in conventional silver salt photography. Regarding photosensitive materials using dyes that have the property of decolorizing by heating or light irradiation as mentioned above, Japanese Patent Laid-Open No. 6
There is a description in Publication No. 3-97940.

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

Binders that can be used in the photosensitive material can be contained in the photosensitive layer alone or in combination. It is preferable to use a mainly hydrophilic binder. Hydrophilic binders are typically transparent or translucent, such as gelatin, gelatin derivatives, cellulose conductors, starch, gum arabic, etc. and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers.

Other synthetic polymeric materials include dispersed vinyl compounds in the form of latex, particularly those that increase the soot stability of photographic materials. The binder has a ratio of 2 to 100% relative to the polymerizable compound.
It is preferable to use it within a range of % by weight. Regarding photosensitive materials using binders, Japanese Patent Application Laid-Open No. 61-6906
There is a description in Publication No. 2. Regarding photosensitive materials using binders together with microcapsules, Japanese Patent Application Laid-open No. 62
There is a description in the publication No.-209525.

In the photosensitive material used in the image forming method of the present invention, it is preferable to use a hydrophilic binder together with a hardening agent.When the hydrophilic binder is hardened, the physical properties of the photosensitive layer when a liquid such as water is added will improve.

There is no particular IIJ limit for the hardening agent used in the photosensitive layer. Known hardeners include aldehydes (e.g., formaldehyde, glyoxal, geltaraldehyde), N-methylol compounds (e.g., dimethylol urea, methylol dimethylhydantoin), dioxane conductors (e.g., 2,3-
dihydroxydioxane), active vinyl compounds (e.g. 1
, 3.5-Triacryloyl-hexahythroS-) riazine, bis(vinylsulfonylacetamide), N.

No-ethylene-bis(vinylsulfonylacetamide)
, N,N'-trimethylene-bis(vinylsulfonylacetamide)), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-5-triazine), mucohalogen acids (e.g., mucochloric acid, mucophene), Onxychlor M
), inoxazoles, dialdehyde starch, 1-chloro-6-hydroxytriazinylated gelatin, and epoxy compounds. The hardening agent is preferably used in an amount of 0.1 to 301% by weight, particularly preferably 0.5 to 10% by weight, based on the hydrophilic pineapple.

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. A photosensitive material using a photopolymerization initiator is described in JP-A-62-161149.

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

A photosensitive material using a water-soluble vinyl polymer as described above may be used by adsorbing a water-soluble vinyl polymer to the silver halide grains described above, as described in Japanese Patent Application Laid-Open No. 63-9165.
There is a description in Publication No. 2.

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 for the series of photosensitive materials mentioned above, and in Research Disclosure Magazine v01゜170.6, 1978. It is described in Monthly issue No. 17029 (pages 9-15).

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

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

Instead of using the image-receiving material described later as a method of using the photosensitive material, the image-receiving layer described above may be provided on the photo-sensitive material and an image may be formed on this layer. It is possible to have the same configuration as t1. Details of the image receiving layer will be described later.

Regarding photosensitive materials using a heat generating layer, Japanese Patent Application Laid-open No. 1983
For photosensitive materials provided with a cover sheet or a protective layer, see JP-A No. 62-210447, and for photosensitive materials provided with a layer containing a base or base precursor, see JP-A No. 62-253140. A photosensitive material provided with a colored layer as an antihalation layer is described in JP-A-63-101842. Further, a photosensitive material provided with a base barrier layer is also described in the above-mentioned Japanese Patent Application Laid-Open No. 62-253140. Further examples of other auxiliary layers and their uses! 3
This is also described in the publications regarding the above-mentioned series of photosensitive materials.

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

Various methods can be used to manufacture photosensitive materials, but the general manufacturing method is to prepare a coating solution by dissolving, emulsifying, or dispersing the components of the photosensitive layer in an appropriate solvent, and then coating. This process consists of applying a liquid onto a support as described above and drying it to obtain a photosensitive material.

Generally, each of the above-mentioned coating liquids is prepared by preparing a liquid composition containing each component and then mixing the respective liquid compositions. The liquid composition may be prepared to contain multiple components. Some of the components of the photosensitive layer can also be added during or after the preparation of the liquid composition or coating solution. Furthermore, as described below, 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 a liquid composition and a coating solution are shown below.

The halogenated L agent can be prepared 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 as follows:
Any one of the one-side mixing pot method, the simultaneous mixing method, or a combination thereof may be used.The back mixing method in which zero particles are formed under conditions in which silver ions are excessive, and the 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).
No. 24, No. 55-158124, and U.S. Pat. No. 3,650,757 (see WJ).

Silver halide emulsions used in the production of photosensitive materials may be of the surface latent image type, in which latent images are mainly formed on the surface of the grains, or may be of the internal latent image type, in which latent images are formed inside the grains. It is also possible to use a direct reversal emulsion, which is a combination of a latent image type emulsion and a nucleating agent. Internal latent image emulsions for this purpose are described in U.S. Pat. No. 2,592,250, U.S. Pat.
No. 136641 has been extensively published. A preferred nucleating agent for combination with the above emulsion is US Pat.
No. 52, No. 4245037, FIN4255511
No. 15. 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 hydrophilic colloids as protective colloids. Examples of hydrophilic colloids include gelatin, gelatin derivatives, and combinations of gelatin and other polymers. Proteins such as graft polymers, albumin, and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose conductors such as cellulose sulfates, sodium alginate, m derivatives such as powdered conductors; and polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide Various synthetic hydrophilic polymeric substances such as mono- or copolymers such as polyvinylimidazole, polyvinylpyrazole, etc. can be mentioned. Among these, gelatin is preferred; in addition to lime-treated gelatin, acid-treated gelatin and enzyme-treated gelatin may also be used, and gelatin hydrolysates and enzymatically decomposed products can also be used.

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

Soluble salts may be removed from the silver halide emulsion after precipitation or physical ripening. In this case, this can be carried out according to the Tardel water washing method or the precipitation method. The silver halide emulsion may be used as it is after heating, but it is usually used after being chemically sensitized.For emulsions for ordinary type sensitive materials, there are known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. 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 and 5B-215644).

In addition, when adding a sensitizing dye to a silver halide emulsion,
The aforementioned Japanese Patent Application Laid-open No. 62-947 and Japanese Patent Application Laid-open No. 62-
It is preferable to add the nitrogen-containing heterocyclic compound at the preparation stage of the silver halide emulsion, as in the light-sensitive material described in JP-A No. 210449, and when the nitrogen-containing heterocyclic compound is added as a compound having the above-mentioned capri-preventing function and/or development accelerating function. In the production of a photosensitive material, a nitrogen-containing heterocyclic compound is preferably added at the formation stage or ripening stage of silver halide grains in the preparation of a silver halide emulsion. The method is described in JP-A-62-161144.

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, the polymerizable compound is used as a medium for preparing the composition of other components in the photosensitive layer, and acid substances, etc. are dissolved, emulsified, or included in the compound. is preferred. Furthermore, as will be described later, when the oil droplets of the polymerizable compound are microencapsulated, components such as a wall material necessary for microencapsulation may be included in the polymerizable compound.

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

Photosensitive compositions containing these silver halides can be obtained by stirring with a homogenizer, slender, 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. Instead of using a copolymer, the photosensitive composition may be prepared by dispersing microcapsules having a silver halide emulsion as a core material in a polymerizable compound. Microcapsules having the above-mentioned silver halide emulsion as a core material A photosensitive composition containing the above is described in JP-A-62-164041.

It is preferable to use the polymerizable compound (including those containing other constituent components like the above photosensitive composition) in the form of an emulsion in an aqueous solvent. Also, JP-A-61
When oil droplets of a polymerizable compound are microencapsulated in a photosensitive material published by Publication No. 275742, a wall material necessary for microencapsulation is added to the emulsion,
Furthermore, a treatment for forming the outer shell of microcapsules can also be carried out at the stage of this emulsion. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

Examples of the above-mentioned microencapsulation method include methods using coacervation of aromatic wood-philic wall-forming materials as described in US Pat. No. 2,800,457 and US Pat. No. 2,800,458; US Pat. Specification of contents and Japanese Patent Publication No. 3B-1957
No. 4, No. 42-446, and No. 42-771. Interfacial polymerization method described in U.S. Patent No. 3,418,250 and No. 3,660,304 Method by precipitation of aromatic polymer: U.S. Pat. No. 3,796,669 Method using the isocyanate-polyol wall material described in U.S. Pat. No. 3,914,511; U.S. Pat. No. 4,001,140, U.S. Pat.
A method using a urea-formaldehyde-based or urea-formaldehyde-resircinol-based wall forming material described in each specification of US Pat. No. 4,025,455; Method using a forming material; In-5-itu method by polymerization of 1,000 yen as described in Japanese Patent Publication No. 36-9168 and Japanese Patent Application Laid-open No. 51-9079; British Patent No. 927807 and British Patent No. 965074. Polymerization dispersion cooling method; US Pat. No. 3,111,407 and British Patent No. 930
Methods for microencapsulating oil droplets of polymerizable compounds include, but are not limited to, methods such as the spray drying method described in the specification of 422 Aroyo, but are not limited to the above. Particularly preferred is a method in which a polymer film is formed as a microcapsule wall after the polymerization.

Regarding photosensitive microcapsules that can be used in the production of photosensitive materials, Japanese Patent Application Laid-open Nos. 169147/1987, 62/169148/1971, and 209437/1982
No. 62-209438, No. 62-209439, No. 62-209440, No. 62-209441,
There is a description in each of the publications No. 62-209447 and No. 62-209437.

Among the above-mentioned emulsions of polymerizable compounds (including microcapsule liquids subjected to microencapsulation treatment), if the polymerizable compound is a photosensitive composition containing silver halide, it can be directly used as a coating solution for photosensitive materials. It can be used as Emulsions other than those mentioned above can be mixed with a composition of other components such as a silver halide emulsion and optionally an organic silver salt emulsion to prepare a coating solution. It is also possible to add other components at the stage of this coating solution in the same manner as in the case of the emulsion described above.

As a method different from the method using microcapsules, silver halide emulsions, polymerizable compounds, color image forming substances,
There is a method in which a mixture of borate compounds is packetized to form a so-called packet emulsion and coated in the same layer. A method for producing a packet emulsion is described in detail in JP-A-58-40551.

When a packet emulsion is used, the reducing agent may be present in the packet or outside the packet.

A photosensitive material is produced by applying the coating solution for the 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.

The electronic image receiving material of the present invention will be explained below. For general image forming methods using image-receiving materials or image-receiving layers, please refer to Japanese Unexamined Patent Publication No. 6
There is a description in Publication No. 1-278849.

As the support for the image-receiving material, baryta paper can be used in addition to the supports that can be used for the photosensitive materials described above. In addition, when using a porous material such as paper as a support for the image-receiving material, Japanese Patent Application Laid-Open No. 62-20953
It is preferable that the image-receiving material has a certain level of smoothness like the image-receiving material described in Bulletin No. 0. Further, an image receiving material using a transparent support is described in JP-A-62-209531.

Image-receiving materials generally have an image-receiving layer 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. Further, the image-receiving layer can also be constructed by combining at least one layer containing a mordant. The mordant may be selected from compounds known in photographic technology and the like, taking into consideration conditions such as the type of color image forming substance. Note that two or more image-receiving layers may be constructed by using a plurality of mordants having mordant power, if necessary.

The image-receiving layer preferably contains a polymer as a binder. As the binder, binders that can be used in the photosensitive layer of the photosensitive material described above can be used. Further, as in the image-receiving material described in JP-A-62-209454, a polymer with low oxygen permeability may be used as a 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 image formation. There is no particular limit to the above thermoplastic compounds, and there are known plastic resins (
It can be arbitrarily selected from among (plastic), wax, etc. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200°C or less.For an image receiving material having an image receiving layer containing thermoplastic compound fine particles as described above, JP-A-62-280
There is a description in No. 071 and 62-280739 Yoyo Publication.

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, in order to smoothly proceed with the curing process (fixing vs. Fl) of the unpolymerized polymerizable compound,
A photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer. Further, regarding an image receiving material having an image receiving layer containing a photopolymerization initiator, see JP-A-62-161149, and regarding an image-receiving material having an image-receiving layer containing a thermal polymerization initiator, see JP-A-62-210444, respectively. There is a description.

The dye or n-rows can be included in the image-receiving layer for the purpose of inscribing characters, symbols, frames, etc. in the image-receiving layer, or for the purpose of providing a particular color to the background of the image. Further, 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 It is preferable to use a dye or pigment that has the property of decolorizing when heated or exposed to light.

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 JP-A-62-251741.

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 this, image information that is unnecessary in the projected image can also be included as a reflected image in the image receiving layer portion containing the white pigment.

The image-receiving layer may be configured as two layers depending on the functions described above. Further, the layer thickness of the image-receiving layer is 1 to 1
It is preferably 00 μm, and more preferably 1 to 20 μm.

Note that a protective layer may be further provided on the image-receiving layer. Furthermore, a layer made of aggregates of fine particles of a thermoplastic compound may be provided on the image-receiving layer. An image-receiving material in which a layer made of aggregates of fine particles of a thermoplastic compound is further provided on the image-receiving layer is described in JP-A-62-210460.

Furthermore, a pressure-sensitive adhesive or a layer containing an adhesive and a release paper may be sequentially laminated on the surface of the support opposite to the surface on which the image-receiving layer is provided. The sticker-like image-receiving material having the above structure is described in Japanese Patent Application Laid-Open No. 63-24647.

Margin C Example 1 below] 2α Santachi Niyoshihi! Gelatin aqueous solution (gelatin 2 in 1000 d of water)
0g of sodium chloride and 3g of sodium chloride kept at 75°C), an aqueous solution of 600 xi containing 21g of sodium chloride and 56g of potassium bromide, and an aqueous solution of silver nitrate (600g of water).
．． At the same time, 0.59 mol of silver nitrate dissolved in d) was added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol %) having an average grain size of 0.35 μm was prepared.

After washing the emulsion with water and desalting it, 51 g of sodium thiosulfate and 4-hydroxy-6-methyl-13,3a, ?
- 20 mg of tetrazaindene was added to perform chemical sensitization at 60°C. The yield of emulsion was 600 g.

Add 28g of benzo aerosol gelatin and 13.2g of benzotriazole to 33g of water.
Dissolved in 000I11. This solution was stirred while being kept at 40°C, and a solution of 17 g of nitric acid IF dissolved in 100 ml of water was added over 2 minutes. Excess salt was precipitated and removed by adjusting the pH of the resulting emulsion. Then P
H was adjusted to 6.30 to obtain a benzotriazole silver emulsion. The yield of emulsion was 400 g.

100 g of trimethylolpropane triacrylate, 0.40 g of the following copolymer, and the following Coil dye (C15
, og, and 2 g of Emmalex NP-8 (manufactured by Nippon Emulsion ■) were dissolved. Above solution 18. To OOg,
0.40 of the borate compound (B-1) of the present invention and about 1.22 of the following developing agent (reducing agent) were added in 1.80 g of methylene chloride.
A solution dissolved in was added. Furthermore, 3.50 g of the silver halide emulsion prepared as above and 3.35 g of benzotriazole silver emulsion were added, and the mixture was stirred for 5 minutes at 15,000 revolutions per minute using a homogenizer to obtain a photosensitive composition. .

(Copolymer) C1)3 C)Is -(-CI+yo-C-)rr (:02O2C41 l Leuco dye a dye developer) Microcab Koru Tetsu 0IJI 18.6% aqueous solution of isopane (manufactured by Tarare ■) 10° 51
g, add 48°56 g of a 2.89% aqueous solution of pectin,
The above-mentioned photosensitive composition was added to an aqueous solution whose pH was adjusted to 4.0 using 10% sulfuric acid, and the mixture was heated using a homogenizer to
The photosensitive composition was stirred at 000 rpm 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 2.82%, formalin 37% aqueous solution 8.56g, ammonium sulfate 8.76g
Add 2.74g of % aqueous solution one by one and heat to 60°C while stirring.
Heating was continued for 2 hours.

Then adjust the pH to 7 using a 10% aqueous sodium hydroxide solution.
．． 0, and 3.62 g of 3069% sodium bisulfite aqueous solution was added to prepare a microcapsule liquid.

10.0g of microcapsule liquid prepared as above
, add 1.0 g of the following 1% aqueous anionic surfactant solution,
Guanidine trichloroacetate 10% (water/ethanol-
50150 volume ratio) solution was added and applied onto a 100 μm thick polyethylene terephthalate using a #40 coating rod, and dried at about 40'C to prepare a photosensitive material (A) according to the present invention. .

(Anionic surfactant) CH*C00CHx CH(CJs)CJ*Na0s
S-CH-COOC1lz-C! l((:Js)CJq
[Example 2] Instead of 0.4 g of borate compound (B-1) used in the preparation of the photosensitive composition of Example 1, borate compounds (B-6), (B-7), ( B-8), (B
The photosensitive material according to the present invention (
B), CC>, (D) and CE) were produced.

[Comparative example]

In the preparation of the photosensitive composition of Example 1, 0.4 of the following hydrazine derivative was used instead of the borate compound (B=1).
A comparative photosensitive material (F) was prepared in the same manner as in Example 1 except that 0 g was added.

(Hydrazine derivative: known polymerization initiator) 11 g of 40% sodium hexametaphosphate aqueous solution was added to 125 g of water, followed by 34 g of zinc 3.5-di-α-methylbenzyl salicylate and 55% calcium carbonate. 82 g of the slurry was mixed 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. Apply this mixture to 301 Im wet 1 on art paper with a basis weight of 43 g/rd.
After applying the film uniformly so as to obtain a color of 11, it was dried to prepare an image-receiving material.

2) Each of the photosensitive materials obtained in Example 1.2 and Comparative Example was heated at 200 lux using a tungsten light bulb.
After imagewise exposure for seconds, each light-sensitive material was heated for 10 seconds, 20 seconds, and 30 seconds on a hot plate heated to 125"C. Then, each photosensitive material was layered with the above image-receiving material, and a 350 kg/cr" pressure roller was applied. The density was measured using a reflection densitometer using a blue positive color image obtained on the image-receiving material.

The above measurement results are shown in Table 1 below.

As is clear from the results in Table 1, the photosensitive material according to the present invention has excellent discrimination (high S/N ratio) in a short development time compared to the case of using a known polymerization initiator. give an image.

[Example 3] Acrylamide 2. Og, methylenebisacrylamide 0.25g, silver behenate emulsion (0.8 as silver behenate)
g), 1-methylamino-4-(m-toluidino)anthraquinone 0.45g, polyvinylpyrrolidone 3.0g
A mixture of 30 d of methanol and 30 d of methanol was dispersed at 110,000 PP for 10 minutes using a high-speed shedding stirrer.

The above dispersion was applied onto a polyethylene terephthalate film to a wet film thickness of 60 μm and dried.

Next, a solution prepared by dissolving 0.15 g of the compound (B-2) of the present invention, 0.2 g of the developer of Example 1, 25 μm of ammonium bromide and 5 μm of ammonium iodide in 5 d of methanol was applied and dried. Furthermore, add 4% gelatin aqueous solution 1
00g, 2ml of 1% sodium dodecylbenzenesulfonate aqueous solution1. A mixture of 0.1 g of formaldehyde sodium bisulfite adduct was coated to a wet film thickness of 5 μm and dried to prepare a photosensitive material.

The above photosensitive material was imagewise exposed for 5 seconds at 2000 lux using a tungsten bulb. Thereafter, it was heated for 20 seconds on a hot plate heated to 110°C.

Next, when it was washed off by immersing it in a methanol bath, a cyan image with good disk cleanliness corresponding to the exposed area was obtained.

[Example 4] 10% by weight of silver chlorobromide (chlorine/bromine, molar ratio 21/1)
, 2 g of silver halide emulsion containing 7% by weight of gelatin, 0.2 g of the compound (B-1) of the present invention, and 0.2 g of the developer of Example 1.
15g, sorbitol O9Ig, 51!1% aqueous solution of sodium p-dodecylbenzenesulfonate 0. ig,
Pentaerythritol tetraacrylate 2.0g, 1
．． A liquid mixture consisting of 0.3 g of 4-bismethylaminoanthraquinone and water was emulsified in an ultrasonic emulsifier for 1 hour, and applied onto a polyethylene film to a dry film thickness of about 10 μm. Furthermore, 4% gelatin aqueous solution 100
g, 1% aqueous sodium dodecylbenzenesulfonate solution 2-, formaldehyde sodium bisulfite adduct 0.
A mixture of 1 g of guanidine trichloroacetic acid and 3.0 g of guanidine trichloroacetic acid was coated and dried to a dry film thickness of 3 μm.

The above photosensitive material was imagewise exposed for 10 seconds at 2000 lux using a halogen lamp. Thereafter, it was heated for 30 seconds on a hot plate heated to 120°C.

Next, when the film was thoroughly washed off using a solution consisting of 2 parts of ethanol and 1 part of water, a clear blue image corresponding to the exposed areas was obtained.

(Example 5) Preparation of pensitoazole silver emulsion 6.5 g of benzotriazole and 10 g of gelatin were mixed with 10 g of water.
Dissolves in 00d. This dissolution is maintained at 50°C and stirred.

Next, a solution of 8.5 g of silver nitrate fIi dissolved in 100 d of water is added to the above solution over a period of 2 minutes.

By adjusting the pH of this emulsion, it was allowed to settle, unnecessary salts were removed, and the pH was adjusted to 6.0 to obtain a benzotriazole silver emulsion with a yield of 400 g.

Preparation method of silver iodobromide emulsion H, 20 g of gelatin and 9.52 g of KBr in 01000-
and 3.32 g of KI. This solution was heated to 50°C.
Keep stirring.

Add 17 g of A g NOi to this solution! 0100
Add the solution dissolved in d over 10 minutes. then 35°
The emulsion was allowed to settle and excess salt was removed by cooling to 50°C and adjusting the pH.

After that, adjust the pH to 6.0 and yield 200g of AgBr.
An emulsion of I (20 mol% I) was obtained.

Preparation of packet emulsion N, N'-diacryloylpiperazine 5g, pentaerythryl tetraacrylate 3g 1 compound of the present invention (
B-1) 0.3g, developer of Example 1 0.3g, 3.3
-bis-(I-ethyl-2methyl-3-indolyl)phthalide Ig, phenylxylylethane 10d and tricresyl phosphate 10- are mixed and dissolved in 110g of 10% gelatin containing 0.5g of sodium dodecylbenzenesulfonate. A dispersion of a color image-forming substance was prepared by emulsifying and dispersing the material.

To 4 g of the silver iodobromide emulsion was added 3,3'-di(γ-sulfopropyl)-5,5'-diphenyl-9ethyloxacarbocyanine sodium salt (4 x 10-' mol per 1 mol of halide). Add methanol solution of 5
After stirring for a minute, 20 g of the color image-forming 1'l dispersion previously prepared and 30 g of benzotriazole silver emulsion were added and mixed.

Add to this 301 d of 10% gum arabic aqueous solution and 100 ml of water.
and p.p. with 1% acetic acid aqueous solution while stirring at 45°C.
Adjusted to H4.80. After stirring for 155 minutes, the mixture was cooled to 'C and stirred for 30 minutes. To this was added 150 d of water containing 0.14 g of chromium alum, and after further stirring for 1 hour, a 5% aqueous sodium carbonate solution was added, left to stand overnight, and the supernatant liquid was removed by decantation. The yield of the packet emulsion thus prepared was 90g, and the average size was about 10t/
It was m.

Manufacturing method of photosensitive material (green-sensitive photosensitive material) The coating solution containing the packet emulsion was coated with a wet film thickness of 5 (LI
Im coated on a polyethylene terephthalate film, and after drying, a gelatin protective film (gelatin: 1 g/n
(containing 2.0 g/g of glinisin trichloroacetic acid) was coated to obtain a light-sensitive material.

The obtained light-sensitive material was exposed to green light using a filter, and then heated uniformly at 120'C for 20 seconds.Then, the light-sensitive material was overlapped with the image-receiving material of Example 1 and passed through a pressure roller. However, a clear magenta image corresponding to the unexposed area was obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1゜ 2゜ 3゜ Display of incidents name of invention person who makes corrections Heisei I photosensitive material Special application No. λ of the year! No. 77 Relationship with the incident

Claims (1)

[Scope of Claims] A photosensitive material comprising at least a silver halide, a reducing agent, a polymerizable compound, and a borate compound represented by the following general formula (I) on a support. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the above formula, R_1 to R_4 are substituents selected from alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, aryl groups, and heterocyclic groups. represents. M represents an alkali metal or a primary to quaternary ammonium group.