JPH02109050A - Production of photosensitive material - Google Patents

Abstract

PURPOSE:To facilitate separation of a photosensitive material from an image receiving material and to improve the quality of a picture by using a photosensitive material contg. microcapsules prepd. by dispersing an oily liquid mixture in aq. liquid contg. a specified amt. of styrene sulfonic acid type polymer. CONSTITUTION:An oily liquid mixture contg. a specified component is dispersed to form an oil-drops shape in aq. liquid contg. a styrene sulfonic acid type polymer (A), and the components of both liquids are allowed to react. Thus, inside walls comprising polyurea, etc., are formed around the oil drops. Then, external walls comprising melamine/formaldehyde resin are formed and photosensitive microcapsules are prepd. by adding melamine and formaldehyde, or a prepolymer (B) of melamine/formaldehyde condensation product to above- described aq. liquid. The amt. of the component(A) to be added is 30-65wt.% basing on the amt. of the component(B). Succeedingly, the liquid dispersion contg. the above-described microcapsules is applied on a base body, and the title photosensitive material is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a method for producing a photosensitive material in which a photosensitive layer containing a silver halide grain-1 reducing agent and a compositable compound is present on a support.

[Background of the invention] A photosensitive material in which a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound is formed on a support forms a latent image of silver halide and an image in which a polymerizable compound is polymerized. It can be used in forming methods. Examples of image forming methods include Japanese Patent Publications No. 45-11149, No. 47-20741, No. 4
There are methods described in various publications such as JP-A No. 9-10697, JP-A-57-138632, and JP-A-5-169143. In these methods, when the silver halide in the imagewise exposed photosensitive layer is developed using a developer, the coexisting reducing agent is oxidized, and the coexisting polymerizable compound (e.g., vinyl compound) is oxidized. Polymerizes to form a polymer (high molecular compound) in an image-wise manner. Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

As an improvement to the above method, a method has been proposed in which a polymer compound can be formed by dry treatment (Japanese Patent Laid-Open No. 61
-69062 and 61-73145). In this method, a photosensitive layer comprising a photosensitive silver salt (silver halide), a reducing agent, a crosslinking compound (polymerizable compound), and a binder or a color image forming substance is supported on a support. A recording material (!f!, optical material) made of This is a method of forming a polymer compound (polymer compound).

A method is already known in which an image is formed by polymerizing a polymerizable compound in a portion where a silver halide latent image is not formed (Japanese Patent Laid-Open Publication No. 260241/1982). This method is a method of suppressing polymerization in the area where the latent image of silver halide is formed and at the same time promoting r(1) in other areas (area where the latent image is not formed).

In the photosensitive material described in L, after an image-like polymer compound is formed on the photosensitive material as described above, this and an image-receiving material are further superimposed and pressure is applied in this state to remove the unpolymerized polymerizable material. It is generally used in an image forming method in which a compound is transferred to an image-receiving material. In this case, the light-sensitive material is preferably such that the silver halide and the polymerizable compound (including the color image forming substance) are housed in the same microcapsule. By introducing microcapsules, even better images can be obtained. JP-A-61-27
No. 5742 and No. 61-278849). Melamine/formaldehyde resin is advantageously used as the wall material for microcapsules because it is relatively tough and dense, prevents the contents contained in the capsule from seeping out, and improves preservability. (Japanese Unexamined Patent Publication No. 62-209439). In addition, the inventor
A patent application has been filed for a microcapsule and a photosensitive material composed of an inner wall made of polyurea resin and/or polyurethane resin containing silver halide particles and an outer wall made of amino aldehyde resin (Japanese Patent Application No. 6).
No. 2-105099! Book III). By forming the capsule with a double-walled outer shell, the capsule wall can be further strengthened and dense.

Incidentally, when preparing a capsule having a wall made of melamine formaldehyde tree Jli, an anionic protective colloid containing a styrene sulfonic acid polymer is preferably used (Japanese Patent Application Laid-open No. 121837/1983).

J: Photosensitive materials containing photosensitive microcapsules in the photosensitive layer as shown below are usually prepared by preparing a microcapsule dispersion containing components such as silver halide, a reducing agent, and a polymerizable compound, and then dispersing this on a support. It is manufactured by applying the method to

According to the inventor's study, when the above-described image forming method is performed using a photosensitive material manufactured in this way, the photosensitive material and image-receiving material come into contact with each other after pressure transfer, and the subsequent The peeling operation may become difficult (peeling inhibition), or, especially when carried out under high temperature and high humidity, some of the image-receiving material may adhere to the photosensitive material, making it impossible to obtain a good transferred image. I realized something.

[Summary of the Invention J An object of the present invention is to provide a method for producing a photosensitive material that can be advantageously used in an image forming method for obtaining a transferred image on an image-receiving material using the above-mentioned image-receiving material. do.

An object of the present invention is to provide a method for producing a photosensitive material, in which layer separation between a photosensitive material and an image-receiving material after pressure transfer can be carried out easily, and a transfer image with good image quality can be obtained.

The present invention provides an oily mixed liquid containing silver halide grains, a reducing agent, an [r-compounding compound, and a polyvalent isocyanate compound, which contains a polyol and/or a polyamine,
And dispersed in the form of oil droplets in an aqueous liquid containing a styrene sulfonic acid polymer in an amount of 30 to 65% by weight based on the content of melamine and formaldehyde or the amount of prepolymer, which will be described later, and the surrounding area of the oil droplets. polyurea and/or
or forming an inner wall made of polycrethane resin and containing silver halide grains; adding melamine and formaldehyde or their prepolymers to the aqueous liquid to form an outer wall made of melamine aldehyde resin around the inner wall; Production of a photosensitive material characterized by comprising: forming a wall to prepare photosensitive microcapsules; and applying a dispersion containing the photosensitive microcapsules to a support and drying them. provide law.

The present invention preferably has the following aspects.

(1) The above styrene sulfonic acid polymer is melamine and formaldehyde or a prepolymer of these! It is contained in an amount ranging from 40 to 60% by weight based on the weight of Tsuji.

(2) The ratio of the inner wall and outer wall above is 1:20 to 10
: It is formed in the range of 1.

(3) The above polymerizable compound is applied to the support at 1 to 20 g/r.
It was coated with a coating amount in the range of 17?

(4) The oily mixed liquid further contains a color image forming substance.

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

[Effects of the Invention] Conventionally, photosensitive microcapsules have been prepared by emulsifying and dispersing oily droplets containing silver halide particles and a polymerizable compound well in an aqueous liquid, achieving a desired capsule size of 47 cm, and uniformly forming a capsule. The capsule is stable and J! 1IyJ was carried out in the presence of an excess of styrene sulfonic acid based polymer relative to the shell forming material melamine/formaldehyde or the prepolymer (65% or more relative to melamine/formaldehyde). Therefore, the prepared capsule dispersion has a high content ratio of hydrophilic styrene sulfonic acid polymer, and photosensitive materials manufactured using this dispersion are likely to suffer from peeling S inhibition as described above. found. In particular, the oily liquid contained in the capsule of the present invention has a relatively low boiling point and is easily volatile, and
Since the image forming process included a heat development process, the bleeding described above was likely to occur. Therefore, the wall thickness of the 5 capsules needs to be thick, and the amount (absolute amount) of the styrene sulfonic acid polymer used increases.
It was found that the above-mentioned inhibition of peeling also tends to be promoted.

In the present invention, the capsule dispersion liquid is prepared in the presence of a certain range of styrene sulfonic acid polymers that can be prepared in good conditions as in the conventional method, so the above-mentioned reduction in emulsion dispersibility and capsule size The content of the styrene sulfonic acid polymer in the prepared capsule dispersion can be reduced without increasing the heterogeneity of the capsule.

Therefore, the photosensitive material produced using the capsule dispersion prepared in this manner can prevent the above-mentioned peeling inhibition and can provide good transferred images.

[Detailed description of the invention] The photosensitive material of the present invention is produced by preparing a coating solution containing a photosensitive microcapsule dispersion and then coating the coating solution on a support.

The method for preparing a photosensitive microcapsule dispersion is as follows: capsules containing silver halide particles around oily droplets (
The process consists of the steps of preparing an outer wall capsule around this inner wall capsule.

The steps will be explained below in order.

In a hydrophobic (oil-based) liquid (hereinafter referred to as
A 5-polyvalent isocyanate compound is dissolved in a photosensitive composition (photosensitive composition). This is dispersed into microdroplets in an aqueous liquid containing a polyol and/or polyamine to prepare a dispersion. However, this aqueous liquid contains a certain amount of styrene sulfonic acid polymer in advance, as will be described later.

Generally, the aqueous liquid mentioned above is an aqueous solution containing a certain amount of styrene sulfonic acid polymer, but when polyol and/or polyamine is used, It is desirable to have a catalyst present that promotes the polycondensation reaction between the compound and the polyamine and/or polyol.

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

In the present invention, the expressions "polyurea resin" and "polyurethane resin" do not necessarily mean a resin having only urea bonds and urethane bonds, respectively. For example, FI4 in which a part of the bonding group of the polyurethane resin is replaced with a urea bond is also included in the polyurethane resin,
The same applies to polyurea resin.

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

When silver halide grains, a reducing agent, and a polymerizable compound (described below) are introduced into a hydrophobic core liquid, the silver halide grains are usually mixed into an emulsion (halogenated A commonly used method is to produce a silver emulsion (silver emulsion) and then mix it with a hydrophobic solvent. Since the aqueous medium of the silver halide emulsion is transferred to the aqueous phase of the dispersion medium during the preparation of the emulsified dispersion for producing microcapsules, almost no water is present inside the cores of the resulting photosensitive microcapsules. Furthermore, as mentioned above, when the silver halide emulsion is transferred from the aqueous medium to the aqueous phase, the silver halide grains are accompanied by water from the core material phase (oil phase) to the dispersion medium phase (aqueous phase). Because of its tendency to migrate, silver halide tends to collect near the interface between the core material phase and the dispersion medium phase.

Therefore, when silver halide grains are introduced into the core material using a silver halide emulsion, the silver halide grains are present at a high concentration near the inner wall or inside the inner wall. It is preferable for the silver halide grains to be positioned as shown in letter L because exposure becomes easier and sensitivity is improved.

The silver halide grains may be introduced into the core material not as a silver halide emulsion as in 1: above, but as a dispersion in which silver halide grains are dispersed in an organic solvent. Alternatively, it is also possible to use a method in which silver halide particles obtained as powder are mixed with a polymerizable compound.

Examples of polyvalent isocyanate compounds, polyamines, and polyols used to form the outer shell of the microcapsules constituting the inner wall as described above are described below.

Examples of polyvalent isocyanate compounds include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-1-lylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, Isocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyldiphenylmethane-
4,4'-diisocyanate, xylylene-1°4-diisocyanate, xylylene-1,3-diisocyanate, 4,4'-diphenylpropane diisocyanate,
trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate,
Butylene-1゜2-diisocyanate, ethyridine diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1,4-diisocyanate, 4.4',4''-triphenylmethanetri isocyanate, toluene-2,4,6-) diisocyanate,
triisocyanates such as polymethylene polyphenylisocyanate, tetraisocyanates such as 4,4'-dimethyldiphenylmethane, 2,2',5°5'-tetraisocyanate, hexamethylene diisocyanate and hexanetriol; an adduct of 2.4-tolylene diisocyanate and brenz catechol,
Examples include polyisocyanate prepolymers such as adducts of tolylene diisocyanate and hexanetriol, adducts of tolylene diisocyanate and trimethylolpropane, and adducts of xylylene diisocyanate and trimethylolpropane. can.

Examples of polyamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine, m-phenylenediamine, piperazine, 2-
Methylbiperazine 52.5-dimethylpiperazine, 2-
Examples include hydroxytrimethylenediamine, diethylenetriamine, triethylenetetraamine, diethylaminopropylamine, tetraethylenepentamine, and amine adducts of epoxy compounds.

Examples of polyols include ethylene glycol, 1.4
-butanediol, catechol, resorcinol, hydroquinone, 1,2-dihydroxy-4-methylbenzene, 1,3-dihydroxy-5-methylbenzene, 3,
4-dihydroxy-1-methylbenzene, 3.5-dihydroxy-1-methylbenzene, 2,4-dihydroxyethylbenzene, 1.3-naphthalenediol, 1.5
-naphthalene diol, 2,7-naphthalene diol,
Examples include 2,3-naphthalene diol.

Next, melamine/formaldehyde or a prepolymer thereof is added to a dispersion containing microcapsules formed of the inner walls of the polyurea resin and/or polyurethane resin, and by adjusting the pH5 temperature, etc., the F2 inner wall External polymerization occurs around the molecule to form a capsule with an outer wall consisting of a melamine-aldehyde resin shell. The above dispersion contains a styrene sulfonic acid polymer in a typical amount of 30 to 65% based on melamine and formaldehyde or a prepolymer thereof, as described in Section 11.

As the above-mentioned styrene sulfonic acid-based polymer, polystyrene sulfonic acid and a copolymer containing styrene sulfonic acid as one component are preferred, and polystyrene sulfonic acid is more preferred.

The copolymer containing styrene sulfonic acid as one component is preferably a copolymer of styrene sulfonic acid and acrylic acid, maleic anhydride, ethylene, or an ethylene 1 derivative. Examples of stiff copolymers include acrylic acid-styrene sulfonic acid copolymers, maleic anhydride-
Styrene sulfonic acid copolymer, acrylic ester-styrene sulfonic acid copolymer, vinyl acetate-styrene sulfonic acid copolymer, vinylpyrrolidone-styrene sulfonic acid copolymer, styrene-styrene sulfonic acid copolymer,
and vinylsulfonic acid-styrenesulfonic acid copolymer.

The styrene sulfonic acid-based polymer may be a free acid, or some or all of the sulfonic acids in the molecule may form a salt. Typical salts include sodium salt, potassium salt, and ammonium salt.
Particularly preferred are sodium salts and potassium salts.

Molecules of the styrene sulfonic acid polymer used in the present invention! 11 is preferably in the range of 5,000 to 2,000,000, and more preferably in the range of 10,000 to 1,
Preferably it is in the range of 500,000. The most preferred range is 100,000 to 1,000,000
range.

In the present invention, it is preferable that the styrene sulfonic acid polymer is contained in an amount ranging from 40 to 60% by weight based on melamine and formaldehyde or a prepolymer thereof.

In addition, the above melamine and formaldehyde or their prepolymers have a concentration of 10 to 60 parts by weight with respect to the polymerizable compound.
Preferably, it is contained in an amount in the range of t%.

Note that methods for forming microcapsules by forming an outer shell made of melamine resin around a hydrophobic liquid dispersed in microdroplets in an aqueous medium include, for example, Japanese Patent Application Laid-open No. 55-15660; 55-47139 and 56-51238, U.S. Patent No. 4,100,
There are methods described in the specifications of No. 103 and No. 4,233,178. In addition, regarding the styrene sulfone m-based polymer described in 1.
It is described in Publication No. 1238.

The above-mentioned known methods can also be used in the method of the present invention.

As described above, microcapsules having a double layer outer shell having an outer wall made of amino aldehyde resin and an inner wall made of polyurea resin and/or polyurethane resin containing silver halide particles are formed. . The outer shell formed by the above method has a double layer outer shell as its basic structure, but this double layer does not necessarily have to have a clear boundary surface, and the outer shell does not necessarily have to have a clear boundary surface. It is sufficient that the outer shell surface and its vicinity are substantially formed of an amino aldehyde layer, while the inner surface of the outer shell and its vicinity are substantially formed of a polyurea resin and/or a polyurethane resin, or a mixture thereof. .

In the present invention, the fl quantity ratio of the inner wall and the outer wall is 1.
:20 to 10:1 is preferable.

When photosensitive microcapsules are manufactured by the method described in 2 above to form a double layer shell, the silver halide particles are more securely contained within the microcapsules without escaping into the aqueous phase. be done. Further, as the outer wall is formed, the outer wall supplements the denseness and toughness of the inner wall, so that the capsule as a whole is given even higher denseness and toughness.

In addition, as a method for forming the outer shell, for example, JP-A-56-1
The methods described in No. 02935 and No. 56-144739 can also be used.

The average particle size of the microcapsules obtained as described above is preferably in the range of 0.5 to 50 μm, more preferably in the range of 3 to 20 μm. The particle size distribution of microcapsules is disclosed in Japanese Patent Application Laid-open No. 63-53.
As in the photosensitive material described in Publication No. 34, it is preferable that the distribution is uniform over a certain value. Further, it is preferable that the film J'J of the microcapsules is within a certain value range with respect to the particle diameter, as in the photosensitive material described in JP-A-63-81336.

When silver halide is contained in microcapsules, the average particle size of silver halide grains is preferably one-fifth or less, and one-tenth or less of the microcapsule's It is even more preferable. By setting the average grain Y-size of the silver halide grains to one-fifth or more F of the average size of the microcapsules, a uniform and smooth image can be obtained.

The photosensitive material of the present invention can be produced by applying the dispersion of photosensitive microcapsules obtained by the method described above as a coating solution onto a support and drying. Optional components described below can be added to this coating liquid II. Moreover, a known method can be used as a coating method.

In the present invention, it is preferable that the dispersion of the polymerizable compound is coated on the support at a coating weight in the range of 1 to 203/rn'.

In the following margins, the silver halide, reducing agent, polymerizable compound, and support that constitute the light-sensitive material will be sequentially explained.

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

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having multiple structures with different compositions on the surface and inside, Japanese Patent Application Laid-open Nos. 57-154232 and 58-10853
No. 3, No. 59-48755, No. 59-52237, US Pat. No. 4,433,048 and European Patent No. 1
It is described in the specification of 00984. Also, JP-A-62
Silver halide grains having a high proportion of silver iodide in the shell portion, such as the photosensitive material described in Japanese Patent No. 183453, may also be used.

There is also 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 photosensitive 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 light-sensitive material, silver halide grains of type 1, which differ in halogen composition, crystal habit, grain size, etc., can also be used in combination.

There are no particular restrictions on the grain size distribution of silver halide grains. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used, as in the photosensitive material described in JP-A-62-210448.

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

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 1 mg in terms of silver, including silver salt, which is an optional component described below.
The range is preferably 0 g/rn'. In addition, when converting only silver halide into silver, it is preferably 1 g/rn' or less, and 1 mg to 500 mg/m
″ is particularly preferable.

A reducing agent that can be used in a light-sensitive material has a function of reducing silver halide and/or a function of promoting (or inhibiting) polymerization of a polymerizable compound. There are various types of reducing agents having the above functions. The reducing agents include hydroquinones, catechols, P-aminophenols, P-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-aminouracils, 4゜5-Dihydroxy-6-amitubirimidines, reductones, amyl reductones, 0- or p-sulfonamidophenols, 0- or p-sulfonamide naphthols, 2
-Sulfonamide indanones, 4-sulfonamide-
5-pyrazolones, 3-sulfonamide indoles,
Examples include 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, it is particularly preferable to use l-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.
Publications No. 1-228441 and JP-A-62-7
No. 0836 5 No. 62-86354, No. 62-8635
No. 5, Japanese Patent Application No. 60-227528, Japanese Patent Application No. 1987-1983
There are descriptions in publications such as No. 8849 and specifications (including those described as developers or hydrazine derivatives). In addition, in conjunction with the above-mentioned reducing agent, "The
The.

ry of the PhoLographic Pr
4th edition, pp. 291-334 (1977)
, Research Disclosure Magazine Vol. 1.170.
No. 17029 (pages 9-15) of June 1978, and QVo1.176 No. 17643 of December 1978
There is also a description in the issue (22-31 Sada). Also, JP-A-62
As in the photosensitive material described in Japanese Patent No. 210446, a reducing agent 1) "precursor" may be used instead of the reducing agent, which can release the reducing agent under heating conditions or in contact with a base. The reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literature can also be effectively used in the photosensitive materials in this specification.Therefore, the "reducing agent" in this specification includes - each of the above-mentioned publications, Included are reducing agents and reducing agent precursors as described in the specification and in the literature. These reducing agents may be used alone, or two or more types of reducing agents may be used in combination as described in each specification. When two or more types of reducing agents are used together, the interaction of the reducing agents is, firstly, to promote the reduction of silver halide (and/or organic silver salt) by so-called superadditivity. In this step, the oxidized form of the first reducing agent produced by the reduction of silver halide (and/or organic silver salt) undergoes an oxidative binary reaction with another reducing agent in which the polymerizable compound is combined. It is conceivable to cause this (or to suppress IR coupling). However, in actual use, reactions such as those described in F may occur simultaneously, so it is difficult to specify which effect is occurring.

Examples of the 14 reducing agents shown in - include pentadecylhydroquinone, 5-t-butylcatechol, p-(N,N-
diethylamino)phenol, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-virazolidone, 2-phenylsulfonylamine-4-hexa Decyloxy-5-t-octylphenol, 2-phenylsulfonylamino-4t-butyl-5-hexadecyloxyphenol, 2-(N-butylcarbamoyl)-4-phenylsulfonylaminonaphthol, 2-(N-methyl-N -octadecylcarbamoyl)-4-sulfonylaminonaphthol, 1-acetyl-2-phenylhydrazine, 1-acetyl-2-(
(p or 0)-aminophenyl)hydrazine, 1-formyl-2-((ρ or 0)-aminophenyl)hydrazine, 1-acetyl-2-((p or 0)-methoxyphenyl) and drazine, 1- Lauroyl-2-((ρ
or. ) ~aminophenyl) hydrazine, 1-1 lythyl-2- (2,6-dichloro-4-cyanophenyl)
hydrazine, 1-trityl-2-phenylhydrazine,
1-phenyl-2-(2,4,6-dolichlorophenyl) and drazine, 1-(2-(2,5-di-t-pentylphenoxy)butyroyl)-2-((p or O)-
Aminophenyl hydrazine, 1- (2-(2,5-
di-t-pentylphenoxy)butyroyl)-2-((
p or 0)-aminophenyl)hydrazine pentadecylfluorocaprylate, 3-indazolinone, 1-
(3,5-dichlorobenzoyl)-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, i-(methoxycarbonylbenzohydryl)-2-phenylhydrazine, 1
-Formyl-2-[4-(2-(2,4-di-t-pentylphenoxy)butyramido)phenyl]hydrazine, 1-acetyl-2-(4-(2-(2,4-di-7-
Bentylphenoxy)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-Trityl-2-[(2-(N-ethyl-N-octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, 1-benzoyl-2-tritylhydrazine, 1-(4-butoxybenzoyl)- 2-1 Lythylhydrazine, 1-(2,4-dime[·xybenzoyl)-
2-tritylhydrazine, 1-(4-dibutylcarbamoylbenzoyl)-21lythylhydrazine, and 1-
(1-naphthoyl)-2-tritylhydrazine and the like can be mentioned.

In the light-sensitive material, the reducing agent is preferably used in an amount of 0.1 to 1500 mol % based on 1 mol of silver (including the above-mentioned silver halide and optional organic 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-developing is used as a method of using photosensitive materials, materials with a high boiling point (for example, a boiling point of 8
It is preferable to use compounds with a temperature of 0° C. or higher. Furthermore, in the embodiment in which the photosensitive layer contains a color image forming substance as an optional component described later, the color image forming substance is immobilized by polymerization and curing of the polymerizable compound, so the polymerizable compound has a plurality of molecules in the molecule. frr, a crosslinkable compound having a merging functional group is preferable. In addition, as will be described later, when forming a transferred image using an image-receiving material,
It is preferable to use a highly viscous substance as the polymerizable compound, as in the photosensitive material described in No. 150079.

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

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

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

Specific examples of polymerizable compounds that can be used in photosensitive materials include rope tyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, hensyl acrylate, furfuryl acrylate, and cyclohexyl acrylate. xyethoxyethyl acrylate, dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate,
Neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyoxyethylated bisphenol A diacrylate, 2,2-dimethyl-3-hydroxypropion Examples include diacrylates of aldehyde and trimethylolpropane condensates, triacrylates of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol condensates, hydroxyboether polyacrylates, polyester acrylates, and polyurethane acrylates.

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

The above polymerizable compounds may be used alone or in combination of two or more. A photosensitive material using a combination of two or more types of polymerizable compounds is described in JP-A-62-210445. Note that a substance in which a polymerizable functional group such as a vinyl group or a vinylidene group is introduced into the chemical structure of a color image forming substance, which is the reducing agent mentioned in IFf or an arbitrary component mentioned later, can also be used as the polymerizable compound. Of course, the use of a reducing agent and a polymerizable compound, or a substance that functions as a color image-forming substance and a polymerizable compound, as in Section F, is also included in the embodiment of the photosensitive material.

In the light-sensitive material, the polymerizable compound is preferably used in an amount of 50,000 to 120,000 parts by weight per 1 part by weight of silver halide. A more preferable usage range is 12 to 1120
It is a 00 weight lit part.

A photosensitive material is formed by providing a photosensitive layer containing the above-mentioned components 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. 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, cellulose acetate, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene. Examples include films such as terephthalate, and papers laminated with resin materials and polymers 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. Preferably young. 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 with excellent Bekk smoothness, 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-63-83340, 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.

1-1 Below, various aspects of the photosensitive material, twenty components that can be included in the photosensitive layer, auxiliary layers that can be optionally provided in the photosensitive material, etc. will be sequentially explained.

Optional components that can be included in the photosensitive layer of the photosensitive material include color image forming substances, sensitizing dyes, organic silver salts, radical generators, various image formation accelerators, thermal polymerization inhibitors, thermal tr
L-polymerization agent initiator image stopper, fluorescent whitening agent, anti-fading agent,
Dyes or pigments for preventing halation or irradiation, pigments that inhibit the property of decolorizing when heated or exposed to light, matting agents, anti-smudge agents, abrasive agents, water release agents, binders, photopolymerization initiators, and polymerizable compounds. Examples include solvents and water-soluble vinyl polymers.

Although a polymer 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 (color developers). 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 Japanese Patent Application Laid-open No. 73145/1983, which was mentioned earlier. 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, can be found in reprints as well as in various literature (for example, "Dye Handbook," edited by the Organic Synthetic Chemistry Association, published in 1972, [Latest Pigment Handbook J Ef
The known ones described in 1972, edited by the Pigment Technology Association, can be used. These dyes or pigments are used after being dissolved or dispersed.

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

Examples of substances that develop color upon contact with another component include various systems that develop color due to acid-base reactions, redox reactions, coupling reactions, chelate formation reactions, etc. between two or more components. For example, pressure-sensitive copying paper (pp. 29-58) and azography (p.
95 pages), known coloring systems such as heat-sensitive coloring by chemical changes (pages 118-120), or the latest dye chemistry - Attractive uses and new developments as functional dyes - 1, a seminar sponsored by the Kinki Chemical T Industry Association. Proceedings pages 26-32, (198
The coloring system described in June 0, 190) can be used.

I-1 Physically, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, spiropyran, etc. used in pressure-sensitive paper, and an acidic substance (color developer) such as acid clay or phenols; aromatic diazonium salts and diazotates,
Systems using azo coupling reactions of diazosulfonates, naphthols, anilines, activated methylenes, etc.; reactions of hexamethylenetetramine with ferric ions and gallic acid, and reactions of phenolphthalein-combrecranes with alkaline earths. Chelate-forming reactions such as reactions with similar metal ions; redox reactions such as reactions between ferric stearate and pyrogallol and reactions between silver behenate and 4-methoxy-1-naphthol can be used.

The color image-forming substance is preferably used in an amount of 0.5 to 20 parts by weight, more preferably 2 to 7 parts by weight, per 100 parts by weight of the compound. In addition, if 5 color developer is used, color former 1ffcf
It is preferably used in a ratio of about 0.3 to 80 parts by weight per 1 part of i.

In addition, when using two types of substances that cause a color-forming reaction when in contact as the color image-forming substances mentioned below, one of the substances that cause a color-forming reaction and a polymerizable compound are placed in microcapsules. A color image can be formed on the photosensitive layer by allowing other substances among the substances contained in the microcapsules and causing the above-mentioned 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.

Sensitizing dyes that can be used in photosensitive materials are especially -1
There is no limitation, 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. Kowara's sensitizing dyes may be used in East Germany, or they may be used in combination. In particular, when supersensitization is targeted, a method of using a combination of sensitizing dyes is common. 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. The amount of the sensitizing dye added is generally about 10-8 to 10-2 mol per 5 mol of halogenide.

The above-mentioned sensitizing dye is preferably added at the stage of preparing a silver halide emulsion, which will be described later. Regarding a light-sensitive material in which a sensitizing dye is added at the stage of forming silver halide grains, JP-A-62-947 describes a method in which a sensitizing dye is added to silver halide grains after the formation of silver halide grains. For light-sensitive materials obtained by adding in the emulsion preparation stage,
Each is described in JP-A-62-210449. Further, specific examples of sensitizing dyes that can be used in light-sensitive materials are also described in 5F JP-A-62-947 and JP-A-62-210449. Also,
As in the photosensitive material described in Japanese Patent Application No. 61-208786 δ, a sensitizing dye sensitive to infrared light may be used in combination.

Addition of milling silver salt to photosensitive materials is particularly effective in heat development processing. That is, when heated to a temperature of 80° C. or higher, the organic silver salt is considered to participate in an oxidation-reduction reaction using the latent image of silver halide as a catalyst. In this case, the silver halide and the organic silver salt are preferably in contact or in close proximity. Examples of the organic compound constituting the -F organic silver salt include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Among them, benzotriazole is particularly preferred. ”-The organic silver salt is generally 0.01 to 10 mol, preferably 0.01 to 10 mol per mol of silver halide.
．． Ol to 1 mol is used. Incidentally, the same effect can be obtained by adding a constituent compound (for example, benzotriazole) to the photosensitive layer instead of the 'tT11 silver salt.

For photosensitive materials using organic silver salts, see JP-A-62-32.
There is a description in Publication No. 46. The organic silver salt as described below is preferably used in an amount of 0.1 to 10 mol, more preferably 0.01 to 1 mol, per mol of silver halide.

A radical generator that participates in the polymerization promotion (or polymerization inhibition) reaction of the reducing agent mentioned above 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.
2-195640 and JP-A-62-195641 describes a photosensitive material using an azo compound.

Five different 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 organic silver salt) and a reducing agent, and those that promote the redox reaction between silver halides (and/or organic silver salts) and reducing agents, and those that promote the redox reaction between silver halides (and/or organic silver salts) and reducing agents, and those that promote the redox reaction between silver halides (and/or organic silver salts) and reducing agents, and those that promote the redox reaction between silver halides (and/or organic silver salts) and reducing agents. It has functions such as promoting the movement of image forming substances.

From the viewpoint of physicochemical functions, image formation accelerators include bases,
They are further classified into base precursors, oils, surfactants, compounds with antifogging and/or development accelerating functions, thermal solvents, compounds with oxygen removal functions, 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;
Ammonium hydroxide; hydroxide of quaternary alkylammonium; hydroxide of other metals, etc. Examples of organic bases include aliphatic amines (trialkylamines,
hydroxyl-cyamines, aliphatic polyamines); aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis[p
-(dialkylamino)phenyl]methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, etc., and those in which a is 7 or more are particularly preferred.

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

The base or base precursor can be used in the photosensitive material in a wide range of amounts. The base or base precursor weighs 100 times the coating film of the photosensitive layer in terms of ff11! jt
% or less, more preferably o,
Il! 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. Further, regarding a photosensitive material using a tertiary amine as a base, see JP-A-62-170954, and regarding a photosensitive material using a fine particle dispersion of a hydrophobic 41 base compound with a melting point of 80 to 180°C. is Japanese Patent Publication No. 1983-2095
No. 23 describes a photosensitive material using a guanidine derivative with a solubility of 0.1% or less in JP-A No. 62-21563.
Specification No. 7-I describes photosensitive materials using hydroxides or salts of alkali or alkaline earth metals, respectively, in Japanese Patent Application No. 1983-96341.

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.
Further, regarding photosensitive materials containing silver, copper, silver compounds, or copper compounds as catalysts for base generation reactions, JP-A-63-4
6446'+ Publication, JP-A No. 63-81338 for photosensitive materials containing -■-2 propiol salts and silver, copper, silver compounds, or copper compounds separated from each other; For photosensitive materials containing acid salts, silver, copper, silver compounds, or copper compounds as well as ligands in the free state, see JP-A-63-97942, using propiolic acid salts as base precursors, Further, regarding a photosensitive material containing a heat-melting compound as a reaction accelerator for a base production reaction, JP-A No. 63-46447 describes using a sulfonylacetate as a base precursor.
Further, JP-A-63-48543 describes a photosensitive material containing a heat-melting compound as a reaction accelerator for a base production reaction, and a photosensitive material using a compound in which an isocyanate or isothiocyanate is bonded to an organic base as a base precursor. are described in Japanese Unexamined Patent Publication No. 63-24242.

When using a base or base precursor in a photosensitive material,
It is preferable that the silver halide, transition agent, and polymerizable compound be contained in the microcapsules described above, and that a base or a base precursor be 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 photosensitive materials using microcapsules containing bases or base precursors, there is also a photosensitive material containing microcapsules containing bases or base precursors dissolved or dispersed in an aqueous water-retaining agent solution, as described in JP-A-62. Japanese Patent Application Laid-open No. 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 the photosensitive material used, see Japanese Patent Application Laid-Open No. 1986-
These are described in Japanese Patent No. 65437. Furthermore, instead of the microcapsules containing a base or base precursor, particles containing a base or a base precursor and a hydrophobic substance in a compatible state may be used, as in the photosensitive material described in JP-A-63-97943. .

The base or base precursor is described in Japanese Patent Application Laid-Open No. 62-2
As described in Japanese Patent No. 53140, 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-63-32
As described in Japanese Patent No. 546, the above-mentioned support may be made porous and a base or 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 pharydinium salts, ammonium salts, and phosphonium salts described 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 thioether compounds, see JP-A-61-151841, and JP-A-62-151841.
No. 151842 discloses a photosensitive material using a 5-polyethylene glycol conductor in Japanese Patent Application Laid-Open No. 151843/1983.
For photosensitive materials using thiol conductors, see JP-A No. 62-151844, and for photosensitive materials using acetylene compounds, see JP-A No. 62-17823.
For photosensitive materials using sulfonamide derivatives, see JP-A-62-183450, and for photosensitive materials using quaternary ammonium salts, see JP-A No. 63-9.
Publication No. 1653 has a description of each.

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 US Pat. No. 3,347,675, derivatives such as oleic acid esters of polyethylene oxide, beeswax, monostearin, -50
High dielectric constant compound with 2- and/or -C〇- group, US Pat. No. 3,667,959, Polar Materials, Research Disclosure Magazine, 1976, 12JI
1,10-decanediol, methyl anisate, biphenyl perate, etc. described on pages 26 to 28 of the issue 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 the shadow 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. A photosensitive material using a compound having 2 or more -F mercapto groups is described in JP-A-62-209443.

A thermal polymerization initiator is a compound that is generally thermally decomposed under heating to generate polymerization initiating species (particularly radicals), and is usually used as an initiator for radical polymerization. Thermal polymerization initiators are described in pages 6 to 18 of "Addition Polymerization/Ring Opening Polymerization J, 1983, Kyoritsu Shuppan," edited by the Editorial Committee of Polymer Experiments, The Polymer Society of Japan.Thermal polymerization initiators teeth,
It is preferably used in a range of 0.1 to 120% by weight, and more preferably in a range of 1 to 10% by weight, based on the polymerizable compound. In addition, in a system in which a polymerizable compound is polymerized in a portion where a silver halide latent image is not formed, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Furthermore, a photosensitive material using a thermal polymerization initiator is described in JP-A-62-70836.

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 immediately after proper development, or a compound that interacts with silver and silver salts. It is a compound that inhibits development. Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with coexisting salts when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include JP-A-60
Oxime esters described in No.-108837 and No. 60-192939, JP-A-60-230133
Examples include compounds that release an acid through Rossen rearrangement as described in the above publication.

Examples of pA electronic compounds that undergo a substitution reaction with a base upon heating include compounds described in JP-A-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.

Heat or light inside the microcapsule! ! A dye that exhibits the property of being decolored by a single irradiation may be included. The dye having the property of being decolored by heating or light irradiation can function as a complement to a yellow filter in a conventional silver salt photographic system. A photosensitive material using a dye having the property of being decolored by heating or light irradiation as described above is described in JP-A-63-97940.

As an anti-smudge agent used in photosensitive materials, it is recommended to use (6
A single particulate material is preferred. Specific examples include starch particles described in British Patent No. 1,232,347, polymer fine powders described in US Pat. No. 3,625,736, etc.
Microcapsules Fl-1 containing no coloring agent as described in British Patent No. 1235991 Specification 8 etc. US Patent No. 27113
Inorganic particles such as cellulose fine powder, talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina described in No. 75 can be mentioned. -I-
The average particle size of the particle distribution is preferably in the range of 3 to 50 μm in volume average diameter, more preferably in the range of 5 to 40 μm. As mentioned above, when the oil droplets of the polymerizable compound are in the form of microcapsules, it is more effective if the particles are larger than the microcapsules.

Binders that can be used in the photosensitive material can be included in the photosensitive layer either alone or in combination.

It is preferable to use a hydrophilic binder as the binder. Typical examples of the aqueous binder are transparent or translucent hydrophilic binders, such as gelatin, derivatives, cellulose derivatives, 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 substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others. Incidentally, a photosensitive material using a binder is described in JP-A-61-69062. Furthermore, a photosensitive material using a binder together with microcapsules is described in JP-A-62-209525.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material for the purpose of polymerizing unpolymerized polymerizable compounds after one image is transferred. 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 R solvents that are miscible with polymerizable compounds encapsulated in microcapsules, Japanese Patent Laid-Open No. 62-2095
There is a description in Publication No. 24.

A water-soluble vinyl polymer may be adsorbed onto multi-layered silver halide grains. ” Regarding photosensitive materials using water-soluble vinyl polymers like Nisho, Japanese Patent Application Laid-Open No. 63-916
There is a description in Publication No. 52.

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 Application Specification 1! regarding the series of photosensitive materials mentioned above. F, and Research Disclosure Vol.

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

It is preferable that the photosensitive layer of the photosensitive material made of the above-mentioned components has a pH value of 7 or less, as in the photosensitive material described in JP-A No. 62-275235.

Layers that can be optionally provided on the photosensitive material include image receiving layer 1 heating layer, antistatic layer, anticurl layer, peeling layer,
Cover sheet or protective layer, base or base precursor-containing layer, base barrier layer, antihalation layer (R
color layer), etc.

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

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. 62-253147. A photosensitive material provided with an n-color layer as an antihalation layer is described in Japanese Patent Application Laid-open No. 101842/1983. In addition, a base barrier layer was provided:
The 8-light material is also described in the above-mentioned Japanese Patent Application Laid-Open No. 62-253140. Furthermore, examples of other auxiliary layers and their usage are also described in the application specification ilΣ related to the above-mentioned series of photosensitive materials.

DETAILED DESCRIPTION The photosensitive material of the present invention is produced by applying a dispersion containing photosensitive microcapsules to a support by RP coating as described above.

Below, method A for producing a silver halide emulsion introduced into a 111 sq. fr concatenation compound will be explained in detail.

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

The reaction format of i) soluble silver salt and i (soluble halide salt) may be one-sided mixing method, simultaneous mixing method, or a combination thereof. Particles are formed under conditions in which silver ions are excessive.
A four-way back mixing method and a Chondral double jet method in which PAg is kept constant can also be employed. Furthermore, in order to accelerate grain growth, the concentration, addition rate or addition rate of silver salts and halogen salts may be increased (JP-A-55-158124, JP-A-55-158124 specification and US Pat. No. 3,650,757). (see specification).

Silver halide emulsions are used in the production of photosensitive materials.

It may be a surface latent image type where the latent image is mainly formed on the particle surface, or an internal latent image type where the latent image is formed inside the particle. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used. Internal latent image emulsions for this purpose are disclosed in U.S. Pat.
No. 6 Specifications Special Publication No. 5B-3534, Japanese Patent Publication No. 5
No. 8-136641 and other publications. A preferred nucleating agent for combination with the above emulsion is U.S. Pat.
No. 7552, No. 4245037, No. 425551
No. 1, No. 4266013, No. 4276364, and OLS No. 2635316 for external use 1! J himself is listed in B i', F.

In the preparation of silver halide emulsions used in the production of light-sensitive materials, it is preferable to use hydrophilic colloids as protective colloids. Examples of hydrophilic colloids include gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose conductors such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc. , sodium alginate, sugar derivatives such as starch derivatives; and 9- or copolymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. A wide variety of synthetic hydrophilic polymer-materials such as conjugates can be mentioned. Among these, gelatin is preferred. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

Silver halide 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. 144319-1982) as silver halide solvents in the stage of forming silver halide grains. )
etc. can be used. Further, in the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be allowed to coexist. Furthermore, LI-like iridium chloride (■ or ■) improves high-light failure and low-light failure.
, a water-soluble iridium salt such as ammonium hexachloroiridium salt, or a water-soluble rhodium salt such as rhodium chloride can be used.

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 Zudel water washing method or the sedimentation method. Is silver halide emulsion still available? &'U may be used as is, but it is usually used after chemical sensitization. Ordinarily, in the case of emulsions for sensitizing materials, well-known sulfur sensitization methods, reduction sensitization methods, blue metal sensitization methods, etc. can be used or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (see JP-A-58-126526 and JP-A-5B-215644).

In addition, when adding a sensitizing dye to a silver halide emulsion,
1 The above-mentioned Japanese Patent Application Laid-Open No. 62-947 and Japanese Patent Application No. 1983
It is preferable to add it at the stage of preparing a silver halide emulsion as in the light-sensitive material described in Japanese Patent No. 55510.

In addition, when a nitrogen-containing heterocyclic compound is added as a compound that achieves the above-mentioned antifogging function and/or development acceleration function, it may be added at the stage of silver halide grain formation or in the preparation of a silver halide emulsion. It is preferable to add it at the ripening stage. A method for producing a photosensitive material in which a nitrogen-containing m-ring compound is added at the stage of forming silver halide grains or at the stage of ripening is disclosed in JP-A-62-16.
No. 1144 is mentioned in the violation.

When the above-described 4i'' silver salt is included in the photosensitive layer, an organic silver salt emulsion can be prepared by a method similar to the method for preparing the silver halide emulsion described above.

1) The compound can be used as a medium in preparing the composition of other components in the photosensitive layer.

For example, as described in ``?η, silver halide (including silver halide emulsion), reducing agent, one-color image forming substance, etc. are dissolved, emulsified, or dispersed in a polymerizable compound (as a photosensitive composition). ) Can be used in the production of photosensitive materials.

In particular, when adding a color image-forming substance, it is preferable to add the fTj-synthesizing compound.

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 described in -1. A photosensitive composition containing stiff silver halide can be obtained by stirring with a homogenizer blender, mixer, or other commonly used stirrer.

In addition, it is often preferable that a cobosomer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit at the m position is dissolved in the polymerizable compound used for preparing the photosensitive composition. Regarding photosensitive compositions containing the above copolymers, JP-A-62
There is a description in Publication No.-209449.

Further, 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 having a silver halide emulsion as a core material is described in JP-A-62-164041.

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

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

Although various exposure means can be used as the two-leg exposure method, a latent image of silver halide is generally obtained by imagewise exposure to radiation including visible light. Type of light source and exposure 1
can be selected depending on the sensitivity wavelength of silver halide (in the case of dye sensitization, the sensitized wavelength) and sensitivity. Further, the original image may be a black and white image or a hexagonal color image.

The photosensitive material is developed at the same time as or after the imagewise exposure described in F. The photosensitive material was published under the Special Publication Act in 1977-111.
Development processing using a developer described in Japanese Patent No. 49 or the like may be performed. As mentioned above, the method described in JP-A No. 61-69062 that performs heat development treatment is a dry treatment, so it has the advantage of being simple to operate and capable of processing in a short time. . Therefore, the latter method is particularly excellent for developing photosensitive materials.

As the heating method in the above heat development treatment, various conventionally known methods can be used. In addition, like the photosensitive material described in JP-A No. 61-294434,
A heat generating layer may be provided on the photosensitive material and used as one stage of heating. Further, as in the image forming method described in JP-A-62-210461, the amount of oxygen present in the photosensitive layer is suppressed.

A heat development process may also be carried out at the same time. The heating temperature is generally 8
The temperature is 0°C to 200°C, preferably 100°C to 160°C. The heating time is generally 1 second to 1 minute, preferably 1 second to 5 minutes, and preferably 1 second to 1 minute.

Incidentally, instead of including the above-described base or base precursor in the photosensitive material, the development process may be carried out while or immediately after adding the base or base precursor to the photosensitive layer. As a method for adding a base or a base precursor, a sheet containing a base or a base precursor (
The method using a base sheet) is the easiest and preferred.

An image forming method using the above base sheet is described in JP-A-63-32546.

The photosensitive material is thermally developed as described above, and the polymerizable compound in the area where the silver halide d) image is formed or the area where the latent image of silver halide is not formed is subjected to;R polymerization. can. In light-sensitive materials, the polymerizable compound in the portion where the silver halide latent image is formed generally undergoes ilj polymerization during the heat development process, but in the light-sensitive material described in JP-A-62-70836 mentioned above, like,
By adjusting the type, amount, etc. of the reducing agent, it is also possible to polymerize the polymerizable compound in areas where no latent image of silver halide is formed.

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

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

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

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

As a support for the image-receiving material, baryta paper can be used in addition to the supports that can be used for the photosensitive materials described above. In addition, when using a porous material such as paper as a support for the image-receiving material, Japanese Patent Application Laid-Open No. 62-209530
It is preferable that the image-receiving material has a certain level of smoothness like the image-receiving material described in the above publication. 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 provided on a support.

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

For example, when using a coloring system consisting of a color former and a color developer, the image receiving layer can contain the color developer. Furthermore, the image-receiving layer can also be configured as a layer containing at least one mordant. The mordant can be selected from compounds known in the photographic technology, taking into consideration conditions such as the type of color image forming substance, and used. Note that, if necessary, the image-receiving layer of the two-layer structure may be constructed using a plurality of mordants having different mordant powers.

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

The image-receiving layer may contain a thermoplastic compound. When the image-receiving layer contains a thermo+1TM compound, it is preferable that the image-receiving layer itself is constituted as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above structure has the advantage that it is easy to form a transferred image, and a glossy image can be obtained by heating after image formation. The above thermoplastic compound is not particularly limited and can be arbitrarily selected from known plastic resins (plastics), waxes, and the like. However, the glass transition point after the thermoplastic phase and the melting point of the wax are preferably 200°C or higher. Regarding the image-receiving material having an image-receiving layer containing thermoplastic compound fine particles as described above,
There are descriptions in No. 280071 and No. 62-280739.

The image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In image formation using an image receiving material,
The color image forming material is transferred together with the unpolymerized polymerizable compound as described below. For this reason, it is important to ensure that the curing process (fixing process) of the unpolymerized polymerizable compound progresses smoothly.
A photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer. For an image-receiving material having an image-receiving layer containing a photopolymerization initiator, see JP-A-62-161149, and for an image-receiving material having an image-receiving layer containing an intermediate initiator, JP-A-62-210444. There are descriptions for each.

The image-receiving layer may be configured as two or more 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 further 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.

The photosensitive material is developed as described above, and the unpolymerized polymerizable compound is transferred to the image-receiving material by applying pressure while the image-receiving materials are pressed together, thereby forming a polymer image on the image-receiving material. Various conventionally known methods can be used as the pressurizing means.

Further, in an embodiment in which the photosensitive layer contains a color image forming substance,
By carrying out a similar development process, the compound 1 is polymerized and cured, thereby immobilizing the color image forming substance in the cured portion. By applying pressure, the uncured portions of the color image-forming material are transferred to the image-receiving material, forming a single color image on the image-receiving material.
ii.

Incidentally, in the method described in 1-, in which an image is formed on the image-receiving material as described above, the image-receiving abrasive may be heated as in the image-forming method described in JP-A No. 62-210459. There is also the advantage that the unpolymerized TiTi-forming compound transferred to the material 1- is synthesized and the retention properties of the resulting image are improved.

Furthermore, patent applications have already been filed for various image recording 3J apparatuses suitable for carrying out the above-described series of image forming methods using photosensitive materials (Japanese Patent Laid-Open Publication No. 147461/1982).

Photosensitive materials include black and white or color photography and printing photosensitive materials, printing photosensitive materials, printing plates, X-ray photosensitive materials, [K medical photosensitive materials (e.g. ultra-f wave diagnostic CRT photosensitive materials), and computer graphics. It has many uses such as hard copy photosensitive materials and H8 materials for copying machines.

Remainder 1 The present invention will be explained in more detail with reference to Examples below. However, the present invention is not limited to these.

[Example 1] "Preparation of photosensitive material" Preparation of halogen (A-1) Add 16 g of gelatin and 0.5 g of sodium chloride to an acidic gelatin aqueous solution (1500 n+fl of water, and adjust to pH 3 with IN sulfuric acid.
2, 300 mff1 of an aqueous solution containing 71 g of potassium bromide and a silver nitrate aqueous solution (0159 mol of silver nitrate dissolved in 300 mff1 of water) were simultaneously heated isothermally for 50 minutes. cm added. One minute after this addition is completed, the following sensitizing dye (
Add 43 ml of 1% methanol solution of 1), and then add 100 ml of aqueous I/I containing 2.9 g of potassium iodide and 100 ml of silver nitrate aqueous solution (100 ml of water) 15 minutes after adding the sensitizing dye.
mj2 with 0.018 mol of silver nitrate dissolved in 5
Added at equal flow rates over a period of minutes. To this emulsion, 10 cc of a 10% alkaline aqueous solution of isobutylene maleic anhydride copolymer was added to precipitate the emulsion. After settling, washing with water and desalting, 12 g of gelatin was added and dissolved, and 0.5 mg of sodium thiosulfate was added to the emulsion. In addition, chemical sensitization was carried out at 60 DEG C. for 15 minutes to prepare 1000 g of a monodispersed 14-hedral silver iodobromide emulsion (A-1) having an average grain size of 0.22 .mu.m.

Sensitized color! (1) Aqueous gelatin solution (20 g of gelatin in 1600 mj2 of water)
and 0.5 g of sodium chloride, adjusted to pH 3.2 with IN sulfuric acid, and kept at 42°C), 200 mQ of an aqueous solution containing 71 g of potassium bromide and a silver nitrate aqueous solution (5Fi0. 59 mol dissolved) were simultaneously added isothermally at 11 over a period of 30 minutes. One minute after this addition was completed, 48 ml of a 1% methanol solution of the following sensitizing dye (2) was added, and from 10 minutes after addition of the sensitizing dye, 100 mfi of an aqueous solution containing 2.9 g of potassium iodide and silver nitrate were added. An aqueous solution (0.018 mol of silver nitrate dissolved in 100 ml of water) was added at reflux over a period of 5 minutes. To this emulsion, add 10 c of a 10% alkaline aqueous solution of isobutylene maleic anhydride copolymer.
After adding c and sedimentation, washing with water and desalting, gelatin 18
Add and dissolve 0.1 mg of thorium thiosulfate.
was added and chemically sensitized at 60°C for 15 minutes to obtain a monodispersed 14-hedral silver iodobromide emulsion with an average grain size of 0.12 μm (
A-2) 1000g was manufactured by:A.

Sensitized color A (2) Halogen A-3 gelatin aqueous solution (20 g gelatin in 1600 mfl water)
Add 0.5 g of sodium chloride and adjust the pH to 3 with IN sulfuric acid.
, 5 and kept at 45℃), and 71g of potassium bromide. 200 mff1 of an aqueous solution containing silver and a silver nitrate aqueous solution (0.59 mol of silver nitrate dissolved in 200 mj2 of water) were added simultaneously over a period of 30 minutes using a meteor shower. After this addition, from 1 bone contact, the sensitizing dye (3)
) was added, and 15 minutes after addition of the sensitizing dye, 100 mfi of an aqueous solution containing 3.65 g of potassium iodide and a silver nitrate aqueous solution (1.00 mf of water) were added.
0.022 g of silver nitrate dissolved in 1 ml) was added evenly over a period of 5 minutes.

To this emulsion, 10 cc of a 10% alkaline aqueous solution of isobutylene maleic anhydride co-[n] was added, sedimented, washed with water, and desalted, and then 10 g of gelatin was added and dissolved.
Add 0.45 mg of sodium thiosulfate to the grains and chemically sensitize at 55°C for 20 minutes to obtain an average particle size of 0.137.
1m monodispersed tetradecahedral material (chemical treatment (A-1) 1000
g was prepared.

Sensitizing dye (3) Add 1.0 g of the above halogenated 2141L agent (A-1) to a 10% aqueous solution of potassium bromide! , 5 ml was added to obtain an aqueous liquid. Next, an aqueous liquid was added to the oily liquid described in 1 to 1 and stirred for 5 minutes at 15,000 revolutions per minute using a homogenizer to obtain a photosensitive composition (A-1) in the form of a W10 emulsion.

(1 [Synthesizing compound) 1 [Synthesizing compound (product name: Kayarat R604
, to 100 g of [unified condiment J), copolymer 1 of Doki,
2g and 15g of the yellow imaging material described below were dissolved. Add the following development accelerator (i) to 90 g of this soluble fi.
(Product name: Nirasan Nonion N5208.5.fE1 made by Ibon Oil & Fat ■) 8g was dissolved. Furthermore, 0.01 g of the following development accelerator (2) and the following reducing agent (1
), and a solution of 6.45 g of Yugen agent (II) below dissolved in 20 g of methylene chloride, and the oily liquid was added. ! Made by l.

(copolymer) (yellow image forming substance) (Reducing agent (■)) (Development accelerator (2)) [;, I+.

In place of the silver halide emulsion (A-1,) used in the preparation of the photosensitive composition (A-1,) of A-2, silver halide emulsion (A-2) of No. 071 was used in the same size and yellow. Photosensitive composition (A-1) was prepared in the same manner as photosensitive composition (A-1), except that 20 g of the following magenta image forming substance and 0.015 g of development accelerator (2) described in +iff were used instead of the image forming substance. Composition (A-2) was prepared.

Requirement 11 (Reducing agent (■)) (Magenta image forming substance) (Cyan image forming substance) In place of the silver halide emulsion (A-1) used in the preparation of the photosensitive composition (A-1) described in F. Except that the same amount of the silver halide emulsion (A-3) described in No. 111f, 16 g of the following cyan image-forming substance in place of the yellow image-forming substance, and 0.0075 g of the development accelerator described in Koki were used.
Photosensitive composition (A-1) was prepared in the same manner as photosensitive composition (A-1).
-3) was prepared.

The above photosensitive composition (A-1) was added with a polyvalent isocyanate compound (trade name: Takenate DIIN, Takenate DIIN,
4.5 g (manufactured by Kogyo) were added and mixed well. This mixed solution was mixed with a portion of the sodium salt of polyvinylbenzenesulfonic acid (trade name: Parsa Tl2O3, manufactured by National Starch Co., Ltd.).
Solution 10 in which a 5% aqueous solution of was adjusted to pH 6.0 using a 20% aqueous solution of phosphoric acid or a 10% aqueous solution of sodium hydroxide.
4 g and stirred for 30 minutes at 9,000 rpm using a homogenizer at 40° C. to obtain a W10/W emulsion.

Separately, 51.8 g of melamine, 85.5 g of a 37% formaldehyde aqueous solution, and 279 g of water were heated to 60°C and stirred.
After 0 minutes, a transparent melamine/formaldehyde initial condensate was obtained.

60 g of the bipedal initial condensate was added and mixed to the above W10/W emulsion, and the pH was adjusted to 6.0 using a 20% aqueous phosphoric acid solution while stirring. Next, the liquid temperature was raised to 60° C. and stirring was continued for 90 minutes to prepare a photosensitive microcapsule dispersion (A) having an outer shell made of a polyurea resin-melamine formaldehyde resin wall.

Furthermore, in order to remove formaldehyde remaining in the capsule dispersion, 27 g of a 40% urea aqueous solution was added, the pH was adjusted to 3.5 using a 20% phosphoric acid aqueous solution, and stirring was continued for 40 minutes. After the reaction is complete, add 10% sodium hydroxide.
The capsule liquid was adjusted to pH 6.5 using an aqueous solution and cooled. The average particle size of the obtained microcapsules was 8μ
It was m. In the above capsule preparation process, use of some sodium salt of polyvinylbenzenesulfonic acid 1x
t is 43% compared to 14 for melamine/formaldehyde
Met.

In the preparation of the photosensitive microcapsule dispersion (A-1) described in F, the same procedure was followed except that the photosensitive composition (A-2) was used instead of the photosensitive composition (A-1) described in F. A photosensitive microcapsule dispersion (A-2) was prepared. The average particle diameter of the obtained microcapsules was 8 μm.

-1m, iL! Photosensitive microcapsule dispersion M (A-
1); In J4, -F sensitive composition (A-1
) The photosensitive microcapsule dispersion (A-3) was prepared in the same manner except that the photosensitive composition (A-3) was used instead of the photosensitive composition (A-3).
) was [J. The average particle diameter of the obtained microcapsules was 8 μm.

Salt) Precursor 40g of the base precursor described in F was dissolved in 4% water of Bobvinyl alcohol (PVA-205, manufactured by Kuraray) 74160.
g, and dispersed using a Dyno Mill at 20° C. until the iV average particle size became 2 μm or less to prepare a base precursor solid dispersion.

A coating III solution for forming a photosensitive layer was prepared by adding water to make the total amount 97 g.

This coating solution was applied to a thick coated paper at a coating weight of 48 g/FI7' and dried at about 60"C to prepare a photosensitive material (A>) according to the present invention.

[Example 2] Each photosensitive microcapsule dispersion liquid described in No. 111 <A-1)
, (A-2) and (A-3), 11.3 g each, surfactant (trade name: Nirasan Nonion N5208.5, [1
4 g of a 5% aqueous solution of the product (manufactured by Honshu Oil & Fats), 10.0 g of the base precursor solid dispersion described in L, 13 g of a 20% aqueous solution of sorbitol, and 1.2 g of wheat starch were mixed. In the preparation of the photosensitive microcapsule dispersions (A-1), (A-2) and (A-3) of Example 1, this mixed solution was further added with 5 % of -i''+Ii sodium salt of polyvinylbenzenesulfonic acid. % aqueous solution instead of 104g, 10% aqueous f
The corresponding photosensitive microcapsule dispersions (B-1) and (B- 2) and (
B-3) was prepared. The average particle size of each of the photosensitive microcapsules obtained was approximately 7.0 μm. In the preparation of these capsules, the amount of the partial sodium salt of polyvinylhenzenesulfonic acid used was 60% of the amount of melamine/formaldehyde.

In preparing the photosensitive material (A) of Example 1, instead of using 11.3 g each of microcapsule dispersions (A-1), (A-2) and (A-3), 1 each of microcapsule dispersions (B-1), (B-2) and (B-3)
A photosensitive material (B) according to the Jf method of the present invention was prepared in the same manner as the photosensitive material (A) except that 9.1 g was used.

[Comparative Example 1] Photosensitive microcapsule dispersion liquid (A-1) of Example 1,
Same as Example 1 except that in the preparation of (A-2) and (A-3), 208 g of a 10% aqueous solution of the sodium salt of polyvinylbenzenesulfonic acid was used instead of 104 g of a 5% aqueous solution. Photosensitive microcapsule dispersions (X-1), (X-2), and (X-3), which were manufactured by the same company and were compatible with each other, were manufactured by A. The average particle diameter of each photosensitive microcapsule obtained was approximately 7.5 μm. In this capsule preparation process, the amount of the partial sodium salt of polyvinylbenzenesulfonic acid used was 173% compared to 41% of melamine formaldehyde.

In the preparation of the photosensitive material (A) of Example 1, microcapsule molecules 11. Solutions (A-1), (A-2) and (A-
Instead of using 11.3 g each of 3), the above photosensitive microcapsule dispersions (X-1), (X-2) and (X-3)
Comparative photosensitive material (X) was prepared in the same manner as photosensitive material (A) except that 15.0 g of each was used.

[Comparative Example 2 Photosensitive microcapsule dispersion liquid (A-1) of Example 1,
In the preparation of (A-2) and (A-3), a 5% aqueous solution of a partial sodium salt of polyvinylbenzenesulfonic acid 1
The corresponding photosensitive microcapsule dispersions (Y-1), (Y-2) and (
Y-3) was prepared. The average particle diameter of each of the photosensitive microcapsules obtained was approximately 7.0 μm. In this capsule preparation step 1, the amount of the sodium salt of polyvinylbenzenesulfonic acid used was 87% of the 111 of melamine formaldehyde. In the preparation of microcapsule dispersions (A-1, (A-2) and (A-3)
Instead of the above photosensitive microcapsule dispersion (y-t
), (Y-2) and (Y-3) using the same rLt, a comparative photosensitive material (Y) was prepared in the same manner as the photosensitive material (A).

[Comparative Example 3] Microcapsule Z-1 During the preparation of the photosensitive microcapsule dispersions (A-1), (A-2) and (A-3) of Example 1, polyvinylbenzenesulfonic acid was The corresponding photosensitive microcapsule dispersions (z-i, ) and (2- 2) and (2-3) were prepared. The average particle diameters of the obtained externally photosensitive microcapsules were approximately 13.0 μm, 15.0 μm, and 11.0 μm, respectively.
It was m. It was also confirmed that these contained giant capsules of 50 μm or more. In these capsule preparation steps, the amount of some sodium salt of polyvinylbenzenesulfonic acid used is 87% of that of melamine/formaldehyde.

In the production of photosensitive material $4 (A) of Example 1, microcapsule dispersions (A-1), (A-2) and (A-3)
), the photosensitive microcapsule dispersion ticz-t>, (Z-2) and (Z-
The photosensitive material (A) except that 15.0 g of each of 3) was used.
A comparative photosensitive material (Z) was prepared in the same manner as in the preparation of .

[Evaluation as a photosensitive material] Next, each photosensitive material (A
,B,

To 125 g of water was added 11 g of a 40% sodium hexametaphosphate aqueous solution, and to this was added 34 g of zinc 3.5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry. , and coarsely dispersed with a mixer.

The liquid was dispersed using a Dynamyl dispersion machine, and 20% of the obtained liquid
8% polyvinyl alcohol water soluble fii 1 for 0g
2g was added and mixed uniformly. Add 70% water to this mixture.
g was added to prepare a coating solution for forming an image-receiving layer. Then, apply this coating solution to a paper support (JIS-
Use a base paper that has a fiber length distribution such that the sum of the Il content% of the 24-mesh residue and the weight Id% of the 42-mesh residue is 30 to 60% as the m-ply length distribution defined by P-8207. The paper support (see JP-A No. 63-186239)) was coated uniformly so that the reference portion 11t weighed 58 g/ba. &, an image-receiving material was prepared by drying at 60°C.

Each photosensitive material was exposed to light at 2000 lux for 1 second using a tungsden light bulb through a continuous filter with a transmission A density of 47 from 0 to 4.0, and then exposed to light for 1 second at 2000 lux on a hot plate heated to 150°C, I-: for 10 seconds. Heated.

Next, each of the two photosensitive materials was mixed with the above image-receiving material under room temperature conditions (20°C, 60% RH). ■Hey, in this state it's 5
00 kg/cm' pressure roller.

Then, each photosensitive material was peeled off from the image-receiving material, and a black positive color image was obtained on each image-receiving material. The minimum density (DIIlin) and maximum density (DlIlax) of the obtained color image were measured using a Macbeth reflection densitometer. Note that under room temperature conditions (20° C., 560% RH), the light-sensitive material had a good all m value of 11 compared to the image-receiving material.

In addition, the atmosphere in the process of obtaining the above transferred image was set to a high temperature, high humidity F.
(30°C, 80% RH). Then, the peeling state of the image after pressure transfer was evaluated.

The measurement results of 1- below are summarized in Table 1.

In addition, in the table, the numerical value in the column "r addition amount" indicates the weight percent of the partial sodium salt of polyvinylhezenesulfonic acid based on the melamine aldehyde. Also, r211fi-like T,!
, y column odor ``tc'', ``Part of the lower iB photosensitive layer or image-receiving layer has peeled off and adhered to one side. , means that the surface of the image is not smooth.

Table 1 Photosensitivity Addition amount Turnip size Minimum concentration material (μm) (Dmin) ¥S==1 Condition A 43 8.0 0.09 Good B
60 7.0 0.07 Good X 173
7.5 0.13 Not possible Y 87 7.0
0.10 - Partially prohibited Z 87 Generation of giant-sized particles As is clear from the results shown in Table 1, there The images are from photosensitive materials (X), (Y) and (Z) for comparison.
) The density of the white background area (minimum density) was lower than that of the image obtained from This means that the capsule preparation was successful. Further, even when images were formed using the photosensitive materials (A) and (B) under high temperature and high humidity, no peeling inhibition occurred.

Claims (1)

[Scope of Claims] An oily mixed liquid containing silver halide grains, a reducing agent, a polymerizable compound, and a polyvalent isocyanate compound, containing a polyol and/or a polyamine, and containing melamine and formaldehyde as described below. A polyurea and/or polyurethane resin is dispersed in an aqueous liquid containing a styrene sulfonic acid polymer in an amount of 30 to 65% by weight based on the amount or prepolymer, and the oil droplets are surrounded by a polyurea and/or polyurethane resin. , forming an inner wall containing silver halide grains; adding melamine and formaldehyde or a prepolymer thereof to the aqueous liquid to form an outer wall of melamine aldehyde resin around the inner wall; 1. A method for producing a photosensitive material, comprising: preparing photosensitive microcapsules; and coating a dispersion containing the photosensitive microcapsules on a support and drying the dispersion.