JPH0266548A - Photosensitive material - Google Patents

Abstract

PURPOSE:To improve the contrast of the subject material and to improve a picture by incorporating silver halide in a photosensitive layer existing in the exterior of a microcapsule and being stuck the silver halide on the surface of the microcapsule. CONSTITUTION:The silver halide is incorporated in the photosensitive layer existing in the exterior of the microcapsule, and is stuck on the surface of the microcapsule. The silver halide enclosed in the microcapsule and that stuck to the surface of the microcapsule are different with each other in the kinds thereof. The silver halide stuck on the surface of the microcapsule is composed of a silver halide particle previously fogged. A polymerizable compd. oozed out from the microcapsule by the action of the silver halide performs a polymerization reaction in the same manner as the compd. enclosed in the microcapsule. The polymerizable compd. unpolymerized is almost completely removed from a part formed the latent image of the silver halide. Thus, the picture with the high contrast and sharpness is obtd.

Description

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

[Background of the Invention] A photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support is.

It can be used in an image forming method in which a latent image of silver saponide is formed and a polymerizable compound is polymerized.

Examples of image forming methods include methods described in Japanese Patent Publication Nos. 11149/1982, 20741/1982, 10697/1987, 138632/1980, and 169143/1980. . In these methods, when the silver halide in the imagewise exposed photosensitive layer is developed using a developer, the coexisting reducing agent is oxidized, and at the same time, the coexisting polymerizable compound (e.g., vinyl compound) is oxidized. is polymerized 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 on the above method, Japanese Patent Application Laid-Open No. 61-69062 discloses a method in which a polymer compound can be formed by dry processing. This method uses a photosensitive silver salt (
A latent image of a photosensitive silver salt is formed by imagewise exposing a recording material (photosensitive material) comprising a photosensitive layer comprising silver halide (silver halide), a reducing agent, a crosslinkable compound (polymerizable compound), and a binder supported on a support. by forming and then heating it,
This is a method in which a polymer (high molecular compound) is formed in the area where the latent image has been formed.

In the photosensitive material as described above, the silver halide, the polymerizable compound, and the reducing agent can be contained in the photosensitive layer in the form of microcapsules. In this way, photosensitive materials using microcapsules provide clear images with high sharpness. Regarding photosensitive materials using microcapsules, see JP-A-61-73145 and JP-A-61-275.
No. 742, No. 61-278849, No. 62-1691
No. 47 and No. 62-183451.

[Summary of the Invention] A photosensitive material using microcapsules provides clear images with high sharpness as described above. However, when the present inventor closely observed the obtained image, it was found that a small amount of unpolymerized polymerizable metal remained in the area where the latent image of silver halide was formed, where the polymerization reaction should proceed. There is. The polymerizable compound remaining in the area where the silver halide latent image is formed causes a decrease in image contrast and stains.

An object of the present invention is to provide a photosensitive material that provides a clearer image with high contrast.

The present invention has a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support, and the photosensitive layer contains the silver halide and the polymerizable compound in microcapsules. Provided is a photosensitive material characterized in that the photosensitive layer outside the microcapsules also contains silver halide, and the silver halide is attached to the surface of the microcapsules. It is something to do.

The photosensitive material of the present invention preferably has the following embodiments.

(1) Solid fine particles of a base or a base precursor are attached to the surface of the microcapsule.

(2) The reducing agent is contained in microcapsules.

(3) At least 70% of the silver halide contained in the microcapsules is contained in the wall material of the microcapsules.

(4) The types of silver halide contained in the microcapsules and the silver halide adhered to the surface of the microcapsules are different.

(5) The silver halide attached to the surface of the microcapsules is a fogged silver halide particle.

(6) The amount of silver halide attached to the surface of the microcapsules is 5 to 200 mol% relative to the amount of silver halide contained in the microcapsules.

(7) The total amount of silver halide contained in the photosensitive layer is in the range of 0.1 mg to 10 g/rn' in terms of silver.

(8) The microcapsules have an average particle diameter of 1 to 30 μm.

(9) The silver halide adhering to the surface of the microcapsules is silver halide particles having an average particle size of o, ooi to 10 μm.

(10) A cationic polymer is attached to the surface of the microcapsule.

[Effects of the Invention] According to research conducted by the present inventors, a trace amount of unpolymerized polymerizable compounds remaining in the area where the silver halide latent image is formed is removed from the microcapsules during storage or thermal development of the photosensitive material. It became clear that it had seeped out.

In a photosensitive material in which silver halide is contained in microcapsules, the polymerization reaction of the polymerizable compound seeping out from the microcapsules does not proceed sufficiently.

The photosensitive material of the present invention is characterized in that the photosensitive layer outside the microcapsules also contains silver halide, and further, this silver halide is attached to the surface of the microcapsules. Due to the action of this silver halide, the polymerization reaction of the polymerizable compound exuded from the microcapsules can proceed in the same manner as inside the microcapsules. As a result, the unpolymerized polymerizable compound is
The silver halide latent image is almost completely removed from the area where it was formed.

Further, since the silver halide is attached to the surface of the microcapsule, the polymerization reaction of the polymerizable compound seeped out from the microcapsule during thermal development proceeds on the surface of the microcapsule. Therefore, the polymerizable compound exuding from the microcapsules is prevented from migrating to the areas in the photosensitive layer where the silver halide latent image is not formed, and the polymerization reaction is prevented from proceeding in those areas. Therefore, in the light-sensitive material of the present invention, the portion where the polymerization reaction proceeds coincides very well with the portion where the silver halide latent image is formed.

As a result, the photosensitive material of the present invention provides very clear images with high contrast.

In addition, the embodiment in which solid fine particles of a base or base precursor are attached to the surface of the microcapsules is because the base or base precursor significantly accelerates the action of the silver halide attached to the microcapsules as described above. , particularly preferred.

[Detailed Description of the Invention] The photosensitive material of the present invention contains silver chloride, silver chloride,
Any grains of silver bromide, 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 disclose
No. 3, No. 59-48755, No. 59-52237, U.S. Patent No. 4433048 and European Patent No. 1
There are descriptions in each specification of No. 00984. Also, JP-A-61
Silver halide grains having a high proportion of silver iodide in the shell portion may be used, as in the photosensitive material described in Japanese Patent No. 183453.

There is 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.

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

There are no particular restrictions on the grain size distribution of silver halide grains. For example, monodisperse silver halide grains 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 the silver halide grains is preferably 0.001 to 5 μm, o,
More preferably, the thickness is from ooi to 2 μm.

In the photosensitive material of the present invention, not only silver halide is contained in the microcapsules, but also silver halide is attached to the surface of the microcapsules. The silver halide attached to the surface of the microcapsule may be the same as the SR halide inside the microcapsule, but it is preferable to use a different type of silver halide.

As the silver halide attached to the microcapsules, it is preferable to use silver halide particles having higher sensitivity or a higher fog value than the silver halide inside the microcapsules.

The silver halide inside the microcapsules was disclosed in JP-A-63
Like the silver halide grains described in -68830,
Unexposed silver halide grains were washed with 1. Og, sodium sulfite 15.0g, hydroquinone 4.0g, sodium carbonate monohydrate 26.7g and potassium bromide 0
．． It is preferable that the silver halide grains have such a low fog value that the amount of developed silver is 5% by weight or less of the total silver amount when developed for 2 minutes at 20° C. in a developer prepared by adding 7 g of water to 12. . The amount of developed silver is more preferably 2% by weight or less of the amount of gold and silver, and particularly preferably 0.01 to 1% by weight.

On the other hand, it is preferable that the silver halide attached to the surface of the microcapsule has a higher sensitivity than the silver halide inside the microcapsule by 0.3 or more in terms of IogE value. Furthermore, those having a high sensitivity of 0.5 to 1.0 in terms of logE value are particularly preferred. The unexposed silver halide at this time is silver halide grains with a high fog value such that the amount of developed silver is 5% by weight or more of the total silver amount when developed in the above developer at 20°C for 2 minutes. It's okay.

As the silver halide attached to the surface of the microcapsules, fogged silver halide particles may be used. A common method for clouding silver halide grains is to chemically fog them at the silver halide emulsion stage using a fogging agent known in conventional silver salt photography. However, silver halide grains can also be covered by exposure or heating.

Note that, for the purpose of forming a full-color image, two or more types of silver halide grains that are sensitive to a specific wavelength and have different sensitivity wavelengths may be contained in different microcapsules. In the photosensitive material of the present invention, the photosensitive wavelengths of the silver halide attached to the surfaces of two or more types of microcapsules can be made to correspond to the photosensitive wavelengths of the silver halide inside the microcapsules, respectively. Alternatively, the silver halide attached to the surface of the microcapsules can be made panchromatic.

The total amount of silver halide contained in the photosensitive layer is preferably in the range of 0.1 mg to 10 g/rn'' in terms of silver, including organic silver salt, which is an optional component described below. In terms of silver, it is preferably 0.1 g/rn'' or less, and particularly preferably 1 mg/rn' to 90 mg/rn'.

The amount of silver halide attached to the surface of the microcapsules is preferably 5 to 200 mol % based on the amount of silver halide contained in the microcapsules.

The state in which silver halide is attached to the microcapsules can be confirmed by observing the surface of the coated sample using a scanning electron microscope.

Various means can be used to attach silver halide to the microcapsules, such as those described below.

(1) A cationic polymer is added to the microcapsule dispersion, the cationic polymer is attached to the surface of the microcapsule, and then a silver halide emulsion is added to the microcapsule dispersion. It can be attached to microcapsules. In this case, it is preferable that ionic substances (protective colloids, etc.) present in the microcapsule dispersion be removed in advance by washing or the like. However, if a cationic polymer is used as a protective colloid, it is not necessary to remove it. Note that the cationic polymer is also effective as a means for attaching solid fine particles of a base or a base precursor, which will be described later, to the surface of the microcapsule.

(2) In the production of microcapsules, the outer shell of the microcapsules may be formed in the presence of silver halide.

(3) Dispersing silver halide in a solvent such as alcohol,
After mixing with the microcapsule dispersion, the solvent may be removed by evaporation.

The method (1) above is particularly preferred because it allows silver halide to be deposited most efficiently. According to the research of the present inventors, by using the method (1) above, silver halide can be attached to microcapsules at a very high rate.

The cationic polymer used to attach the silver halide to the microcapsules may include, for example, a homopolymer containing a quaternary ammonium salt; a copolymer of a homopolymer containing a quaternary ammonium salt and a vinyl compound such as styrene. . Specifically, cationically modified polyvinyl alcohol (especially polyvinyl alcohol modified with aminoalkyl acrylate) is useful. Also useful are acid-treated gelatin, polyethyleneimine, and the like.

The molecular weight of the above cationic polymer is preferably in the range of 50,000 to 500,000. In addition, the amount used is microcapsules with an average particle diameter of 3 to 20 μm (specific gravity of 0.8 to 1
, 2) in a weight ratio of 0.05 to 50% (more preferably 0.5 to 20%).

In the photosensitive material of the present invention, solid fine particles of a base or a base precursor are preferably attached to the surface of the microcapsules.

Examples of preferable bases include, as an inorganic base, zinc hydroxide or a combination of zinc oxide and a chelating agent such as sodium picolinate, and hydroxides of various metals, and as an organic base, a heterocyclic amine. , amidines, cyclic amidines, guanidines, cyclic guanidines, and the like.

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

In the photographic material of the present invention, the base or base precursor preferably has a melting point of 70 to 210°C.

Further, the base or base precursor is preferably hydrophobic, and specifically, the solubility in water at 25°C is
It is preferably 0.1% by weight or less. Furthermore, it is preferable that the pKa value of the base or the base generated from the base precursor is 7 or more.

In the light-sensitive material of the present invention, it is particularly preferable to use a salt of an amidine derivative or a salt of a guanidine derivative described below as a base precursor.

That is, a base precursor consisting of a salt of a carboxylic acid and an organic base, in which the organic base has a partial structure corresponding to an atomic group obtained by removing one or two hydrogen atoms from an amidine represented by the following formula (I). A base precursor which is a second- to fourth-order base consisting of two to four bases and one or more hydrocarbon residues or heterocyclic residues as a linking group of the partial structure can be particularly preferably used.

\ [In the above formula (I), R1, R2, R3 and R4 are each a hydrogen atom,
A monovalent group selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, and a heterocyclic residue (each having - or more substituents; and any two groups selected from RI, R2, R3 and R4 are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle (preferably consisting only of carbon atoms and nitrogen atoms). In addition, a base precursor consisting of a salt of a carboxylic acid and an organic base, in which the organic base converts one hydrogen atom from guanidine represented by the following formula (I[)] or a second- to fourth-order base (preferably, A base precursor having a total number of carbon atoms (within 6 times the number of the partial structures) can also be particularly preferably used.

\ [In the above formula (11), R3, R4 and R5 are each from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic residue. A selected monovalent group (the multiple group may have - or more substituents), and any two groups selected from R1)j2 R3, R4 and R5 are: The base or base precursor may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle (preferably a heterocycle consisting only of carbon atoms and nitrogen atoms). Preferably, it is attached to the surface of the capsule. The average particle diameter of the solid fine particles of the base or base precursor is preferably 0.01 to 10 μm, and 0.0
More preferably, the thickness is 5 to 5 μm.

The base or base precursor can be used in the photosensitive material in a wide range of amounts. The base or base precursor is suitably used in an amount of 100% by weight or less, more preferably 0.1% by weight of the coating film of the photosensitive layer.
A range of from 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.

In the photosensitive material of the present invention, it is preferable that the photosensitive layer contains fine particles of the base or base precursor as described above, and that 30% or more of the particles are attached to the surface of the microcapsules. More preferably, 50% or more of the particles, particularly preferably 70% or more of the particles, are attached to the surface of the microcapsule.

The state of adhesion of the fine particles of the base or base precursor can be easily calculated by observing the photosensitive material using an optical microscope or an electron microscope after manufacturing the photosensitive material.

In order to attach the base or base precursor fine particles to the microcapsules, various means as described below (substantially the same as the means for attaching silver halide to the microcapsules described above) can be used.

(1) Fine particles of a base or base precursor are dispersed in a medium containing a cationic polymer, and this dispersion is added to a dispersion of microcapsules, whereby fine particles of a base or base precursor are microencapsulated together with a cationic polymer. can be attached to. in this case,
Ionic substances present in the microcapsule dispersion (
Protective colloids, etc.) are preferably removed by washing or the like in advance. However, if a cationic polymer is used as a protective colloid, it is not necessary to remove it.

(2) In the production of microcapsules, the outer shell of the microcapsules may be formed in the presence of fine particles of a base or base precursor.

(3) Fine particles of the base or base precursor may be dispersed in a solvent such as alcohol, mixed with the microcapsule dispersion, and then removed by evaporating the solvent.

The means (1) above can be particularly preferably used.

Hereinafter, in addition to the silver halide mentioned above, each component constituting the photosensitive material will be sequentially explained. The photosensitive material having the above structure will be simply referred to as "r photosensitive material" hereinafter.

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 above reducing agents include hydroquinones, catechols, p-aminophenols, p-phinidine diamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, and 5-aminouracil. 4゜5-dihydroxy-6-aminopyrimidines, reductones, amyl reductones, 0- or P-sulfonamidophenols, 0- or p-sulfonamidonaphthols, 2
-Sulfonamide indanones, 4-sulfonamide-
5-pyrazolones, 3-sulfonamide indoles,
Examples include sulfonamide vilazolepenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, hydrazines, and the like. 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 1-phenyl-3-pyrazolidones as the reducing agent.

Regarding various reducing agents having the above functions, please refer to JP-A-61-183640, JP-A No. 61-188535, and JP-A-61-188535.
Publications No. 1-228441 and JP-A-62-7
No. 0836, 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). Regarding the above-mentioned reducing agent, please refer to “The-
The.

ry of the Photographic Pr
4th edition, pp. 291-334 (1977)
, Research Disclosure Magazine Vol.1.170.1
There are also descriptions in No. 17029 (pages 9-15) of June 1978, and No. 17643 (pages 22-31) of the same magazine, Vol. 176, December 1978. Also, JP-A-62-
As in the photosensitive material described in Japanese Patent No. 210446, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base may be used in place of the reducing agent. 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 material used in this specification. Therefore, the term "r-reducing agent" in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literatures. These reducing agents may be used alone, but as described in each of the above specifications, two or more types of reducing agents may be used in combination. When two or more types of reducing agents are used together, the interaction of the reducing agents is, first, to promote the reduction of silver halide (and/or organic silver salt) through so-called superadditivity; , causing polymerization of the polymerizable compound via a redox reaction with other reducing agents coexisting with an oxidized form of the first reducing agent generated by reduction of silver halide (and/or organic silver salt); (or suppressing polymerization), etc. However, in actual use, the reactions described above can occur simultaneously, so it is difficult to specify which effect is occurring.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p-(N,N-diethylamino)phenol, 1-phenyl-4-methyl-
4-hydroxymethyl 3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenylsulfonyl Amine-4-t-butyl-
5-hexadecyloxyphenol, 2-(N-butylcarbamoyl)-4-phenylsulfonylaminonaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol, 1-acetyl-2-phenylhydrazine , l-acetyl-2-((
p or 0)-aminophenyl)hydrazine, 1-formyl-2-((p or 0)-aminophenyl)hydrazine, 1-acetyl-2-((p or 0)-methoxyphenyl) and drazine, 1-lauroyl -2-((p or 0)-aminophenyl)hydrazine, 1-trityl-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 0)-aminophenyl) Hydrazine, 1-(2-(2,5-di-
t-pentylphenoxy)butyroyl't-2-((p
or o)-aminophenyl)hydrazine pentadecylfluorocaprylate, 3-indazolinone, 1-(
3,5-dichlorobenzoyl)-2-phenylhydrazine, 1-trityl-2-[((2-N-butyl-N-octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, 1-(4- (2,5-di-t-pentylphenoxy)butyroyl) = 2-((p or O)
-methoxyphenyl)hydrazine, 1-(methoxycarbonylbenzohydryl)-2-phenylhydrazine, 1
-Formyl-2-[4-(2-(2,4-di-t-pentylphenoxy)butyramido)phenyl]hydrazine, 1-acetyl-2-[4-(2-(2,4-di-t-
pentylphenoxy)butyramido)phenyl]hydrazine, 1,-trityl-2-[(2,6-dichloro-4
-(N.

N-di-2-ethylhexyl)carbamoyl)phenyl]hydrazine1,1-(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-)lythylhydrazine, 1-(,2,4- Examples include dimethoxybenzoyl)-2-tritylhydrazine, 1-(4-dibutylcarbamoylbenzoyl)-2-tritylhydrazine, and 1-(1-naphthoyl)-2-tritylhydrazine.

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

In the photosensitive material of the present invention, the reducing agent can be placed inside or outside the microcapsules, or both.

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and any known polymerizable compound can be used. In addition, when heat development treatment is planned as a method of using the photosensitive material, it is recommended to use a material with a high boiling point (for example, a boiling point of 80
℃ or higher) is preferably used. 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. A crosslinkable compound having a polymerizable functional group is preferable. Furthermore, as will be described later, when forming a transferred image using an image-receiving material, Japanese Patent Application No. 15007-1986
It is preferable to use a highly viscous substance as the polymerizable compound, as in the photosensitive material described in No. 9.

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

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

Specific examples of polymerizable compounds that can be used in photosensitive materials include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, and ethoxyethoxyethyl acrylate. Acrylate, dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate,
Diacrylate of polyoxyethyleneated bisphenol A, diacrylate of 2,2-dimethyl-3-hydroxypropionaldehyde and trimethylolpropane condensate, triacrylate of 2,2-dimethyl-3-hydroxypropionaldehyde and pentaerythritol condensate , hydroxypolyether polyacrylates, polyester acrylates, polyurethane acrylates, and the like.

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 the above-mentioned reducing agent or a color image forming substance which is an optional component described later can also be used as the polymerizable compound. Needless to say, the use of a reducing agent and a polymerizable compound, or a substance that serves both as a color image forming substance and a polymerizable compound, as described above, is also included in the embodiment of the photosensitive material.

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

In the light-sensitive material of the present invention, the silver halide field and the polymerizable compound are contained in microcapsules. It is generally preferable that the oil droplets of the polymerizable compound are in the form of microcapsules. Various known techniques can be applied to the microcapsules without particular limitations. The microcapsules may contain optional components such as reducing agents or color image forming substances.

There are no particular restrictions on the wall material that constitutes the outer shell of the microcapsules. Regarding photosensitive materials using microcapsules with outer shells made of polyamide resin and/or polyester resin, Japanese Patent Application Laid-Open No. 62-209437 describes microcapsules with outer shells made of polyurea resin and/or polyurethane resin. The photosensitive material used is described in JP-A-62-209438, and the photo-sensitive material using microcapsules having an outer shell made of amino aldehyde resin is described in JP-A-62-209.
No. 439 describes a photosensitive material using microcapsules having an outer shell made of gelatin.
No. 440 discloses a photosensitive material using microcapsules having an outer shell made of epoxy resin, as described in Japanese Patent Laid-Open No. 62
JP-A-209441 discloses a photographic material using a microcapsule having a composite resin shell containing a polyamide resin and a polyurea resin; Photosensitive materials using microcapsules having the above-mentioned properties are described in JP-A-62-209442.

In addition, when using aldehyde-based microcapsules, it is preferable to keep the amount of residual aldehyde below a certain value, as in the photosensitive material described in JP-A-63-32535.

It is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsule. Regarding photosensitive materials containing silver halide in the wall material of microcapsules, JP-A No. 6
There is a description in Publication No. 2-169147. Also, JP-A-6
As described in Japanese Patent No. 3-15239, it is preferable that the number of silver halide grains contained in a microcapsule is 5 or more.

Furthermore, two or more microcapsules containing at least one different component may be used in combination, such as silver halide, a reducing agent, a polymerizable compound, and a color image forming substance which is an optional component described below. good. In particular, when forming a full-color image, it is preferable to use three or more types of microcapsules containing different color image-forming substances in different hues. For photosensitive materials containing two or more types of microcapsules, JP-A-62-19
There is a description in Publication No. 8850.

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

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

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. It is preferable to have. In addition, when using a paper support, a paper support with low water absorption such as the photosensitive material described in JP-A No. 63-38934, and a paper support with a constant water absorption rate such as the photosensitive material described in JP-A No. 63-47754 can be used. Paper support having Bekk smoothness of JP-A-63-8133
A paper support with a low shrinkage rate such as the photosensitive material described in JP-A No. 9, a paper support with low air permeability such as the photosensitive material described in JP-A-63-81340, and a paper support as described in JP-A-63-97941. A paper support having a pH value of 5 to 9, such as the photosensitive material described above, can also be used.

The following optional components that can be included in the photosensitive layer of the margin photosensitive material include color image forming substances, sensitizing dyes, organic silver salts, radical generators, various image formation accelerators, thermal polymerization inhibitors, and thermal polymerization initiators. agent, development stopper, fluorescent whitening agent, antifading agent, dye or pigment for preventing halation or irradiation, pigment that has the property of decolorizing by heating or light irradiation,
Examples include matting agents, anti-smudge agents, plasticizers, water release agents, binders, photopolymerization initiators, solvents for polymerizable compounds, 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 the above-mentioned Japanese Patent Laid-Open No. 73145/1983. Regarding photosensitive materials using dyes or pigments as color image forming substances, see JP-A-62-187346, and about photosensitive materials using leuco dyes, see JP-A-62-209436. For photosensitive materials using leuco dyes, see JP-A No. 62-251741, and for photosensitive materials using yellow coloring leuco dyes, see JP-A Nos. 62-288827 and 62-288.
No. 828 describes a photosensitive material using a cyan color-forming leuco dye, and Japanese Patent Application Laid-Open No. 63-53542 discloses a photosensitive material using a cyan color-forming leuco dye.

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

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

Examples of substances that develop color upon contact with another component include various systems that develop color due to acid-base reactions, redox reactions, coupling reactions, chelate formation reactions, etc. between two or more components. For example, pressure-sensitive copying paper (pp. 29-58) and azography (p.
95 pages), known coloring systems such as heat-sensitive coloring by chemical changes (pages 118-120), or the preliminary draft of the seminar ``Latest Pigment Chemistry - Attractive Applications and New Developments as Functional Dyes - 1'' hosted by the Kinki Chemical Industry Association. Collection, pp. 26-32, (198
It is possible to use the coloring system described in June 19, 2013).

Specifically, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran, which is used in pressure-sensitive paper, and an acidic substance (coloring agent) such as acid clay or phenols: an aromatic diazonium salt or Systems that utilize azo coupling reactions between diazotate, diazosulfonates, naphthols, anilines, active methylenes, etc.; reactions between hexamethylenetetramine and ferric ions and gallic acid; and reactions between phenolphthalein and combreculanes. Chelate-forming reactions such as reactions with alkaline earth metal ions; redox reactions such as reactions between ferric 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 a proportion of 0.5 to 20 parts by weight per 100 parts by weight of the polymerizable compound,
More preferably, it is used in a proportion of 2 to 7 parts by weight.

Further, when a color developer is used, it is preferably used in a proportion of about 0.3 to 80 parts by weight per 1 part by weight of the color former.

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

The sensitizing dye that can be used in the light-sensitive material is not particularly limited, and silver halide sensitizing dyes known in the photographic technology can be used. The above-mentioned sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Includes styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. Particularly when the purpose is supersensitization, it is common to use a combination of sensitizing dyes. 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 sensitizing dye added is generally 10-8 to 10-8 per mole of silver halide.
It is about 2 moles.

The above-mentioned sensitizing dye is preferably added at the stage of preparing a silver halide emulsion, which will be described later. Regarding a light-sensitive material obtained by adding a sensitizing dye at the stage of forming silver halide grains, JP-A-62-947 discloses that a sensitizing dye is added to a silver halide emulsion after the formation of silver halide grains. The photosensitive materials obtained by adding these materials in the preparation stage are described in JP-A No. 62-210449. Further, specific examples of sensitizing dyes that can be used in light-sensitive materials are also disclosed in the above-mentioned JP-A-62-947 and JP-A-62-947.
It is described in the publication No.-210449. In addition, like the photosensitive material described in Japanese Patent Application No. 61-208786,
An infrared light-sensitive sensitizing dye may also be used.

Addition of organic silver salts to photosensitive materials is particularly effective in thermal development processing. That is, when heated to a temperature of 80° C. or higher, the organic silver salt is considered to participate in an oxidation-reduction reaction using the latent image of silver halide as a catalyst. In this case, the silver halide and the organic silver salt are preferably in contact or in close proximity. Examples of the organic compound constituting the 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 above organic silver salt is generally 0.01 to 10 mol, preferably 0.01 mol per mol of silver halide.
Use 1 to 1 mole. Note that the same effect can be obtained by adding an organic compound (for example, benzotriazole) constituting the organic silver salt to the photosensitive layer instead of the organic silver salt. A photosensitive material using an organic silver salt is described in JP-A-62-3246. The organic silver salt as described above is preferably used in an amount of 0.1 to 10 mol, more preferably 0.01 to 1 mol, per 1 mol of silver halide. The organic silver salt is preferably added to the photosensitive layer outside the microcapsules.

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

A photosensitive material using silver triazene as the radical generator is described in JP-A No. 62195639, and a photosensitive material using silver diazotate is described in JP-A No. 62-1.
95640, and JP-A-62-195641 describes a photosensitive material using an azo compound.

Various image formation accelerators can be used in the photosensitive material. Image formation accelerators include those that promote the redox reaction between silver halide (and/or organic silver salt) and a reducing agent, and 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 a light-sensitive material and an image-receiving material or an image-receiving layer (the two layers will be described later). It has functions such as promoting the movement of image-forming substances.

From the viewpoint of physicochemical functions, image formation accelerators include bases,
Base precursor (base and base precursor are described above), oil, surfactant, compound having capri-preventing function and/or development accelerating function, hot solvent,
It is further classified into compounds that have an oxygen removal function.

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.

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

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

A compound having an antifogging function and/or a development accelerating function can be used for the purpose of obtaining a clear image (an image with a high S/N ratio) having a high maximum density and a low minimum density. Note that a photosensitive material using an antifoggant as a compound having an antifogging function and/or a development accelerating function is described in JP-A-62-151838, and a photosensitive material using a compound having a cyclic amide structure is described in JP-A-62-151838. For photosensitive materials using thioether compounds, see JP-A-61-151841, and JP-A-62-151841.
No. 151842 describes photosensitive materials using polyethylene glycol derivatives, and Japanese Patent Application Laid-Open No. 151843/1983
For photosensitive materials using thiol derivatives, see JP-A-62-151844, and for photosensitive materials using acetylene compounds, see JP-A-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 U.S. Patent No. 3,347,675, derivatives such as oleic esters of polyethylene oxide, beeswax, monostearin, -50
Compounds with high dielectric constant having 2- and/or -C〇- groups, polar substances described in U.S. Pat. No. 3,667,959, 1,10-decane described in Research Disclosure magazine, December 1976 issue, pages 26-28 Diol, methyl anisate, biphenyl perate, etc. are preferably used. 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 influence of oxygen (oxygen has a polymerization inhibiting effect) during development. Examples of compounds having an oxygen removing function include compounds having two or more mercapto groups. Incidentally, a photosensitive material using a compound having two or more mercapto groups is described in JP-A-62-209443.

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

Thermal polymerization initiators are described in pages 6 to 18 of "Addition Polymerization/Ring Opening Polymerization J, 1983, Kyoritsu Shuppan," edited by the Editorial Committee of Polymer Experiments, The Polymer Society of Japan.Thermal polymerization initiators Specific examples include azobisisobutyronitrile, 1
．． 1'-azobis(l-cyclohexanecarbonitrile), dimethyl-2,2'-azobisisobutyrate,
2゜Azo compounds such as 2-azobis(2-methylbutyronitrile) and azobisdimethylvaleronitrile, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydro Examples include organic peroxides such as peroxide, inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, and sodium p-toluenesulfinate. The thermal polymerization initiator is 0 for the polymerizable compound.
．． It is preferably used in a range of 1 to 120% by weight, and more preferably in a range of 1 to 10% by weight. 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. Regarding photosensitive materials using thermal polymerization initiators, Japanese Patent Application Laid-Open No. 62-70836
There is a description in the bulletin.

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 suppresses development. Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include JP-A-60-1
Examples include oxime esters described in JP-A No. 08837 and No. 60-192939, and compounds that release an acid by Rossen rearrangement described in JP-A No. 60-230133.

Examples of electrophilic 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.

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

The anti-smudge agent used in the photosensitive material is preferably a particulate material that is solid at room temperature. As a specific example, British Patent No. 1
Starch particles described in the specification of No. 232347, fine polymer powders described in the specification of US Pat. No. 3,625,736, etc., microcapsule particles containing no color former as described in the specification of British Patent No. 1,235,991, etc., and US Pat. No. 2,711,375. Examples include inorganic particles such as cellulose fine powder, talc, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina. The average particle size of the particles is preferably in the range of 3 to 50 μm, more preferably in the range of 5 to 40 μm in volume average diameter. 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 photosensitive materials can be contained in the photosensitive layer alone or in combination. It is preferable to use a mainly hydrophilic binder. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. including synthetic polymeric materials such as water-soluble polyvinyl compounds.

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

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

A water-soluble vinyl polymer may be adsorbed onto the silver halide grains described above. Regarding photosensitive materials using water-soluble vinyl polymers as mentioned above, Japanese Patent Application Laid-Open No. 63-9165
There is a description in Publication No. 2.

In addition to those mentioned above, examples of optional components that can be included in the photosensitive layer and how they are used can also be found in the application specifications for the series of photosensitive materials mentioned above, and in Research Disclosure Magazine v01゜170. June 1978. No. 17029 (pages 9-15).

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

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

Instead of using the image-receiving material described below as a method of using the photosensitive material, the above image-receiving layer may be provided on the photosensitive material and an image may be formed on this layer. The image-receiving layer provided on the photosensitive material 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. 62-253140. A photosensitive material provided with a colored layer as an antihalation layer is described in JP-A-63-101842. Further, a photosensitive material provided with a base barrier layer is also described in the above-mentioned Japanese Patent Application Laid-Open No. 62-253140. Furthermore, examples of other auxiliary layers and their usage are also described in the above-mentioned series of applications relating to light-sensitive materials.

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

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

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

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

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

The reaction format between soluble silver salt and soluble halogen salt is as follows:
Either one side mixing method, simultaneous mixing method or a combination thereof may be used. A back-mixing method in which particles are formed under conditions in excess of silver ions and a Chondrold double-jet method in which PAg is kept constant can also be employed. In addition, to accelerate particle growth,
The concentration, amount, or rate of addition of silver salts and halogen salts may be increased (Japanese Patent Application Laid-Open No. 1581-1581).
No. 24, No. 55-158124, and U.S. Pat. No. 3,650,757).

The silver halide emulsion used in the production of light-sensitive materials may be of the surface latent image type, in which latent images are mainly formed on the grain surfaces, or of the internal latent image type, in which the latent images are formed inside the grains. Direct reversal emulsions combining internal latent image type emulsions and nucleating agents can also be used. Internal latent image emulsions suitable for this purpose are disclosed in U.S. Pat. No. 2,592,250, U.S. Pat.
No. 6641, various publications, etc., contain detailed information. A preferred nucleating agent for combination with the above emulsion is US Pat. No. 3,227,552
No. 4245037, No. 4255511, No. 4266013, No. 4276364, and OLS No. 2635316.

In the preparation of silver halide emulsions used in the production of 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; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfate esters, sugar derivatives such as sodium alginate, starch derivatives; and polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole A wide variety of synthetic hydrophilic polymeric materials can be mentioned, such as single or copolymers such as polyvinylpyrazole, polyvinylpyrazole, and the like. Among these, gelatin is preferred. As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and gelatin hydrolysates or enzymatically decomposed products may also be used.

Silver halide emulsions contain ammonia, organic thioether derivatives (see Japanese Patent Publication No. 47-386), sulfur-containing compounds (see Japanese Patent Application Laid-Open No. 53144319), etc. as silver halide solvents in the stage of forming silver halide grains. 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. Further, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium chloride (■ or ■) and ammonium hexachloroiridium salt, or water-soluble rhodium salts 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 Tardel water washing method or the sedimentation method. The silver halide emulsion may be used as it is after ripening, but it is usually used after being chemically sensitized. In emulsions for conventional sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing heterocyclic compounds (Japanese Patent Application Laid-Open No.
8-126526, 58-215644).

In addition, when adding a sensitizing dye to a silver halide emulsion,
The aforementioned Japanese Patent Application Laid-Open No. 62-947 and Japanese Patent Application No. 1988-
It is preferable to add it at the stage of preparing a silver halide emulsion as in the photographic material described in No. 55510. In addition, when adding a nitrogen-containing heterocyclic compound as a compound having the above-mentioned antifogging function and/or development accelerating function, it should be added during the formation stage or ripening stage of silver halide grains in the preparation of a silver halide emulsion. is preferred. A method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added at the stage of forming or ripening silver halide grains is described in JP-A-62-161144.

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

In the production of photosensitive materials, the polymerizable compound can be used as a medium in preparing the composition of other components in the photosensitive layer. For example, silver halide (including silver halide emulsions), reducing agents, color image forming substances, etc. can be dissolved, emulsified or dispersed in a polymerizable compound and used in the production of photosensitive materials. Particularly when a color image forming substance is added, it is preferable to include a polymerizable compound therein. Furthermore, as will be described later, when the oil droplets of the polymerizable compound are microencapsulated, components such as a wall material necessary for microencapsulation may be included in the polymerizable compound.

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

Photosensitive compositions containing these silver halides can be obtained by stirring with a homogenizer, blender, mixer, or other commonly used stirrers.

In addition, it is preferable that a copolymer consisting of a hydrophilic repeating unit and a hydrophobic repeating unit is dissolved in the polymerizable compound used for preparing the photosensitive composition. Regarding photosensitive compositions containing the above-mentioned copolymers, JP-A-62-
There is a description in 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 the above-mentioned silver halide emulsion as a core material is described in JP-A-62-164041.

It is preferable to use the polymerizable compound (including those containing other constituent components like the above photosensitive composition) in the form of an emulsion in an aqueous solvent. It is also possible to add a wall material necessary for microcapsulation to this emulsion and further perform a treatment to form the outer shell of the microcapsules at the stage of this emulsion. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

Examples of the above-mentioned microencapsulation methods include a method using coacervation of aromatic hydrophilic wall-forming materials as described in US Pat. No. 2,800,457 and US Pat. No. 2,800,458; US Pat. Specification, and Special Publication No. 38-1957
4, No. 42-446, and No. 42-771; Interfacial polymerization method described in U.S. Pat. No. 3,418,250 and No. 3,660,304; Method by precipitation of aromatic polymer; U.S. Pat. No. 3,796,669 Method using the isocyanate-polyol wall material described in U.S. Pat. No. 3,914,511; U.S. Pat. No. 4,001,140, U.S. Pat.
No. 087376 and No. 4,089,802 A method using an aromatic urea-formaldehyde-based or urea-formaldehyde-resircinol-based wall-forming material; a wall-forming material such as melamine-formaldehyde resin or hydroxypropyl cellulose described in U.S. Pat. No. 4,025,455 Methods using forming materials: In-5-itu method by polymerization of monomers described in Japanese Patent Publication Nos. 36-9168 and 51-9079; polymerization described in British Patent Nos. 927807 and 965074 Distributed cooling method: US Patent No. 3,111,407 and British Patent No. 930
Examples include the spray drying method described in the specification of No. 422 Yoyo. Although the method for microcapsulating oil droplets of a polymerizable compound is not limited to the above, a method in which a core substance is emulsified and then a polymer film is formed as a microcapsule wall is particularly preferred.

Regarding photosensitive microcapsules that can be used in the production of photosensitive materials, Japanese Patent Application Laid-open Nos. 62-169147, 62-169148, 62-209437,
No. 62-209438, No. 62-209439, No. 62-209440, No. 62-209441, No. 6
There are descriptions in each of the publications No. 2-209447 and No. 62-209437.

The microcapsule dispersion liquid subjected to the microencapsulation treatment can be used as it is as a coating liquid for photosensitive materials. A coating solution can then be prepared by mixing the silver halide emulsion and optionally a composition of other components such as an organic silver salt emulsion. It is also possible to add other components at the stage of this coating solution in the same manner as in the case of the emulsion described above.

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

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

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

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

The photosensitive material is developed at the same time as the imagewise exposure or after the imagewise exposure. 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 Japanese Patent Application Laid-Open No. 61-69062 which performs heat development treatment is a dry treatment, and therefore has the advantage of being simple to operate and capable of processing in a short time. Therefore, the development process for photosensitive materials is as follows:
The latter is especially good.

As the heating method in the above heat development treatment, various conventionally known methods can be used. In addition, like the photosensitive material described in JP-A No. 61-294434,
A heat generating layer may be provided on the photosensitive material and used as a heating means. Further, as in the image forming method described in JP-A-62-210461, heat development may be carried out while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 80°C to 200°C, preferably 100°C to 160°C.
It is ℃. The heating time is generally 1 second or more, preferably 1 to 5 minutes, and more 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 can be thermally developed as described above to polymerize the polymerizable compound in the area where the silver halide latent image is formed or the area where the silver halide latent image is not formed. In light-sensitive materials, the polymerizable compound in the area where the latent image of silver halide is generally polymerized in the heat development process described above.
As in the photosensitive material described in Japanese Patent No. 70836, by adjusting the type, amount, etc. of the reducing agent, it is also possible to polymerize the polymerizable compound in the area where the silver halide latent image is not formed.

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

When the photosensitive material is constructed like the photosensitive material described in 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 forming a polymer image on an image-receiving material, when a dye or a pigment is used as a color image-forming substance, the image-receiving material may be composed only of the above-mentioned support.

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

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

The image-receiving layer may contain a thermoplastic compound. When the image-receiving layer contains a thermoplastic compound, 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 that a glossy image can be obtained by heating after image formation. The thermoplastic compound is not particularly limited and can be arbitrarily selected from known plastics, waxes, and the like. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200° C. or lower. An image receiving material having an image receiving layer containing thermoplastic compound fine particles as described above is disclosed in Japanese Patent Application Laid-Open No. 62-2800.
There is a description in No. 71 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. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of smoothly proceeding with the curing process (fixing process) of the unpolymerized polymerizable compound. Regarding an image receiving material having an image receiving layer containing a photopolymerization initiator, see JP-A-62-161149,
Image-receiving materials having an image-receiving layer containing a thermal polymerization initiator are described in JP-A-62-210444.

A dye or pigment can be included in the image-receiving layer for the purpose of writing characters, symbols, frames, etc. on the image-receiving layer, or for the purpose of making the background of an image a specific color. Further, a dye or a pigment may be included in the image-receiving layer for the purpose of making it easier to distinguish between the front and back sides of the image-receiving material. As the dye or pigment, various known substances including dyes or pigments that can be used in image formation can be used, but there is a risk that the dye or pigment may damage the image formed in the image-receiving layer. In some cases, it is preferable to lower the dyeing density of the dye or pigment (for example, make the reflection density 1 or less), or to use a dye or pigment that has the property of being decolored by heating or light irradiation.

An image-receiving material having an image-receiving layer containing a dye or pigment that has the property of being decolored by heating or light irradiation is described in JP-A-62-251741.

Furthermore, when a white pigment such as titanium dioxide or barium sulfate is added to the image-receiving layer, the image-receiving layer can function as a white reflective layer. When the image-receiving layer functions as a white reflective layer, the white pigment is a thermoplastic compound! per g, 10g
It is preferable to use the amount in the range of 100 g to 100 g.

When the dye or pigment described above is contained in the image-receiving layer, it may be contained uniformly or unevenly distributed in a portion. For example, a part of the reflected image can be made into a projected image by forming the support described later from a material having light transmittance and including the white pigment in a part of the image-receiving layer.

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

The image-receiving layer may be configured as two or more layers depending on the functions described above. 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.

Furthermore, a pressure-sensitive adhesive or a layer containing an adhesive and a release paper may be laminated in this order on the surface of the support opposite to the surface on which the image-receiving layer is provided. The sticker-like image receiving material having the above structure is disclosed in Japanese Patent Application Laid-open No. 63-24647 by the present applicant.
There is a description in the bulletin.

The photosensitive material is developed as described above, and by pressing the image-receiving material in a stacked state, the unpolymerized polymerizable compound is transferred to the image-receiving material, and a polymer image can be obtained on the image-receiving material. can. Regarding the above pressurizing means,
Various conventionally known methods can be used.

Further, in an embodiment in which the photosensitive layer contains a color image forming substance,
By performing a similar development treatment, the polymerizable compound is polymerized and cured, thereby immobilizing the color image forming substance in the cured portion. Then, by pressing the photosensitive material and the image-receiving material in a superimposed state, the uncured portion of the color image-forming substance is transferred to the image-receiving material, and a color image can be obtained on the image-receiving material.

After forming an image on the image-receiving material as described above, the image-receiving material may be heated as in the image forming method described in Japanese Patent Application Laid-Open No. 62-210459. The above method also has the advantage that the unpolymerized polymerizable compound transferred onto the image-receiving material is polymerized and the storage stability of the obtained image is improved.

Additionally, the applicant has already filed patent applications for various image recording apparatuses suitable for carrying out the above-described series of image forming methods using photosensitive materials. Typical of these devices are an exposure device that forms a latent image by imagewise exposure, a heat development device that hardens and immobilizes the portion corresponding to the formed latent image, and a developed photosensitive device that (Japanese Unexamined Patent Publication No. 82-147461), which is composed of a transfer device that superimposes an image-receiving material on a material and pressurizes them; A structure equipped with a fixing device that uses either pressure or heat (Japanese Patent Application No. 60-28970)
3) etc.

Photosensitive materials include black and white or color photography and printing photosensitive materials, printing photosensitive materials, printing plates, X, 11! It has many uses, such as photosensitive materials, medical photosensitive materials (for example, ultrasonic diagnostic CRT imaging photosensitive materials), computer graphics hard copy photosensitive materials, photocopying machine photosensitive materials, and the like.

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] Nigelatin aqueous solution containing 3 1 halogen (24 g of gelatin in 1200 ml of water)
and 1.2 g of sodium chloride, and diluted with IN sulfuric acid p)
13.2 and kept warm at 60°C), 600 rnJZ of an aqueous solution containing 117 g of potassium bromide and an aqueous silver nitrate solution (0.74 mol of silver nitrate dissolved in 600 mL of water) were simultaneously added over a period of 15 minutes. Added at flow rate. 5 minutes after this addition is complete, potassium iodide 4
．． 200 mJZ of an aqueous solution containing 3 g was added over 5 minutes. To this dispersion, 1.2 g of poly(isobutylene-monosodium co-maleate) was added and precipitated, washed with water and desalted, 24 g of gelatin was added and dissolved, and further 5 mg of sodium thiosulfate and the following sensitizing dye were added. 0.47 g was added and chemical sensitization was carried out at 60° C. for 15 minutes to obtain a silver halide emulsion (A>) with a yield of 1000 g.

(Sensitizing Dye) In 100 g of the following polymerizable compound (Kayarad R-604, manufactured by Nippon Kayaku ■), the following copolymer 1, sg and 15 g of the following color image forming substance were dissolved. Next, 7.0 g of the following reducing agent (I) and the following reducing agent (
II) 7.5 g, 2 g of the following surfactant and 20 g of methylene chloride were dissolved to form a homogeneous solution.

Next, 2.5 g of a 10% aqueous solution of potassium bromide was added to 10 g of silver halide emulsion (A), stirred for 5 minutes, and the mixture was added to the above homogeneous solution. This mixed solution was stirred for 5 minutes at 15,000 revolutions per minute using a homogenizer while keeping the temperature at 25° C. to obtain a photosensitive composition consisting of a W10 emulsion.

(Polymerizable compound) (Reducing agent (1)) 1:H30-C112 C120(:QC:H-OH2 (copolymer) el+3 →e112-C←8°C(hc2Hs (color image forming substance) →CH, -( : ←2゜CO21; H2CH20H (Reducing agent (■)) A polyvalent isocyanate compound (Takenate D11ON, manufactured by Takeda Pharmaceutical Company Limited) was added to the photosensitive composition obtained as above.
4.5 g was added and stirred for 5 minutes. This mixture was mixed with sodium salt of polyvinylbenzenesulfonic acid (Versa
TL 502, manufactured by National Starch Co., Ltd.) was added to 210 g of a 10% aqueous solution of W.
A 10/W emulsion was obtained.

Separately, 34.5 g of melamine and 37 g of formaldehyde
% aqueous solution was added to 186 g of water, heated to 60°C,
The mixture was stirred for 30 minutes to obtain a transparent aqueous solution of melamine/formaldehyde initial condensate.

While stirring the above W10/W emulsion at 25°C, 80 g of an aqueous solution of the initial condensate was added, and 2
The pH was adjusted to 6.0 using 0% aqueous solution. Then,
This was heated to 60°C and stirring continued for 90 minutes.

Then, add 30g of urea 40% aqueous solution and add 20g of phosphoric acid.
The pH was adjusted to 3.5 using % aqueous solution. This mixed solution was heated to 60° C. and continued to be stirred for an additional 40 minutes. After this was allowed to cool to room temperature, the pH was adjusted to 7.0 using a 10% aqueous solution of sodium hydroxide to obtain a dispersion of photosensitive microcapsules having capsule walls made of melamine formaldehyde resin.

The dispersion of photosensitive microcapsules obtained as described above was placed in a centrifuge and rotated at 1000 revolutions per minute for 30 minutes to sediment the capsules.
An equal amount of distilled water was added.

The above washing step was repeated two more times under the same conditions.

The thus obtained dispersion of washed photosensitive microcapsules was adjusted to have the same solid content concentration as before washing.

40g of the following base precursor was added to cation-modified polyvinyl flucol (PVA-C31B-2A, Kuraray ■).
The mixture was dispersed in 160 g of a 3% aqueous solution of A. This dispersion was finely dispersed using a Dyno Mill at 3000 revolutions per minute for 2 hours to obtain a 20% solid dispersion (A) of a base precursor.

Margin below (base precursor) To 40 g of the dispersion of photosensitive microcapsules washed as described above, 8 g of the solid dispersion of base precursor (A) was added and stirred for 20 minutes. Next, 2 g of silver halide emulsion (A) was added to this and stirred for 10 minutes.

Add 10g of a 20% aqueous solution of sorbitol and 5% of Emarex NP-8 (manufactured by Nippon Emulsion ■) to the above dispersion.
6 g of the aqueous solution was added and then distilled water was added to prepare a coating solution for a photosensitive layer having a total amount of 75 g.

This coating solution was applied onto a polyethylene terephthalate film (support) at a coating weight of 45 g/m'',
After drying, a photosensitive material (I) according to the present invention was prepared.

Regarding the photosensitive material (I), when observing the state in which silver halide was attached to the microcapsules using a scanning electron microscope, it was found that the silver halide (accommodated in the microcapsules) added to the photosensitive layer outside the microcapsules was Substantially all of the silver halide (100 mol % based on the amount of silver halide present) was attached to the microcapsules.

Furthermore, when the photosensitive layer of the photosensitive material CI) was observed using a microscope, it was found that 70% of the solid fine particles of the base precursor
% or more were attached to the microcapsules.

[Example 2] Aqueous gelatin solution (24 g of gelatin in 1200 mL of water)
and 1.2 g of sodium chloride, and the pH was adjusted with IN sulfuric acid.
3.2 and kept warm at 60°C), 600 mfi of an aqueous solution containing 117 g of potassium bromide and an aqueous silver nitrate solution (0.74 mol of silver nitrate dissolved in 600 mIL of water) were simultaneously added over 15 minutes. Added at flow rate. Five minutes after this addition was complete, 4.3% of potassium iodide was added.
200 mL of an aqueous solution containing g was added over 5 minutes. To this dispersion, 1.2 g of poly(isobutylene-monosodium co-maleate) was added and precipitated, washed with water and desalted, 24 g of gelatin was added and dissolved, and 0.0 g of thiourea dioxide (fogging agent) was added. 05% aqueous solution 5+
L ml of a 0.1% aqueous solution of nJZ and chloroauric acid was added and ripened at 60° C. for 30 minutes, yielding 1000 g of a silver halide emulsion (B) with a fogged surface.

3 of the cation-modified polyvinyl alcohol used in the preparation of the solid dispersion (A) of the base precursor in Example 1 of the precursor.
A solid dispersion (B) of a base precursor was prepared in the same manner as in Example 1, except that 160 g of a 2% aqueous solution of acid-treated gelatin was used instead of 160 g of the 2% aqueous solution.

In addition, in preparing the photosensitive material (I) of Example 1, 2 g of silver halide emulsion (B) was used in place of 2 g of silver halide emulsion (A) added to the coating solution for the photosensitive layer, and a base A photosensitive material (n) according to the present invention was prepared in the same manner as in Example 1, except that 8 g of the solid dispersion of a base precursor (B) was used in place of 8 g of the solid dispersion of the precursor (A).

Regarding the photosensitive material (II), when observing the state in which silver halide was attached to the microcapsules, it was found that the silver halide added to the photosensitive layer outside the microcapsules (the silver halide contained in the microcapsules) (100 mol % based on the amount) was substantially all attached to the microcapsules.

In addition, when the photosensitive layer of the photosensitive material (IT) was observed using a microscope, it was found that among the solid fine particles of the base precursor,
More than 70% of the particles were attached to the microcapsules.

[Comparative Example 1] In the preparation of the photosensitive material (I) of Example 1, the same procedure as that of Example 1 was performed, except that the silver halide emulsion (A) was not added to the coating solution for the photosensitive layer. Similarly, comparative photosensitive material (III)
It was created.

[Comparative Example 2 1 color and no history] In the preparation of the photosensitive material (11) of Example 2, the same procedure as Example 1 was performed except that the silver halide emulsion (B) was not added to the coating solution for the photosensitive layer. Similarly, comparative photosensitive material (IV)
It was created.

2.5g of sodium hexametaphosphate in 123g of water
was dissolved, and 22 g of zinc 3.5-di-α-methylbenzylsalicylate and 53 g of 55% calcium carbonate slurry were mixed therewith, and the solution was dispersed using a Dynamyl disperser. To 40 g of the obtained liquid, 10 g of an 8% by weight polyvinyl alcohol aqueous solution, 4 g of a 10% by weight gelatin aqueous solution, 1.6 g of zinc chloride and 34 g of water were added and mixed uniformly. This mixed solution was applied onto art paper having a basis weight of 70 g/d to a wet film thickness of 90 μm, and then dried to prepare an image-receiving material.

Each of the photosensitive materials obtained in Example 1.2 and Comparative Example 1.2 was exposed imagewise through an optical wedge using a tungsten bulb, and then exposed to hot water at 150°C. It was placed on a plate and heated for 15 seconds. Next, each photosensitive material was overlapped with the above-mentioned image receiving material, and in that state, 55
The sample was passed through a pressure roller of 0 kg/cm''. The maximum density and minimum density of the positive color image obtained on the image-receiving material were measured using a Macbeth densitometer.

The above measurement results are shown in Table 1. Note that r silver halide J in Table 1 indicates the type of silver halide (inner) contained in the microcapsules and the type of silver halide (outer) attached to the surface of the microcapsules. Also, r
"Base precursor" indicates the type of solid dispersion of the base precursor.

Table 1 Photosensitivity Hemi Eno Kita Base Highest Lowest Material (Inner) (Outer) Precursor Concentration Concentration ■ (II) (A) (A) (A) (B) (A) (B) 1.29 1. 30 0.06 0.06 (III) (A) - (A) 1.15
(IV) , (A) - (B) 1.12
0.14 0.16 As is clear from the results shown in Table 1, the photosensitive materials (I) and ('II) of the present invention, in which silver halide is attached to photosensitive microcapsules, have extremely high contrast. gave a clear image.

Claims (1)

[Scope of Claims] 1. A photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound is provided on a support, and the silver halide and the polymerizable compound are photosensitive in a state accommodated in microcapsules. The photosensitive material contained in the layer is characterized in that the photosensitive layer outside the microcapsules also contains silver halide, and the silver halide is attached to the surface of the microcapsules. photosensitive material.