JPH0242445A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain high sensitivity and contrast by allowing a non- photosensitive silver salt and silver halide in the isolated state from each other. CONSTITUTION:The non-photosensitive silver salt and the silver halide are allowed to coexist in the isolated state from each other in the photosensitive material formed by incorporating the silver halide, reducing agent, polymerizable compd., and the non-photosensitive silver salt on a base and incorporating at least the polymerizable compd. among these materials into the photosensitive layer in the state of housing the same into microcapsules. The reaction of the non-photosensitive silver salt with the material absorbed on the silver halide is obviated in this way and the degradation of the sensitivity during preservation of the photosensitive material and the degradation of the contrast of the image are obviated and the development acceleration is maintained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive material having a photosensitive layer containing silver halide, a reducing agent, and a polymerizable compound on a support. More specifically, the present invention relates to a photosensitive material in which the photosensitive layer further contains a non-photosensitive silver salt.

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

Examples of image forming methods include the methods described in Japanese Patent Publication No. 11149/1980, Japanese Patent Publication No. 47-20741, Japanese Patent Publication No. 49-10697, Japanese Patent Application Laid-Open No. 138632/1982, and Japanese Patent Publication No. 58-169143. . In these methods, when the silver halide in the imagewise exposed photosensitive layer is developed using a developer, the coexisting reducing agent is oxidized, and 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. Regarding the above dry image forming method, Japanese Patent Application Laid-open Nos. 61-73145 and 61-183
No. 640, at-tea No. 5335, at-tea No. 61-275
This is also described in various publications such as No. 742 and No. 61-278849.

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

It is already known to introduce a non-photosensitive silver salt into the photosensitive layer as an improvement of the above-mentioned photosensitive materials (Japanese Unexamined Patent Application Publication No. 1983-1999).
Publication No. 3246). According to this photosensitive material, the presence of the organic silver salt further promotes the redox reaction (oxidation-reduction reaction catalyzed by the latent image of silver halide) that causes the polymerization reaction of the polymerizable compound. The development time can be shortened, and the dependence on heating time can be alleviated.

[Summary of the Invention] An object of the present invention is to provide a photosensitive material that has high sensitivity and provides clear images with good contrast.

In the present invention, a photosensitive layer contains silver halide, a reducing agent, a polymerizable compound, and a non-photosensitive silver salt on a support, and at least the polymerizable compound among these is contained in microcapsules. An object of the present invention is to provide a photographic material characterized in that the non-photosensitive silver salt and the silver halide are present in a state of being isolated from each other.

In the present invention, the r spacing taJ means that the respective substances are arranged in a physically non-contact state, and that the non-contact state does not change during storage and transportation at room temperature (environmental temperature).

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

(1) The silver halide is contained in a microcapsule containing the polymerizable compound, and the non-photosensitive silver salt is present outside the microcapsule.

(2) The non-photosensitive silver salt is contained in a microcapsule separate from the microcapsule containing the polymerizable compound.

(3) The non-photosensitive silver salt is present in a layer different from the layer containing silver halide (if the silver halide is contained in microcapsules, the layer in which the microcapsules are present) are doing.

(4) The non-photosensitive silver salt is a silver salt selected from the group consisting of benzotriazole silver, acetylene silver and silver chloride.

(5) The content of the non-photosensitive silver salt is in the range of 0.01 to 50 mol% based on silver halide.

(6) The average particle size of the non-photosensitive silver salt is in the range of 0.01 to 5 μm.

(7) The photosensitive layer contains a compound capable of adsorbing silver halide.

[Effects of the Invention] As described above, the non-photosensitive silver salt participates in the redox reaction catalyzed by the latent image of silver halide, and has the function of promoting development. For this reason, non-photosensitive silver salts are usually used in contact with or in close proximity to silver halide (for example, non-photosensitive silver salts are used in the process of preparing photosensitive compositions (polymerization) in the production of photosensitive materials. It is added in the form of a non-photosensitive silver emulsion to the silver halide emulsion in the step of dispersing an aqueous phase containing a silver halide emulsion in an oil phase containing a chemical compound.Also, the composition is encapsulated. In some cases the non-photosensitive silver salt will be present in the capsule together with the silver halide).

According to studies conducted by the present inventors, it has been found that although the photosensitive material produced by the method described above achieves the effect of accelerating development, it is accompanied by a decrease in sensitivity and a decrease in contrast. In this case, by placing a non-photosensitive silver salt in contact with or in close proximity to silver halide, substances adsorbed to the silver halide (e.g., antifoggants, thermal solvents, etc.) are removed from the non-photosensitive silver. It is thought that this occurs because it reacts with salt, causing a decline in its original function.

According to the light-sensitive material of the present invention, since the non-photosensitive silver salt is isolated from the silver halide, no reaction occurs with substances adsorbed on the silver halide as described above. Therefore, a decrease in sensitivity and a decrease in image contrast are less likely to occur during storage of the photosensitive material, and therefore the development can be accelerated without these disadvantageous effects.

DETAILED DESCRIPTION OF THE INVENTION There are various embodiments of the method of separating the non-photosensitive silver salt from the photosensitive silver halide according to the present invention. In the present invention,
Particularly preferred is a method in which a capsule wall containing a polymerizable compound is used as an isolation means.

That is, this is a method in which silver halide is contained in a capsule containing a polymerizable compound, and a non-photosensitive silver salt is present outside the capsule (photosensitive capsule) to isolate it. In addition,
As the capsule wall material in this case, melamine resin is preferable. Other methods include a method of accommodating and isolating a non-photosensitive silver salt in a capsule other than the above-mentioned capsule (photosensitive capsule), or a method of separating the non-photosensitive silver salt in a layer containing silver halide (a layer containing silver halide). If silver is contained in microcapsules, the layer in which the microcapsules are present)
There is also a method of isolating it by making it exist in a separate layer.

To make the non-photosensitive silver salt exist outside the photosensitive capsule,
A method in which a photosensitive capsule dispersion (not containing a non-photosensitive silver salt) is prepared, and then a non-photosensitive silver salt is added in the form of an emulsion to a coating solution containing this dispersion for forming a photosensitive layer. is available. In addition, in order to accommodate the non-photosensitive silver salt in a capsule separate from the photosensitive capsule, oil droplets containing the non-photosensitive silver salt are formed using an appropriate solvent, and then the oil droplets are added to the photosensitive capsule manufacturing method. A method of encapsulation using a method similar to that can be used. Furthermore, in order to make the non-photosensitive silver salt exist in a layer separate from the layer containing silver halide, a coating solution consisting of an emulsion containing the non-photosensitive silver salt is coated on the support. A method can be used in which a layer containing salt is formed and then a layer containing silver halide is provided on this layer. In this case, the non-photosensitive silver salt and the silver halide may be housed in different microcapsules.

There are no particular limitations on the non-photosensitive silver salt that can be used in the photosensitive material of the invention. They can be appropriately selected from conventionally known ones and used alone or in combination.

In addition, non-photosensitive silver salts include non-photosensitive silver salts, photosensitive silver salts,
Then, the photosensitive material containing the color image forming substance in the photosensitive layer is exposed to light, and the photosensitive material is made from the same photosensitive material with an amount of light that is 100 times the minimum amount at which immobilization of the image form of the color image forming substance is observed. A silver substance in which immobilization of image-forming color image-forming substances is not observed when a light-sensitive material from which only silver halide has been removed is exposed.

Examples of non-photosensitive silver salts include silver salts of aliphatic or aromatic carboxylic acids, silver salts of compounds containing a mercapto group or a thiocarbonyl group having alpha hydrogen, or compounds containing an imino group, or sensitized silver salts. Examples include untreated silver halides such as silver chloride and silver bromide.

Examples of silver salts of aliphatic carboxylic acids include behenic acid,
stearic acid, oleic acid, lauric acid, caproic acid,
myristic acid, palmitic acid, maleic acid, fumaric acid,
Mention may be made of the silver salts of tartaric acid, furoic acid, linoleic acid, liluic acid, adipic acid, sebacic acid, succinic acid, acetic acid, butyric acid or camphoric acid. Silver salts of fatty acids and carboxylic acids having halogen atoms or hydroxyl groups or thioether groups of these fatty acids can also be used.

Examples of silver salts of aromatic carboxylic acids include benzoic acid,
3.5-dihydroxybenzoic acid, ortho-meta-, para-methylbenzoic acid, 2.4-dichlorobenzoic acid, acetamidobenzoic acid, p-phenylbenzoic acid, gallic acid, tannic acid, phthalic acid, terephthalic acid, salicylic acid Examples include silver salts with phenylacetic acid, phenylacetic acid, and pyromellitic acid. Also, 3-carboxymethyl-4-methyl-4-
Silver salts of other carboxyl group-containing compounds such as thiazoline-2-thione and the like can also be used.

Examples of the silver salt of a compound having a mercapto group or a thiocarbonyl group having α hydrogen include 3-mercapto-4-phenyl-1,2,4-triazole, 2-mercaptobenzimidazole, 2-mercapto-5-amino Thiadiazole, 2-mercaptobenzthiazole, S-alkylthioglycolic acid (12 to 22 carbon atoms)
), dithiocarboxylic acids such as dithioacetic acid, thioamides such as thiostearamide, 5-carboxy-1-methyl-2-phenyl-4-thiopyridine,
Mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-
Mention may be made of silver salts such as mercapto compounds such as 5-benzylthio-1,2,4-triazole (described in US Pat. No. 4,123,274).

As a silver salt of a compound having an imino group,
30270 or 45-18416 or derivatives thereof, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, halogen-substituted benzotriazoles such as 5-chlorobenzotriazole,
Carboimidobenzotriazoles such as butylcarboimidobenzotriazole, JP-A-58-118639
Nitrobenzotriazoles described in Publication No. 58-
Sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or hydroxybenzotriazole described in US Pat. No. 118638, US Pat.
Silver salts such as 1,2,4-triazole, IH-tetrazole, carbazole, saccharin, imidazole and derivatives thereof described in No. 20,709 can be mentioned.

Also, Research Disclosure Magazine 17029 (1
Organometallic salts other than silver salts and copper stearate described in JP-A-60-22153 (June 1978)
A silver salt of a carboxylic acid having an alkynyl group such as phenylpropiolic acid described in Japanese Patent No. 5 can be used.

Furthermore, a silver salt compound represented by the following general formula (1) can also be used.

R-C=C-Ag...(1) [In the above formula (1), R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, or a heterocyclic group (provided that , each of the above groups may have a substituent)] In the above formula (1), R is preferably a substituted or unsubstituted phenyl group.

The non-photosensitive silver salt mentioned above is
The details are described in Publication No. 2-3246.

Moreover, among the compounds represented by the above general formula (1),
In particular, a non-photosensitive silver salt having a PAg of 8 or more (measured value when dispersed in water with a pH of 6.4) is effective when the photosensitive layer contains a hydrazine compound.

Specifically, the following silver salts of acetylene compounds having a mercapto group can be mentioned.

The details of the silver salt of the acetylene compound mentioned above are described in Japanese Patent Application No. 1982-214796.

The average particle size of the above non-photosensitive silver salt is preferably in the range of 0.01 to 5 μm, more preferably in the range of 0.01 to 5 μm.

Further, the content of the non-photosensitive silver salt is preferably in the range of 0.01 to 50 mol % based on silver halide.

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

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

The halogen composition of the silver halide grains may be uniform on the surface and inside or may be non-uniform. 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
It is described in the 00984 specification. Also, JP-A-62
Silver halide grains having a high proportion of silver iodide in the shell portion may be used, as in the photosensitive material described in Japanese Patent No. 183453.

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

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

For the silver halide used in the 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 light-sensitive material, the average grain size of the silver halide grains is preferably from o,oot to 5 μm, and from 0.0 to 5 μm.
More preferably, the thickness is 0.001 to 2 μm.

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

A reducing agent that can be used in a light-sensitive material has a function of reducing silver halide and/or a function of promoting (or inhibiting) polymerization of a polymerizable compound. There are various types of reducing agents having the above functions. The reducing agents include hydroquinones, catechols, p-aminophenols, p-phenylenediamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-
Pyrazolones, 5-aminouracils, 4゜5-dihydroxy-6-aminopyrimidines, reductones, amylreductones, O- or p-sulfonamidophenols, O- or p-sulfonamidonaphthols,
2-sulfonamide indanones, 4-sulfonamide-5-pyrazolones, 3-sulfonamide indoles, sulfonamide virazopenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamide ketones, hydrazines etc. 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 r-reducing agent 1 in this specification includes the reducing agents and reducing agent precursors described in each of the above-mentioned publications, specifications, and literature. 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-phenyl Sulfonylamino-4-7-butyl-5-hexadecyloxyphenol, 2-(N-butylcarbamoyl)-4-phenylsulfonylaminonaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol , 1-acetyl-2-phenylhydrazine, 1-acetyl-2-(
(p or 0)-aminophenyl)hydrazine, 1-formyl-2-((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, l
-phenyl-2-(2,4,6-)dichlorophenyl)
and dorazine, 1-(2-(2,5-di-t-pentylphenoxy)butyroyl)-2-((p or 0)-aminophenyl)hydrazine, 1-(2-(2,5-di-t -pentylphenoxy)butyroyl)-2-((P
or 0)-aminophenyl)hydrazine pentadecylfluorocaprylate, 3-indazolinone, 1-(
3,5-dichlorobenzoyl)-2-phenylhydrazine, l-trityl-2-[((2-N-butyl-N-octylsulfamoyl)-4-methanesulfonyl)phenyl]hydrazine, 1-(4- (2,5-di-t-pentylphenoxy)butyroyl)-2-((p or 0)
-methoxyphenyl)hydrazine, 1-(methoxycarbonylbenzohydryl)-2-phenylhydrazine, 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]hydrazine, 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-Tritylhydrazine, 1-(2,4-dimethoxybenzoyl)-2
-tritylhydrazine, 1-(4-dibutylcarbamoylbenzoyl)-2-tritylhydrazine, and 1-
(1-naphthoyl)-2-tritylhydrazine and the like can be mentioned.

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

The polymerizable compound that can be used in the photosensitive material is not particularly limited, and any known polymerizable compound can be used. In addition, when heat development treatment is planned as a method of using the photosensitive material, it 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.

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

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

Compounds with ethylenically unsaturated groups that can be used in photosensitive materials include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides, and maleic anhydride. 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.

The polymerizable compound is contained in microcapsules. Various known techniques can be applied to the microcapsules without particular limitations. An example of a photosensitive material in which oil droplets of a polymerizable compound are in the form of microcapsules is described in JP-A-61-278441.

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.

When silver halide is contained in microcapsules containing the above polymerizable compound, it is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsules.

A photosensitive material containing silver halide in the wall material of microcapsules is described in JP-A-62-169147. Preferably, the microcapsules contain a reducing agent.

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, please refer to JP-A-62198.
There is a description in Publication No. 850.

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 @thickness of microcapsules is
As in the photosensitive material described in Publication No. 6, it is preferable that the particle diameter is within a certain range.

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

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

Optional components that can be included in the photosensitive layer of the photosensitive material include color image forming substances, sensitizing dyes, radical generators, various image formation accelerators, thermal polymerization inhibitors, thermal polymerization initiators,
Development stopper, fluorescent whitening agent, antifading agent, dye or pigment for preventing halation or irradiation, pigment that has the property of decolorizing when heated or exposed to light, matting agent, anti-smudge agent, plasticizer, water release agent , binders, photopolymerization initiators, solvents for polymerizable compounds, water-soluble vinyl polymers, etc.

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.

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. 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 the sensitizing dye added is generally about 10-8 to 10-2 mol per mol of silver halide.

The above-mentioned sensitizing dye is preferably added during the preparation stage of the silver halide emulsion described below. 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-62210449. 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.

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

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

Various image formation accelerators can be used in the photosensitive material. Image formation accelerators include those that promote the redox reaction between silver halide (and/or organic silver salt) and a reducing agent, and those that promote the redox reaction between silver halides (and/or organic silver salts) and reducing agents, and those that promote the redox reaction between silver halides (and/or organic silver salts) and reducing agents, and those that promote the redox reaction between silver halides (and/or organic silver salts) and reducing agents, and those that promote the redox reaction between silver halides (and/or organic silver salts) and reducing agents. It has functions such as promoting the movement of image forming substances.

From the viewpoint of physicochemical functions, image formation accelerators include bases,
Base precursor, oil, surfactant, compound having a function of promoting adsorption to silver halide (specifically, a compound having a function of preventing fogging and/or a function of promoting development)
, thermal solvents, and compounds with oxygen removal functions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Therefore, the above classification is for convenience, and in reality, one compound often has multiple functions.

Examples of various image formation accelerators are shown below.

Examples of preferred bases include, as inorganic bases, alkali metal or alkaline earth metal hydroxides; alkali metal or alkaline earth metal primary phosphates, borates;
carbonates, metaborates; combinations of zinc hydroxide or zinc oxide with chelating agents such as sodium picolinate;
Ammonium hydroxide; hydroxide of quaternary alkylammonium; hydroxide of other metals, etc. Examples of organic bases include aliphatic amines (trialkylamines,
hydroxylamines, aliphatic polyamines); aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis[p-
(dialkylamino)phenylcomethanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, etc., and those having a pKa of 7 or more are particularly preferred.

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

The base or base precursor can be used in the photosensitive material in a wide range of amounts. The base or base precursor 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 40% by weight is useful. In the present invention, the base site and/or base precursor may be used alone or as a mixture of two or more.

Incidentally, a photosensitive material using a base or a base precursor is described in Japanese Patent Application No. 60-227528. Further, for a photosensitive material using a tertiary amine as a base, see JP-A-62-170954, and for a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound with a melting point of 80 to 180°C. Japanese Patent Publication No. 82-20952
No. 3 describes a photosensitive material using a guanidine derivative with a solubility of 0.1% or less in JP-A No. 62-215637.
In the specification of the patent application No. 1987, for photosensitive materials using hydroxides or salts of alkali metals or alkaline earth metals,
Each of these is described in the specification of No.-96341.

Furthermore, regarding a photosensitive material using an acetylide compound as a base precursor, JP-A-63-24242 discloses a photosensitive material using a propiolate as a base precursor.
Furthermore, regarding photosensitive materials containing silver, copper, silver compounds, or copper compounds as catalysts for base-forming reactions, JP-A-63-46
No. 446 discloses the above propiolic acid salt and the above silver, copper,
Regarding a photosensitive material containing a silver compound or a copper compound in a state separated from each other, JP-A-63-81338 discloses that in addition to the above-mentioned propiolic acid salt and the above-mentioned silver, copper, silver compound, or copper compound, coordination in a free state JP-A-63-97942 describes a photosensitive material containing a base precursor, and JP-A-63-9794 describes a photosensitive material that uses a propiol salt as a base precursor and further contains a heat-melting compound as a reaction accelerator for the base production reaction. No. 46447 describes a photosensitive material that uses a sulfonylacetate as a base precursor and further contains a heat-melting compound as a reaction accelerator for the base production reaction. Photosensitive materials using compounds to which cyanate or inthiocyanate are bonded are described in JP-A-63-24242.

When using a base or base precursor in a photosensitive material,
It is preferable that silver halide, a reducing agent, and a polymerizable compound are contained in the microcapsules described above, and a base or a base precursor is present in the photosensitive layer outside the microcapsules. Or, JP-A-62-2095
As in the photosensitive material described in Japanese Patent No. 21, the base or base precursor may be contained in separate microcapsules. In addition to the photosensitive materials using microcapsules containing bases or base precursors, there is also a photosensitive material containing microcapsules containing bases or base precursors dissolved or dispersed in an aqueous water-retaining agent solution, as described in JP-A-62. Japanese Unexamined Patent Publication No. 209522 discloses a photosensitive material in which solid fine particles carrying a base or a base precursor are housed in microcapsules, and JP-A-62-209526 discloses a photosensitive material in which microcapsules containing a basic compound having a melting point of 70°C to 210°C is used. Regarding the photosensitive material used, see Japanese Patent Application Laid-Open No. 1986-
Each of these is described in Japanese Patent No. 65437. Furthermore, instead of the microcapsules containing a base or base precursor, particles containing a base or a base precursor and a hydrophobic substance in a compatible state may be used, as in the photosensitive material described in JP-A-63-97943. .

The base or base precursor is described in Japanese Patent Application Laid-Open No. 62-2
As described in Japanese Patent No. 53140, it may be added to an auxiliary layer other than the photosensitive layer (a layer containing a base or a base precursor, which will be described later). Furthermore, JP-A-63-32
As described in Japanese Patent Application No. 546, the above-mentioned support may be made porous and a base or a base precursor may be contained in the porous support.

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

Examples of the surfactant include 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
Regarding photosensitive materials using thiol derivatives,
Regarding photosensitive materials using acetylene compounds, see JP-A No. 62-151844, and JP-A No. 62-1782 regarding photosensitive materials using acetylene compounds.
32, for photosensitive materials using sulfonamide derivatives, see JP-A-62-183450, and for photosensitive materials using quaternary ammonium salts, see JP-A-63-1999.
Publication No. 91653 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. 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 4, 1983, Kyoritsu Publishing, edited by the Editorial Committee of Polymer Experiments, The Polymer Society of Japan.Thermal polymerization initiators is preferably used in a range of 0.1 to 120% by weight, more preferably in a range of 1 to 10% by weight based on the polymerizable compound.Note that a latent image of silver halide is not formed. In a system in which a partial polymerizable compound is polymerized, it is preferable to add a thermal polymerization initiator to the photosensitive layer.Photosensitive materials using a thermal polymerization initiator are described in JP-A-62-70836. There is.

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
Oxime esters described in JP-A No. 08837 and JP-A-60-192939, and compounds that release acid by Rossen rearrangement described in JP-A No. 60-230133 can be mentioned.

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.

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. Hydrophilic binders are typically transparent or translucent, such as natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, etc., and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc. Contains synthetic polymeric materials such as water-soluble polyvinyl compounds.

Other synthetic polymeric materials include dispersed vinyl compounds, especially in the form of latexes, which increase the dimensional stability of photographic materials. 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.

Examples of optional components that can be included in the photosensitive layer in addition to those mentioned above and their usage can be found in the application specifications related to the above-mentioned series of photosensitive materials and Research Disclosure Vol.

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

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

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

In the photosensitive material of the present invention, the photosensitive silver halide and the non-photosensitive silver salt are separated by the above-mentioned isolation means (isolation method), and in a particularly preferred embodiment, a capsule is used as the isolation means. The method for manufacturing the photosensitive material will be explained.

A typical manufacturing method consists of the following steps. That is, the process of preparing a photosensitive composition by dissolving, emulsifying or dispersing components of the photosensitive layer other than the non-photosensitive silver salt (polymerizable compound, silver halide, etc.) in an appropriate solvent; A step of encapsulating the composition to prepare a photosensitive capsule dispersion, a step of adding a non-photosensitive silver salt emulsion to the photosensitive capsule dispersion to prepare a coating solution, and applying the coating solution to a support, It consists of a drying process.

Generally, the above-mentioned photosensitive composition is prepared by preparing a liquid composition containing each component and then mixing the respective liquid compositions. The above liquid composition is
It 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. moreover,
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 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 a hydrophilic colloid (eg, gelatin) as a protective colloid.

Silver halide emulsions are prepared by using ammonia, organic thioether derivatives (see Japanese Patent Publication No. 47-386), and sulfur-containing compounds (see Japanese Patent Application Laid-Open No. 144319-1987) as silver halide solvents in the stage of forming silver halide grains.
etc. can be used. Further, in the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be allowed to coexist. Furthermore, for the purpose of improving high-light failure and low-light failure, iridium chloride (■ or ■),
Water-soluble iridium salts such as ammonium hexachloroiridium salts 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. Although the silver halide emulsion may be used unripe, 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. 58
-126526, No. 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. 55/510.

In addition, when adding a nitrogen-containing heterocyclic compound as a compound having the above-mentioned capri-preventing function and/or development accelerating function, it should be added at the stage of forming or ripening 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 prepared using a homogenizer, blender, or mixer.

It can be obtained by stirring with 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. Also, JP-A-61
When oil droplets of a polymerizable compound are microencapsulated as in the photosensitive material described in Japanese Patent No. 275742, a wall material necessary for microencapsulation is added to this emulsion,
Furthermore, a treatment for forming the outer shell of microcapsules can also be carried out at the stage of this emulsion. Further, a reducing agent or other optional components may be added at the stage of the emulsion.

Examples of the above-mentioned microencapsulation method include a method using coacervation of aromatic wood-philic wall-forming materials as described in U.S. Pat. No. 2,800,457 and U.S. Pat. No. 2,800,458; U.S. Pat. Specification of contents and Japanese Patent Publication No. 3B-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 Method using the isocyanate wall material described in U.S. Pat. No. 4,001,140;
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 Method using the forming material: In-5-itu method by polymerization of 1,000 yen as described in Japanese Patent Publication No. 36-9168 and Japanese Patent Application Laid-open No. 51-9079; described in British Patent No. 927807 and British Patent No. 965074 Polymerization dispersion cooling method; US Pat. 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 the polymerizable compound into oil droplets is not limited to the above, a method in which a core material is emulsified and then a polymer film is formed as the microcapsule wall is particularly preferred.

A coating solution is prepared by adding the non-photosensitive silver salt emulsion according to the present invention and other optional components as desired to the photosensitive microcapsule dispersion prepared as described above, and then the coating solution is applied to a support. The photosensitive material of the present invention is produced by coating and drying. 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 performed 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 16°C.
It is 0°C. The heating time is generally 1 second or more, preferably 1 second 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, the photosensitive material is subjected to development and pressurized to destroy the microcapsules and cause a coloring reaction. A color image can be formed on a photosensitive material by bringing two types of 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 on a support.

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

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

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 above thermoplastic compound is not particularly limited and can be arbitrarily selected from known plastic resins (plastics), waxes, and the like. However, the glass transition point 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. 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.

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

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

The photosensitive material is developed as described above, and 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.

In addition, the present applicant has already filed patent applications for various image recording devices suitable for carrying out the above-described series of image forming methods using photosensitive materials (Japanese Patent Laid-Open No. 1983-1411).
Publication No. 7461, etc.).

Photosensitive materials include black and white or color photography and printing photosensitive materials, printing photosensitive materials, printing plates, X-ray photosensitive materials, medical photosensitive materials (for example, ultrasonic diagnostic CRT photosensitive materials), computer graphic hard copy photosensitive materials, It has many uses, such as photosensitive materials for copying machines.

The present invention will be explained in more detail by the following examples. However, the present invention is not limited to these.

[Example 1] [Preparation of photosensitive material] Sensitivity of gold salt - 6.5 g of benzotriazole and 10 g of gelatin were added to 1 part of water.
0100O! dissolved in This solution was kept at 50°C and stirred. Next, add 8.5 g of silver nitrate to 10,100 O of water! was added to the above solution over a period of 2 minutes. By adjusting the pH of this, unnecessary salts are precipitated and removed, and then p
H was adjusted to 6.0, and benzotriazole silver was obtained in a yield of 400 g.

Preparation of Halogen Milk
and 1.2 g of sodium chloride, and diluted with IN sulfuric acid p)
13.2 and kept warm at 60°C), 600 mjL 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 added to it while stirring. Additions were made simultaneously at equal flow rates over 15 minutes. One minute after this addition was completed, 47 cc of a 1% methanol solution of the following sensitizing dye was added.
Furthermore, 15 minutes after the completion of the dye addition, 200 mL of an aqueous solution containing 4.3 g of potassium iodide was added over 5 minutes. To this emulsion, 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 was added and the mixture was heated at 60°C for 15 min.
Chemical sensitization was carried out for a minute to obtain a silver halide emulsion with a yield of 1000 g.

To 100 g of sensitizing dye W O emulsion trimethylolpropane triacrylate (Aronix M-309, manufactured by Toagosei Kagaku ■), 0.40 g of the following copolymer and Pergus Script Red 1-6-B (manufactured by Ciba Geigy) were added. OOg was dissolved. Then, the above solution 24. To OOg, 1.29 g of the following hydrazine derivative (reducing agent), 1.22 g of the following developer (reducing agent), 0.36 g of Emarex NP-8 (manufactured by Nippon Emulsion ■), and 0.003 g of the following mercapto compound, Furthermore, add methylene chloride 4, oog,
An oily liquid was obtained.

On the other hand, 0.46 g of a 10% aqueous solution of potassium bromide was added to 3.00 g of the silver halide emulsion described above and stirred for 5 minutes.
An aqueous liquid was obtained.

Next, an aqueous liquid was added to the above oily liquid and stirred for 5 minutes at 15,000 revolutions per minute using a homogenizer to obtain W10.
A photosensitive composition in the form of an emulsion was obtained.

Margin below (copolymer) (Hydrazine derivative) C2H.

(Developer) (Mercapto compound) Sodium salt of polyvinylbenzenesulfonic acid (Ver.
sa TL 500 (manufactured by National Starch) 10
% aqueous solution was adjusted to pH 3.5 using a 20% aqueous solution of phosphoric acid. On the other hand, in the photosensitive composition, Takenate DII
ON (polyvalent isocyanate compound, manufactured by Narita Pharmaceutical Co., Ltd.)
0.90 g was added to the above aqueous solution. This mixed solution was heated to 40° C. and stirred for 30 minutes at 7000 rpm using a homogenizer to obtain a W10/W emulsion.

Separately, melamine 13.20g and formaldehyde 37%
Add 21.6 g of aqueous solution and 70.8 g of distilled water,
C. and stirred for 30 minutes to obtain a transparent aqueous solution of melamine/formaldehyde precondensate.

Aqueous solution of this initial condensate13. OOg, above W10
/W emulsion was added and the pH was adjusted to 6.5 using a 20% aqueous solution of phosphoric acid. Next, this was heated to 50°C and stirred for 120 minutes. Furthermore, the pH was adjusted to 7.0 using an IN sodium hydroxide aqueous solution to obtain a photosensitive microcapsule dispersion having capsule walls made of melamine formaldehyde resin.

To 2.50 g of the photosensitive microcapsule dispersion prepared above with ratio A, 1.0 g of a 5% aqueous solution of the following surfactant, 2.3 g of a 20% solid dispersion of the following base precursor, and 20% sorbitol were added. 3.0 g of the solution and 0.7 g of the silver benzotriazole were added, followed by 3.3 g of a 20% corn starch aqueous dispersion and 7.0 g of distilled water, and the mixture was thoroughly stirred to prepare a coating solution. This coating liquid was applied onto cast coated paper (manufactured by Sanyo Kokusaku Valve ■) with a basis weight of 65 g/rn'' using a #40 wire bar, and dried at about 40°C to form a photosensitive material (A) according to the present invention. It was created.

(Surfactant) (Base precursor) [Example 2] Di-sensitivity ≦ Salt - 3.4 g of sodium chloride and 40 g of gelatin in 100 g of water
It was dissolved at 100O. This solution was kept at 40"C and stirred. Next, 34.4 g of sodium chloride was added to 600 mL of water.
A solution prepared by dissolving 100 g of silver nitrate in 600 mJ2 of water were simultaneously added to the above solution at a rate of 150 mJl per minute over a period of 4 minutes. By adjusting the pH of this solution, unnecessary salts were precipitated and removed, and the pH was adjusted to 6.4 to obtain 600 g of non-photosensitive silver chloride.

In Example 1 of Sensitivity B, the procedure was the same as in Example 1, except that 0.3 g of the non-photosensitive silver chloride prepared above was used instead of silver benzotriazole when preparing the photosensitive material. In this way, a photosensitive material (B) according to the present invention was prepared.

[Example 3] Sensitivity to Salt - 5 g of the following acetylene compound was dissolved in 50 m2 of methanol. Next, 10.5 g of gelatin and 4.7 g of silver nitrate
g was dissolved in 3 QmfL of water, and the above solution was added while maintaining the temperature at 50°C and stirring. After stirring for 30 minutes, unnecessary salts are precipitated and removed by adjusting the pH.
was adjusted to 6.4, and acetylene silver was obtained in a yield of 350 g.

In Example 1, when preparing a photosensitive material, the acetylene silver 0 prepared above was used instead of benzotriazole silver.
．． A photosensitive material (C) according to the present invention was prepared in the same manner as in Example 1 except that 7 g was used.

[Comparative Example 1] Preparation 1 of W O emulsion Example 1 except that 6 g of benzotriazole silver was added to the aqueous phase (W) when preparing the W10 emulsion (photosensitive composition) in Example 1. A W10 emulsion (photosensitive composition) was prepared in the same manner as above.

,,'4D Example 1 was carried out in the same manner as in Example 1, except that the photosensitive composition described above was used and benzotriazole silver was not added to the coating solution. A comparative photosensitive material (D) was prepared by the following operations.

[Comparative Example 2] In Example 1 of Sensitivity E, except that silver benzotriazole was not added to the coating solution when preparing the photosensitive material,
A comparative photosensitive material (E) was prepared in the same manner as in Example 1.

11 Hayashi Kotatsu L 11 g of 40% sodium hexametaphosphate aqueous solution was added to 125 g of water, and further mixed with 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 5.5% calcium carbonate slurry. and roughly dispersed with a mixer. Disperse the liquid with a Dynamyl dispersion machine, and 2 of the obtained liquid
00g to 50% SBR latex 6g and 8%
55 g of polyvinyl alcohol aqueous solution was added and mixed uniformly. This mixed solution was placed on baryta paper with a basis weight of 43 g/d.
After uniformly coating the film to a wet film thickness of μm, it was dried to prepare an image receiving material.

[Evaluation as a Photosensitive Material] Each of the photosensitive materials (A-D) obtained above was evaluated in the following manner.

Each photosensitive material was exposed to light at 200 lux using a tungsten bulb through a filter with a continuous density pattern.
After exposure for seconds, this was placed on a hot plate at 155° C. and heated for 10 seconds. Next, each photosensitive material was stacked on the above-mentioned image receiving material, and in that state, 450 kg /
The maximum density (Dmax) and minimum density (Dmin) of the magenta positive color image obtained on the image-receiving material were measured using a Macbeth densitometer. Sensitivity was measured.

The above results are summarized in Table 1. In Table 1, the sensitivity is expressed as the logarithm of the amount of exposure required to make the image density 0.5.

Table 1 As is clear from the results shown in Table 1, the photosensitive materials (A), (B) and (C) according to the present invention, which contain the non-photosensitive silver salt in a state separated from the silver halide, , high sensitivity and high contrast.

Claims (1)

[Claims] 1. A photosensitive material containing silver halide, a reducing agent, a polymerizable compound, and a non-photosensitive silver salt on a support, and at least the polymerizable compound among these is contained in a photosensitive layer in a state accommodated in microcapsules. A photosensitive material characterized in that the non-photosensitive silver salt and the silver halide exist in a state of being isolated from each other.