JPH0333748A - Recording material and recording method - Google Patents

Abstract

PURPOSE:To form a polymer image by a rapid processing which is of a dry type or for which an extremely slight volume of water is used by incorporating a photosensitive layer contg. a photosensitive silver halide, polymerizable compd., thermo- or photopolymn. initiator, and specific reducing agent on a base. CONSTITUTION:The photosensitive layer contg. the photosensitive silver halide, the polymerizable compd., the thermo- or photopolymn. initiator, and the reducing agent expressed by formula I or II is provided on the base. In the formula I, II, R<1> denotes a hydrogen atom, alkyl group, aryl group or heterocyclic group; R<2> to R<6> dentoe a hydrogen atom halogen atom, or monovalent org. group, such as alkyl group, sulfonyl amino group or sulfamoyl amino group; R<2> to R<6> may be respectively the same or different and any two may combine to form a ring. The recording material is heated simultaneously with or after image exposing or is further irradiated uniformly with light after the heating, by which polymerizable compd. in the exposed part is polymerized and the polymer image is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a recording material and a recording method in which the BAFi photosensitive silver halide of the present invention is used as a photosensor and a polymer image is formed in the exposed area by heating.

``Prior art'' The technology of using organic ultraviolet light absorbers or organic dyes as photosensors or polymerization initiators to form polymer images in the same way as exposed images is well known, but it generally has low sensitivity and requires long-term use. Exposure is required. Therefore, although it has various useful features, its applications are currently limited due to this sensitivity restriction.

Therefore, in order to solve this problem of sensitivity, research has been conducted on a method of using silver halide as a photosensor and generating two radicals during or after the development process to cause a polymerization reaction. For example, Tokko Sho at-ilty, same <47
-JOJJr%sameg7-6111. &A-2/723
, same 7-/, 2ta! , same ψ7-/gubu67, same 4t
7-/g6tt, same 4!7-/1164? , Same 4! A-
/lJ! 7% same 177-/rjtlr! , 447-2
07171. Same geter/14F, same ay-iz7o, same 4'P-106ri 7 publication, JP-A-17-197-/JrlsJ2
,same! 7-/12431% same j7-/7403! ,same!
l-107!2 ri, same! r-/J W/4tj and the same! ? A method of causing a polymerization reaction by radicals generated from a reducing agent oxidized during the development process of silver halide, as described in the publication No. -/7φPψγ, published by Tokko Shoφ/-/11
As described in Japanese Patent Publication No. 42, a method of generating radicals from one peroxide through an oxidation-reduction reaction between developed silver and a peroxide to cause a polymerization reaction, as described in Japanese Patent Publication No. 3P-λ17. A method of causing a polymerization reaction by generating radicals from peroxide through an oxidation-reduction reaction between silver ions remaining in unexposed areas and peroxide, as shown in U.S. Patent No. 3,0 Kota, /
As stated in IA No. ', silver halide is mixed with iron (
1) A method of developing with salt and causing a polymerization reaction with radicals generated from the peroxide through an oxidation-reduction reaction between the iron(1) salt remaining in the unexposed area and the peroxide, JP-A-Shoj! -/4'2WJP
As described in the publication, after developing silver halide,
This method involves directly causing a polymerization reaction using a reducing agent remaining in the unexposed area. In principle, these methods are thought to be able to form polymer images with a sensitivity close to that of silver halide, but
Both methods require wet processing in the process, which is a major constraint on equipment design.

An improved method of this method is disclosed in Japanese Patent Application Laid-Open No. 61-62042.
, Samebu/-73/ψ! An organic silver salt is used as shown in No. 1, and this generates radicals during the development process.

Method for causing polymerization reaction, JP-A-4/-7J3172-4
/-211J+4#, same j/-, 2bu0214/same jJ
-70136% 12-1/43! As in f), there is a method in which a photo or thermal polymerization initiator is used and a polymer image is formed in an (anti)image-like manner by the polymerization inhibiting ability of a developer (or its oxidized product). These are devised to allow silver development to proceed smoothly by heating under non-aqueous conditions, but the developing agent or reducing agent in all of them is extremely susceptible to oxidation, and it is difficult to further improve the stability over time of storage. I had high hopes.

"Problems to be Solved by the Invention" An object of the present invention is to further improve the prior art described above. That is, the object is to provide an image recording material and an image recording method that have high sensitivity, can form polymer images by dry processing or rapid processing using a very small amount of water, and have excellent storage stability. .

"Means for Solving the Problems" The mechanism of action of the recording material of the present invention is based on the fact that "only the unexposed areas significantly inhibit the polymerization reaction in a place where the polymerization reaction occurs in the same way." There is.

This concept itself is already known.
-701Jt, 4/-71J442% 6ko 116
31. There is a description of this in 6/-2pi3φ4t2. According to these, among a group of reducing agents widely known as developing agents in the field of silver halide photography, certain substances are said to enhance the above-mentioned effect, and J-pyrazolidone is particularly preferred. Derivatives are listed.

The present inventor focused on these descriptions, conducted extensive structural analysis of reducing agents in order to solve the above problems, and performed molecular design based on this analysis. As a result, a completely new group of compounds - general formula (
1), (If)- was found.

The object of the present invention is to provide a record having a photosensitive layer on a support, which contains at least a photosensitive silver halide, a polymerizable compound, a thermal or photopolymerization initiator, and a reducing agent represented by the following general formula [I] or [II]. Achieved by materials.

General formula (1) In general formula (II), R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R2-R6 represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. group, acyl group, acyloxy group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxy group, aryloxy group, sulfonyl group, sulfamoyl group, sulfenyl group, sulfinyl group, amino group,
Acylamino group, alkoxycarbonylamino group, carbamoylamino group, sulfonylamino group or sulfonylamino group
Represents a monovalent organic group of amoylamino group, B2-R6
They may be the same or different, and any two may be linked to form a ring. Furthermore, general formula (1)
Alternatively, the reducing agent represented by (If) may be linked at any position to form a multimer. Further, it may form a salt. Among these, substituents other than the hydrogen atom of R1, the hydrogen atom of R2-R6, and the halogen atom may be further substituted with a substituent.

Furthermore, by heating the recording material of the present invention at the same time as image exposure, or after image exposure, or by further uniformly irradiating light after heating, the polymerized acid compound in the exposed area is polymerized to form a polymer image. This is achieved by a recording method that forms.

Next, general formulas (I) and (II) will be further explained.

The alkyl group represented by B1-R6 has a carbon number of %
/~2λ is preferable. These may have a linear structure, a branched structure, or a cyclic structure. Aryl groups represented by R1-R6 include phenyl groups, naphthyl groups, anthracenyl groups, phenanthrenyl groups, etc. Among them, phenyl group is preferred. These include alkyl groups, aryl groups, halogen atoms, alkoxy groups, alkoxycarbonyl groups,
Amide group, sulfonyl group, carboxyl group, acyl group,
It may be substituted with a hydroxyl group, a cyano group, a nitro group, an amino group, a carbamoyl group, a sulfamoyl group, or the like.

As the heterocyclic group represented by R1-R6, for example,
Examples include a pyridyl group, a pyrimidyl group, an imidazolyl group, a thiazoyl group, a succinimide group, and a hydantoinyl group. These may be fused with a benzene ring, a naphthalene ring, etc., and in the case of a fused ring, they may be bonded through a heterocycle, benzene ring, naphthalene ring, etc. Furthermore, these heterocyclic groups may be substituted with a halogen atom, an alkyl group, an alkoxy group, a nitro group, or the like.

The halogen atom represented by R and R may be any of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom,
Chlorine and bromine atoms are preferred.

Examples of the acyl group represented by R2-R6 include an acetyl group, a benzoyl group, and a nicotinoyl group. It may be substituted with a halogen atom, a nitro group, etc.

Examples of the acyloxy group represented by 82 to R6 include an acetoxy group, a benzoyloxy group, a thio7enecarbonyloxy group, and these may be further substituted with an alkyl group, a halogen atom, a cyano group, etc. good.

Examples of the carbamoyl group represented by R2-R6 include dimethylcarbamoyl group, n-propylcarbamoyl group, phenylcarbamoyl group, etc., but even if these are further substituted with an alkyl group, aryl group, halogen atom, etc. good.

As the alkoxycarbonyl group represented by R-R,
Examples include an ethoxycarbonyl group and an isopropyloxycarbonyl group, which may be further substituted with a halogen atom, an aryl group, a hydroxyl group, and the like.

Examples of the aryloxycarbonyl group represented by RR include a phenoxycarbonyl group and a naphthoxycarbonyl group, which may be further substituted with an alkyl group, a halogen atom, a nitro group, and the like.

The alkoxy group represented by R-R is a methoxy group,
Examples include ethoxy groups and benzyloxy groups, which may be further substituted with aryl groups, halogen atoms, and the like.

Examples of the aryloxy group represented by R-R include phenoxy and naphthoxy groups, which may be further substituted with an alkyl group, a halogen atom, and the like.

Examples of the sulfonyl group represented by R2-R6 include a methanesulfonyl group, a benzenesulfonyl group, and a trifluoromethanesulfonyl group, which may be further substituted with an alkoxy group, a halogen atom, or the like.

The sulfamoyl group represented by R2-R6 is a diethylsulfamoyl group, a phenylsulfamoyl group,
Examples include benzylsulfamoyl group, etc.
These may be further substituted with an alkyl group, an alkoxy group, a halogen atom, or the like.

Examples of the sulfenyl group represented by R-R include Fi, methanesulfenyl group, benzenesulfenyl group, etc., but these also include alkyl groups, aryl groups,
It may be substituted with an alkoxy group, a halogen atom, etc.

Examples of the sulfinyl group represented by R2-R6 include ethanesulfinyl group, benzenesulfinyl group, etc., but these also include alkyl groups, aryl groups,
It may be substituted with an alkoxy group, a halogen atom, etc.

Examples of the amino group represented by R and R include an unsubstituted amino group, a dimethylamino group, a phenylamino group, an isopropylamino group, etc., and these may be further substituted with a halogen atom, an aryl group, a cyano group, etc. Good too.

Examples of the acylamino group represented by B2-R6 include an acetylamino group, a benzoylamino group, a furoylamino group, and these may be further substituted with an alkyl group, an aryl group, a halogen atom, an alkoxy group, etc. .

The alkoxycarbonylamino group represented by R2-R6 is an ethoxycarbonylamino group.

Examples include an N-methyl-ethoxycarbonylamino group and a phenoxycarbonylamino group, which may be further substituted with an alkyl group, an aryl group, a halogen atom, and the like.

Examples of the carbamoylamino group represented by R2-R6 include a (dimethylcarbamoyl)amino group and a (phenylcarbamoyl)amino group, which may be further substituted with an alkyl group, an aryl group, a halogen atom, a cyano group, etc. may have been done.

As the sulfonylamino group represented by R2-R6,
Examples include a methanesulfonylamino group, a benzenesulfonylamino group, and a l-thiophenesulfonylamino group, which may be further substituted with an alkyl group, an aryl group, a halogen atom, a hydroxyl group, and the like.

Examples of the sulfamoylamino group represented by R2-R6 include (dimethylsulfamoyl)amino group, (phenylsulfamoyl)amino group, etc.
These may be further substituted with an alkyl group, an aryl group, a halogen atom, or the like.

As the organic group represented by R2-R6, any monovalent organic group other than the above can be applied, and R2-R6 may be the same or different, and any two may be linked to form a ring. You can leave it there.

Note that the reducing agent represented by the general formula (1) or (II) may be linked at any position to form a multimer,
Furthermore, it may be in the form of a salt such as a hydrochloride or a sulfate.

Next, typical examples of reducing agents that can be used in the present invention will be shown, but the present invention is not limited thereto.

Compound represented by the general formula [■] (1) (Co) (3) (4t) 0 <1> ■ (7) (2) (//) (lr) (10) (lCo) C2H6 General formula ( n) compound represented by Compounds represented by can be easily synthesized by known methods.Many of the specific examples listed above are, for example, synthesized by Ulli Eisner.
r), Joseph Kutha
n), Chemica f) k-L/Buse (Chemica
l Reviews), Volume 72, No. 1, No. 1
~Dako Page (/1974), Jose 7 Coutin (Jos
ef Kuthan), x --Ku/l/7
7-S) (A, Kurfirst), Industry-77 Engineering Chemistry Product Research and Development (Indu
try and Engineering Chemi
Try, Product Reach and
Development) Volume 27 No. 2 (lji, r
h6. You can synthesize them by referring to them.

In the present invention, as the reducing agent, the compounds described above may be used alone, or several types may be used in combination.

In the present invention, the reducing agent may be used to reduce the total amount of silver in the photosensitive layer (including silver halide and optional components, which will be described later).
It is preferably used in an amount of 0.1 to 1500 mol % based on the silver salt (including silver salt).

A more preferable usage range is 10 to 500 mol%.

In addition, in the present invention, the above-mentioned reducing agent may be used in combination with other reducing agents, which are generally known as developing agents in the field of silver salt photography, such as hydroquinones, catechols, p-amino Phenols, p-phenylenethiamines, 3-pyrazolidones, 3-aminopyrazoles, 4-amino-5-pyrazolones, 5-amino-uracils, 4,5-dihydroxy-6-aminopyrimidines , reductones, amyl reductones, 0- or p-sulfonamidophenol % 0- or p
-Sulfonamide naphthols, 2-sulfonamide indanones, 4-sulfonamide-5-pyrazolones,
Examples include 3-sulfonamide indoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, and α-sulfonamide ketones.

Specific examples of the above developer include pentadecylhydroquinone, 5-t-butylcatechol, p-(N,N-diethylamino)phenol, l-phenyl-4-methyl-
4-Hydroxymethyl-3-pyrazolidone, l-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenyl Sulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2-(N-butylcarbamoyl)-4-phenylsulfonylaminonaphthol, 2-(N-methyl-N-octadecylcarbamoyl)-4-sulfonylaminonaphthol etc. can be mentioned.

Regarding various reducing agents (developing agents) that can be used in combination with the reducing agent of the present invention, please refer to "Th
e Theory of the Photography
hic Process 4th edition, pp. 291-334 (1
977〉, Research Disclosure Magazine Vol. 1.
170. No. 17029 (pages 9-15), June 1978, and Vol. 176. There is also a description in No. 17643 (pages 22-31) of December 1978.

When two or more types of reducing agents are used together, the interaction between the reducing agents is firstly due to the so-called superadditivity of halogenated IN! (and/or an organic silver salt), and secondly, other reductions in which the oxidized form of the first reducing agent produced by the reduction of the halogenated II < and/or m silver salt) coexists. Possible methods include causing polymerization of the polymerizable compound (or suppressing polymerization) via an oxidation-reduction reaction with the agent. However, in actual use, the reactions described above can occur simultaneously, so it is difficult to specify which effect is occurring.

Hereinafter, in addition to the reducing agent used in the present invention, silver halide, polymeric acid compound, thermal polymerization initiator, and support constituting the recording material will be sequentially explained.

In the present invention, any grains of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used as silver halide in the present invention. .

The halogen composition of silver halide grains may be uniform or non-uniform on the surface and inside.9 Regarding silver halide grains having a multilayer structure with different compositions on the surface and inside, Japanese Patent Laid-Open No. 57 -154232, 58-10853
No. 3, No. 59-48755, No. 59-52237, U.S. Patent No. 4433048 and European Patent No. 1
00984 This winter there is a description in the 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 no particular restriction on the crystal habit of the silver halide grains; for example, tabular grains having an aspect ratio of 3 or more may be used, as in the light-sensitive material described in JP-A-62-210455.

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

In the silver halide used in the present invention, two or more types of silver halide grains different in halogen composition, crystal habit, grain size, etc. can also be used in combination.

Regarding the grain size distribution of silver halide grains, especially +b
There is no Q limit. 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 this recording material, the average grain size of the silver halide grains is preferably from o, ooi to 5 μm,
．． More preferably, the thickness is 0.001 to 2 μm.

The amount of silver halide contained in the photosensitive layer is preferably in the range of 0.1 mg to 10 g/n (in terms of silver including silver salt, which is an arbitrary component described later). In terms of silver, it is preferably 0.1 g/n (or less, and particularly preferably 1 mg to 90 mg/-).

The polymerizable compound that can be used in the present invention is not particularly limited and any known polymerizable compound can be used, but it is preferable to use a compound with a high boiling point (for example, a boiling point of 80°C or higher) that is difficult to volatilize when heated. A preferable embodiment in which the photosensitive layer contains a color image forming substance as an optional component described later is intended to immobilize the color image forming substance by polymerizing and curing the polymerizable compound. Preferably, it is a crosslinkable compound having multiple polymerizable functional groups.
Furthermore, as will be described later, when forming a transferred image using an image-receiving material, it is preferable to use a highly viscous substance as a polymerizable compound, as in the photosensitive material described in JP-A-62-162147. .

Note that the polymerizable compound that can be used in the present invention is described in the application specifications for a series of photosensitive materials described above and below.

The polymerizable compound used in the present invention is generally a compound having addition polymerizability or ring-opening polymerizability.

Examples of the compound having addition polymerizability include compounds having an ethylenically unsaturated group, and compounds having ring-opening polymerizability include compounds having an epoxy group, and compounds having an ethylenically unsaturated group are particularly preferred.

Compounds having an ethylenically unsaturated group that can be used in the present invention include acrylic acid and its salts, acrylic esters, acrylamides, methacrylic acid and its salts, methacrylic esters, methacrylamides,
Examples include maleic anhydride, 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 the present invention include acrylic esters such as n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate to ethoxyethoxyethyl acrylate, Dicyclohexyloxyethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate/neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Examples include hexaacrylate, polyoxyethyrenated bisphenol A diacrylate, hydroxypolyether polyacrylate, polyester acrylate, and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Mention may be made, for example, of methacrylate and dimethacrylate of polyoxyalkylated bisphenol A.

The above-mentioned polymerizable compounds may be used alone or in combination of two or more types. A photosensitive material using a combination of two or more types of polymerizable compounds is described in JP-A-62-210445. Furthermore, the above-mentioned reducing agents (including hydrazine derivatives, the same shall apply hereinafter) or substances in which a polymerizable functional group such as a vinyl group or vinylidene group is introduced into the chemical structure of the color image forming substance, which is an optional component described below, are also considered polymerizable compounds. Can be used as As mentioned above, it goes without saying that the use of a reducing agent and a polymerizable compound, or the use of a substance that serves both as a color image type material and a polymerizable compound, is also included in type a of the photosensitive material.

In the present invention, the polymerizable compound is preferably used in a range of 5 to 120,000% by weight based on silver halide, and more preferably in a range of 12 to 12,000M% by weight.
It is.

The thermal polymerization initiator that can be used in the present invention is generally a compound that thermally decomposes under heating to generate a polymerization initiator (particularly a radical), and is usually used as an initiator for radical polymerization. Regarding thermal polymerization initiators, please refer to "Addition Polymerization/Ring-Opening Polymerization J.
(1983, Kyoritsu Shuppan), pages 6 to 18, etc. Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1,1°-azobis(1-cyclohexanecarbonitrile), dimethyl-2°2'-azobisisobutyrate, 2,2'-azobis (2-methylbutyronitrile), azo compounds such as azobisdimethylvaleronitrile, organic peroxides such as benzoyl peroxide, di-t-peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc. Examples include inorganic peroxides such as oxides, hydrogen peroxide, potassium persulfate, and ammonium persulfate, and sodium p-)luenesulfinate. The thermal polymerization initiator is 0.0% relative to the polymerizable compound. It is preferable to use it in a range of / to /λ0 parts by weight, and more preferably in a range of 1 to IO parts by weight.

The photopolymerization initiator that can be used in the present invention is a carbonyl compound (eg, acetophenone).

benzoins, ketones such as benzyl, diacetyl, and benzophenone, quinones such as anthraquinones, naphthoquinones, and phenanthrenequinones), organic sulfur compounds, peroxides, halogen compounds, optical semiconductors (e.g., zinc oxide, titanium dioxide, etc.) ), metal ions (e.g. iron (
I) ions, metal carbonyls, metal complexes, uranyl salts, etc.), azo and diazo compounds, photoreducible dyes, etc. can be used.

Regarding the photopolymerization initiator that can be used in the present invention,
Qster et al., “Chemical Review J Vol. 6r (IP41), pages 2!~/!/,” Kosar, “Light-8 intensive 8systemsJ”
(John Wiley & 5ons, / '?
A 7th year) ljl-lde 2 pages, Buttons and Fine Chemicals Vol. /6, ivy? , (1917)! There are also descriptions on pages ~/ri (especially Table 2).

A photopolymerization initiator f′i using a photoreducible dye is generally composed of a photoreducible dye and a hydrogen-donating compound, and it is thought that radicals capable of initiating polymerization are generated by the reaction between the photoexcited dye and the hydrogen-donating compound. It is being Photoreducible pigments include methylene bluech, tnin, rose bengal,
Erythrosin-B.

Eosin, rhodamine, 70xin-B, safranin,
Acry7 Lavin, Riboflavin, Fluoretuscein, Uranine, Benzoflavin, N, N.

N/, N/-tetra-n-butylthionine, N
,N.

N', N'-tetramethyl-←'-dodecyl safranin, acridine orange, acridine yellowta, IO-
Examples include carbonyl compounds such as phenanthrenequinone and penzanthrone.

Examples of hydrogen-donating compounds include β-diketones such as dimedone and acetylacetone, triethanolamine, jetanolamine, monoethanolamine, dimethylamine, diethylamine, tetramethylethylenediamine, triethylamine, and 7-enylhydrazine. amine 11. Examples include sulfinic acids such as p-toluenesulfinic acid, benzenesulfinic acid, Lp-(N-acetylamino)benzenesulfinic acid, and salts thereof, N-phenylglycine, L-ascorbic acid, thiourea, allylthiourea, and the like.

The molar ratio of the photoreducible dye to the hydrogen-donating compound is Q, θQ! mol to 3 mol, preferably 0.0! The amount ranges from 7 to 7 moles. It was a cabinet. ! , When using a carbonyl compound such as 10-7 enanthrenequinone as a photoreducible dye,
Since the binder acts as a hydrogen donating compound, it is not always necessary to use a hydrogen donating compound.

In the image recording method of the present invention, the photopolymerization initiator is preferably used in an amount of 0.0007 mol to 0.1 mol per mol of the polymerizable compound.

It is more preferable to use it in a range of 0.001 mol to o, oj mol.

The recording material of the present invention is formed by providing a photosensitive layer containing the i component as described above on a support.

Regarding this support, it is necessary to be able to withstand the temperature during the heat treatment, but there are no other particular restrictions.

Materials that can be used for the support of the recording material of the present invention include glass, paper, high-quality paper, coated paper, cast coated paper, synthetic paper, metals and their analogues, polyester,
Examples include films of acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene terephthalate, etc., 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 has a certain level of smoothness according to the method defined by waviness, like the support used in the photosensitive material described in JP-A No. 2 Koko No. 05P12. In addition, when using a paper support, it is preferable to use a paper support with low water absorption such as the photosensitive material described in JP-A-63-38934, or JP-A-63-47754. Paper support having a certain Bekk smoothness like the photosensitive material described in the publication, JP-A-63-813
A paper support with a low shrinkage rate such as the photosensitive material described in JP-A No. 39, a paper support with low air permeability such as the photosensitive material described in JP-A-63-81340, and JP-A-63-97941.
It is also possible to use a paper support having a pH (i) of 5 to 9, as in the photosensitive material described in the above publication.

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 below.

The photosensitive material preferably has a polymerizable compound dispersed in the photosensitive layer in the form of oil droplets. Examples of photosensitive materials in which the polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets are described in Japanese Patent Laid-Open No. 6
There is a description in Publication No. 2-78552. Inside the oil drop above,
Regarding photosensitive materials containing halogenated wax in oil droplets, which may contain other components in the photosensitive layer such as silver halide, reducing agent, color@image@preceptive substance, etc., JP-A-Sho 62-20
No. 9450 and No. 62-164040 this winter, and JP-A-62-183451 describes a photosensitive material further containing a reducing agent in the oil droplets.

In addition, when silver halide is included in the oil droplet, the number of silver halide particles contained in the oil droplet is increased to 5 as described in JP-A-63-15239. It is preferable to set it as more than one.

It is more 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 any particular limitations. An example of a photosensitive material in which oil droplets of a polymerizable compound are in the form of microcapsules is disclosed in Japanese Patent Laid-Open No. 61-27.
There is a description in Publication No. 5742.

There are no particular restrictions on the wall material that constitutes the outer shell of the microcapsules. For photosensitive materials using microcapsules with outer shells made of polyamide resin and/or polyester resin, see Japanese Patent Application Laid-Open No. 62-209437. Regarding a photosensitive material using microcapsules having an outer shell made of polyurea tree uh and/or polyurethane resin, see JP-A-62-209438. For materials, see Japanese Patent Application Laid-Open No. 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 8IV11 aldehyde below a certain value, as in the photosensitive material described in JP-A-63-32535 by the present applicant.

When silver halide is contained in microcapsules, it is preferable that silver halide be present in the wall material constituting the outer shell of the microcapsules.For photosensitive materials containing silver halide in the wall material of the microcapsules, Japanese Unexamined Patent Publication 1986
There is a description in the publication No.-169147.

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. 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.A photosensitive material containing 24114 or more microcapsules. For details, see JP-A-62-
There is a description in the 198850 publication.

The average particle size of the microcapsules is preferably 3 to 20 μm.The particle size distribution of the microcapsules is uniformly distributed over a certain value, as in the photosensitive material described in JP-A-63-5334. It is preferable that microcapsules or IIAK are used, especially microcapsules
As in the photosensitive material described in 81336, it is preferable that the RUB is within a certain value for the particle diameter.

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. By setting the average grain size of the silver halide grains to one-fifth or less of the average size of the microcapsules, which is more preferred, a uniform and smooth image can be obtained.

Optional components that can be included in the photosensitive layer of the photosensitive material include color image forming substances, sensitizing dyes, organic silver salts, radical generators, and various image formation accelerators (e.g., bases, base precursors, oils, interfaces, etc.). activator, anti-fogging function and/or
or a compound having a development accelerating function, a thermal solvent, a compound having an oxygen removal function, etc., a thermal polymerization inhibitor, a development stopper, a fluorescent whitening agent, an antifading agent, a haley silane or an anti-irradiation dye, or Examples include pigments, dyes that can be decolored by heating or light irradiation, capping agents, anti-smashing agents, plasticizers, water release agents, binders, photopolymerization opening agents, solvents for polymerizable compounds, water-soluble vinyl polymers, and the like.

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. Further, for photosensitive materials using dyes or pigments as color image forming substances, see JP-A-62-187346, and for photosensitive materials using leuco dyes, see JP-A-62-187346.
209436, JP-A-62-251741 for photosensitive materials using triazene compounds, and JP-A-62-288827 and JP-A-62-288828 for photosensitive materials using yellow coloring leuco dyes.
JP-A No. 63-53542 describes photosensitive materials using cyan color-forming leuco dyes.

Dyes and pigments, which are substances that color themselves, can be found on the market as well as in various literature (for example, "Dye Handbook," edited by the Organic Synthetic Chemistry Association, published in 1970; "Latest aIn Handbook," edited by Japan III Materials Technology Association. , published in 1972) can be used. These dyes or pigments are used either dissolved or dispersed.

On the other hand, examples of substances that develop color due to some kind of energy such as heating, pressurization, 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, campling reactions, chelate-forming reactions, etc. between two or more components.

For example, Hiroyuki Moriga's ``Introductory/Special Paper Chemistry J (Showa 5)
Known coloring systems such as pressure-sensitive copying paper (pages 29-58), azography (pages 87-95), thermal coloring by chemical change (pages 118-120), or Kinki Kagaku Utilize the coloring system etc. described in the seminar ``Latest Pigment Chemistry - Attractive Utilization and New Developments as Functional Pigments'' hosted by an industrial association, pages 26-32 (June 19, 1980). Specifically, a coloring system consisting of a coloring agent with a partial structure such as lactone, lactam, or spiropyran used in pressure-sensitive paper and an acidic substance (color developer) such as acid clay or phenols; A system that utilizes the azocamping reaction of group diazonium salts, diazofutes, diazosulfonates [and naphthols, anilines, activated methylenes, etc.]; reactions of hexamethylenetetramine with ferric ions and gallic acid; Chelate-forming reactions such as the reaction between complexons and alkaline earth metal ions; redox reactions such as the reaction between ferric nistearate and pyrogallol; and the reaction between silver behenate and 4-methoxy-1-naphthol. can.

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. Especially when the purpose is supersensitization, it is common to use a combination of sensitizing dyes. be. In addition, along with the sensitizing dye, a dye that itself does not have a spectral sensitizing effect, or a substance that does not substantially absorb visible light but exhibits supersensitization may be used in combination.The amount of the sensitizing dye added is as follows: -i to 10-'' to 1 mole of halogenated acetate
It is about 0.04 mole.

The above-mentioned sensitizing dye is preferably added at the tII production step of the silver halide emulsion described below.For light-sensitive materials obtained by adding the sensitizing dye at the stage of forming silver halide grains, JP-A-62 947, a sensitizing dye is added to a silver halide emulsion after silver halide grain formation!
Regarding photosensitive materials obtained by adding PI in the step of producing PI, there are descriptions in JP-A-62-210449. Further, specific examples of sensitizing dyes that can be used in light-sensitive materials are also described in the above-mentioned JP-A-62-947 and JP-A-62-210449.

Further, as in the photosensitive material described in JP-A-62-184738, a sensitizing dye sensitive to infrared light may be used in combination.

Addition of 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 silver salt containing 81 is considered to participate in an oxidation-reduction reaction catalyzed by the latent image of silver halide. In this case, it is preferable that the silver halide and the organic silver salt are in contact with each other or in close proximity.The organic compound constituting the silver halide is preferably an aliphatic or aromatic carboxylic acid, a mercapto group, or an α- Examples include thiocarbonyl group-containing compounds having hydrogen, imino group-containing compounds, and the like. Among them, benzotriazole is particularly preferred, as mentioned above! ! ! The salt is halogenated to -a in an amount of 0.0. Ol to 10 mol, preferably 0.01 to 1 mol is used. 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.

For photosensitive materials using organic silver salts, see JP-A-62-32.
There is a description in Publication No. 46.

The photosensitive layer is coated with the aforementioned reducing agent to promote polymerization (or polymerization 1).
A photosensitive material using triazene silver as the radical generator, in which a radical generator involved in the reaction may be added, is disclosed in JP-A-62-19563.
9, a photosensitive material using silver diazotate is described in JP-A-62-195640, and a photo-sensitive material using an azo compound is described in JP-A-62-195641.

Various image formation accelerators can be used in the photosensitive material. The image formation accelerator is one that promotes the redox reaction between silver halide (and/or iS! salt) and a reducing agent. , promoting the transfer of image-forming substances from the photosensitive material to the image-receiving material or image-receiving Ni (these will be described later).

From the viewpoint of physicochemical functions, image formation accelerators include bases,
They are further classified into base precursors, oils, surfactants, compounds with antifogging and/or development accelerating functions, thermal solvents, compounds with oxygen removal functions, and the like. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Therefore, the above classification is for convenience, and in reality, one compound often has multiple functions.

Examples of the image formation accelerator include a base, a base precursor, an oil, a surfactant, a compound having an antifogging iR and/or a development accelerating function, a thermal solvent, and a compound having an oxygen removing function.

Examples of preferred bases include, as inorganic bases, alkali metal or alkaline earth metal hydroxides; alkali metal or alkaline earth metal tertiary phosphates, borates;
carbonates, mekuborates; combinations of lead hydroxide or zinc oxide with chelating agents such as sodium picolinate;
Ammonium hydroxide; hydroxide of quaternary alkyl ammonium; hydroxide of other metals, etc.; ); aromatic amine l1l (N-alkyl substituted aromatic amines,
N-hydroxylalkyl-substituted aromatic amines and bis(p-(dialkylamino)phenyl)methanes),
Examples include heterocyclic amines, amidines, cyclic amidines, granicines, cyclic guanidines, etc., especially those with pKa
is preferably 7 or more.

As a base precursor, there is a compound that is decarboxylated by heating.
aM and base salt, intramolecular nucleophilic substitution reaction, Ronsen rearrangement,
Preferably used are compounds that release bases by causing some kind of reaction when heated, such as compounds that release amines through reactions such as Beckmann rearrangement, and compounds that generate bases by electrolysis or the like. Specific examples of base precursors include guanidine trichloroacetic acid, piperidine trichloroacetic acid, morpholine trichloroacetic acid, P-)luidine trichloroacetic acid, 2-picoline trichloroacetic acid, guanidine phenylsulfonylacetate, 4-chlorophenylsulfonylacetate guanidine, 4-methyl Examples include guanidine -sulfonylphenylsulfonylacetate and guanidine 4-acetylaminomethylpropiolate.

The base or base precursor can be used in the light-sensitive material of the present invention in a wide range of amounts. A base or a base precursor may be used to overwhelm the coating film of the photosensitive layer! i converted to 100
It is appropriate to use the base and/or the base precursor in an amount of 2% by weight or less, and more preferably a range of 40% by weight from 0, tmm% to 40% by weight. Good too.

Incidentally, a photosensitive material using a base or a base precursor is described in JP-A-62-264041. Furthermore, regarding photosensitive materials using tertiary amines as bases or base precursors, JP-A No. 62-1709
54 describes a photosensitive material using a fine particle dispersion of a hydrophobic organic base compound with a melting point of 80 to 180°C, and JP-A-62-209523 discloses that a guanidine derivative having a solubility of 0.1% or less is used. The photosensitive material used is described in JP-A-63-70845, and the photo-sensitive material using an alkali metal or alkaline earth metal hydroxide or salt is described in JP-A-62-209448.

Furthermore, regarding a photosensitive material using an acetylide compound as a base precursor, JP-A-62-24242 discloses that an acetylene carboxylate is used as a base precursor, and silver, copper, a silver compound, or a copper compound is added in a base generation reaction. For photosensitive materials containing catalysts, see JP-A No. 6
No. 3-46446 discloses a photosensitive material containing the acetylene carboxylate and the silver, copper, silver compound or digested compound separated from each other in JP-A No. 63-813.
No. 3 & No. 1 discloses a photosensitive material containing the above-mentioned acetylene carboxylate and the above-mentioned silver, copper, a silver compound, or a ligand in a free state in addition to the copper compound, in JP-A-63-97.
No. 942 describes the use of acetylene as a base precursor.
Regarding a photosensitive material that uses carvone 111 and further contains a heat-fusible compound as a reaction accelerator for the base production reaction, JP-A-63-46446 describes a photosensitive material that uses sulfonylacetate as a base precursor and further contains a heat-fusible compound as a base production reaction promoter. For photosensitive materials containing compounds as reaction accelerators for production reactions, see JP-A-63-48543, and for photosensitive materials using compounds in which isocyanate or isothiocyanate is bonded to organic bases as base precursors, see JP-A-63-24242. There are descriptions in each publication.

When a base or a base precursor is used in the photosensitive material of the present invention, silver halide,
A photosensitive material containing a reducing agent, a polymerizable compound, and a triazene compound, and preferably having a base or a base precursor present in the photosensitive layer outside the microcapsules, or a photosensitive material described in JP-A-62-209521. The base or base precursor may be contained in a separate microcapsule, such as in the case of a photosensitive material using a microcapsule containing a base or base precursor, in addition to the above specification. A photosensitive material housed in microcapsules in a dissolved or dispersed state is disclosed in Japanese Patent Application Laid-Open No. 62-20952.
No. 2 discloses a photosensitive material in which solid fine particles carrying a base or a base precursor are housed in microcapsules, and JP-A No. 62-209526 discloses a photosensitive material having a melting point of 70°C to 20°C.
A photosensitive material using microcapsules containing a basic compound at 10 DEG C. is described in JP-A-63-65437. In addition, instead of the microcapsules containing the above 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 Japanese Patent No. 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 auxiliary N (a layer containing a base or a base precursor, which will be described later) other than the photosensitive layer.

Furthermore, as described in JP-A-63-32546, the above-mentioned support may be made porous and a base or a base precursor may be contained in this 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 with the aim of obtaining a clear image with a high maximum density and a low low density (image with a high S/N ratio). Regarding photosensitive materials using antifoggants as compounds having antifogging and/or development accelerating functions, please refer to JP-A-6-2-15.
1838, JP 62-151841 for photosensitive materials using compounds having a cyclic amide structure, and JP 62-151842 for photosensitive materials using ζ thioether compounds, polyethylene glycol For photosensitive materials using derivatives, see JP-A-62
For photosensitive materials using thiol derivatives, see JP-A-151843, and for photosensitive materials using acetylene compounds, see JP-A No. 62-151844.
178232, a photosensitive material using sulfonamide derivatives is described in JP-A-62-183450, and a photo-sensitive material using quaternary ammonium derivatives is described in JP-A-63-91653. be.

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, -3o
Compounds with high y: ratio having w- and/or -C〇- groups, polar substances described in U.S. Pat. -Decanediol, 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 oxygen removal an 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.

A development stopper that can be used in photosensitive materials is a compound that neutralizes the base or reacts with the base to reduce the base concentration in the film and stop development immediately after proper development, or a compound that interacts with silver and silver salts. It is a compound that inhibits development. Specific examples include acid precursors that release acids when heated, m-electron compounds that cause ItfA reactions with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include JP-A-60-408837 and JP-A-60-192939.
Oxime esters described in this winter publication, JP-A-60-23
Examples include compounds that release an acid through Ronsen rearrangement as described in Publication No. 0133. 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 haley silane or irradiation. The material is described in JP-A-63-29748.

When the photosensitive layer of the photosensitive material is 84m using the above-mentioned microcapsules, the microcapsules may contain a dye having the property of decolorizing by heating or light irradiation. A dye having the above function can function as an equivalent to a yellow filter in a convensiranal silver salt photographic system.

Regarding photosensitive materials using dyes having the property of decolorizing by heating or light irradiation as mentioned above, Japanese Patent Application Laid-Open No. 63-9
There is a description in Publication No. 7940.

The anti-smudge agent used in photosensitive materials is preferably a particulate material that is solid at room temperature.
Starch particles described in US Pat. No. 2,322,347, fine polymer powders as described in US Pat. No. 3,625,736, etc., microcapsule particles containing no color former as described in British Patent No. 1,235,991 [IW, etc., US Pat. No. 2,71137]
Examples include inorganic particles such as cellulose fine powder, curcum, kaolin, bentonite, waxite, zinc oxide, titanium oxide, and alumina described in Book No. 5 M. The average particle size of the above particles is 3 to 50 in volume average diameter.
The range is preferably .mu.m, and the range of 5 to 40 .mu.m is more preferred.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 and image-receiving materials described below can be contained alone or in combination in the photosensitive layer or image-receiving material N (described later). It is preferable to use a mainly hydrophilic binder. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as gelatin, gelatin derivatives,
These include natural materials such as cellulose derivatives, starch, gum arabic, etc., and synthetic polymeric materials such as water-soluble polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc.

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 Japanese Patent Application Laid-Open No. 2003-110010, Sho, g/-6POA, No. 2. Also,
A photosensitive material using a binder together with microcapsules is described in JP-A No. 2012-121.

When using a solvent for a polymerizable compound in a photosensitive material, it is preferable to encapsulate the solvent in a microcapsule separate from the microcapsule containing the polymerizable compound. For photosensitive materials using organic solvents, see Japanese Patent Application Laid-Open No. 62-2095.
There is a description in Publication No. 24.

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

In addition to those mentioned above, examples of arbitrary components that can be included in the photosensitive layer and their use B can also be found in the above-mentioned series of patent publications related to photosensitive materials, and in Research Disclosure LgVo1.170.G, 1978. It is described in No. 17029 (9 to 15 shells).

The photosensitive layer of the photosensitive material comprising the above-mentioned components preferably has a pHl1 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, a cover sheet or a protective layer, a layer containing a salt or a base precursor, and a base. Barrier/Layer/Haley Silane Prevention M(
colored layer), etc.

Instead of using the image-receiving layer on the image-receiving material, which will be described later as a method of using the photo-sensitive material, the image-receiving layer may be placed on the photo-sensitive material to form an image thereon. The same t1 precept as the image receiving layer provided can be used. Details of the image receiving layer will be described later.

In addition, regarding photosensitive materials using a heating layer,
1-294434, and JP-A No. 62-210447 regarding photosensitive materials provided with a cover sheet or a protective layer.
JP-A-62-253140 describes a photosensitive material provided with a layer containing a base or base flexor, and JP-A-63-101842 describes a photosensitive material provided with a colored layer as a Halley silane prevention layer. Each is listed in the official bulletin. 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 patent publications related to the above-mentioned series of photosensitive materials.

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

Of photosensitive materials! Although various methods can be used to prepare the components of the photosensitive layer, a common manufacturing method is to
Prepare a coating solution by dissolving, emulsifying or dispersing it in a suitable solvent, and apply the coating solution to the support as described above.
This process consists of obtaining a photosensitive material by drying.

-a, each of the above-mentioned coating liquids is prepared by preparing a liquid Ux product containing each component for each component, and then mixing each liquid composition. The above liquid composition has each component individually! The constituent components of the photosensitive layer (-), which may be manufactured by II or may be prepared to contain multiple components, may be added during or after the preparation of the liquid composition or coating solution. You can also do it. Furthermore, as described below, −
Alternatively, a method can also be used in which an oily (or aqueous) composition containing two or more components is further emulsified in an aqueous (or oily) solvent to prepare a secondary composition.

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

In the production of photosensitive materials, silver halide is
Preferably, silver halide emulsions are prepared by IYJ.There are various methods known in photography for preparing silver halide emulsions, but there are no particular restrictions on the production of light-sensitive materials.Silver halide emulsions can be prepared by acid method. It can be prepared using either the neutral method or the ammonia method. The reaction method for soluble root salts and soluble halogen salts may be one-sided mixing method, simultaneous mixing method, or a combination thereof. Back mixing method in which 0 particles are mixed under 11 conditions of root ionization, and pAg is kept constant. The Chondrald double jet method can also be used. Furthermore, even if the silver halide emulsion is an R-plane image-following type in which a latent image is mainly formed on the grain surface,
It is also possible to use a direct reversal emulsion which is a combination of an internal latent image type emulsion and a nucleating agent, which may be an internal latent image type formed inside the grains.

In the preparation of silver halide emulsions used in the production of light-sensitive materials, hydrophilic colloids (eg, gelatin) can be used as protective colloids. In addition, a water-soluble vinyl polymer may be added to the silver halide emulsion in place of gelatin or in combination with gelatin, and regarding photosensitive materials in which the water-soluble vinyl polymer compound is in contact with silver halide grains. is described in JP-A-63-91652.

The silver halide emulsion is prepared by using ammonia, an organic thioether derivative (see Japanese Patent Publication No. 47-386) and a yellow-containing compound (see Japanese Patent Publication No. 144319-1986) as a silver halide solvent. reference)
etc. can be used. In addition, in the process of particle formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, etc. may coexist.Iridium chloride (! (2), water-soluble iridium salts such as ammonium hexachloroiridium salt, or water-soluble rhodium salts such as rhodium chloride.

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

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

In addition, when adding a sensitizing dye to a silver halide emulsion,
JP-A-62-947 and JP-A-62-2104 mentioned above
It is preferable to add the nitrogen-containing heterocyclic compound at the stage of preparation of the silver halide emulsion as in the light-sensitive material described in Japanese Patent No. 49, and the nitrogen-containing heterocyclic compound is added as a compound having the above-mentioned capri-preventing function and/or development accelerating function. In some cases, it is preferable to add nitrogen-containing nitrogen at the stage of forming or ripening silver halide grains in the preparation of a silver halide emulsion. ! [A method for producing a photosensitive material in which a ring compound is added at the stage of forming silver halide grains or at the PIyfi stage is described in JP-A-62-16144.

When the above-mentioned organic silver salt is included in the photosensitive layer, a silver salt emulsion containing 81 silver salts can be prepared by a method similar to the method for preparing the silver halide emulsion described above.

In the production of photosensitive materials, polymerizable compounds can be used as a medium in preparing the composition of other components in the photosensitive layer, such as silver halide (including silver halide emulsions), reducing agents, A color image-forming substance or the like can be dissolved, emulsified or dispersed in a polymerizable compound and used in the production of a photosensitive material. Particularly when adding a color image forming substance, it is preferable to include the polymerizable compound in the polymerizable compound. The polymerizable compound may contain components such as wall materials necessary for this purpose.

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

Photosensitive &lIrl1. containing these silver halides. The product 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.For photosensitive compositions containing the above-mentioned copolymer, , Japanese Patent Publication No. 1986-
There is a description in No. 209449.

Alternatively, instead of using the above copolymer, a photosensitive animal may be prepared by dispersing microcapsules having a silver halide emulsion as a core material in a polymerizable compound. Photosensitive m-parallel containing microcapsules is described in JP-A-62-164041. Polymerizable compounds (including those containing other constituents like the photosensitive compositions mentioned above) are aqueous. It is preferable to use the emulsion as an emulsion in a solvent. In addition, when oil droplets of a polymerizable compound are microencapsulated as in the photosensitive material described in JP-A-61-275742, microcapsules are used. It is also possible to add a wall material necessary for the emulsion to the emulsion and further perform a treatment to form the outer shell of the microcapsules at the stage of the 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 a wood-loving wall-forming material as described in US Pat. No. 2,800,457 and US Pat. No. 2,800,458; US Pat. Specification and Japanese Patent Publication No. 38-1957
4, No. 42-446, and No. 42-771; interfacial polymerization methods described in U.S. Patent No. 3,418,250 and U.S. Pat. No. 3,660,304; method by precipitation of polymer; U.S. Pat. No. 3,796,669; - Method using polyol wall materials; Method using isocyanate wall materials described in U.S. Pat. No. 3,914,511; U.S. Pat. Nos. 4,001,140, 4,087,376 and 4,089,802
1. A method using the urea-formaldehyde-based or urea-formaldehyde-resircinol-based wall forming material published this winter;
A method using wall-forming materials such as formaldehyde 4MlT1 and hydroxypropyl cellulose;
9168 and Japanese Unexamined Patent Publication No. 51-9079 published this winter, in 5-itu method by polymerization of monomers; British Patent No. 9
27807 and 965074; the spray drying method described in U.S. Pat. No. 3,111,407 and British Patent No. 930,422; Although the method of microencapsulation is not limited to the above, it is particularly preferable to emulsify the core material and then form a polymer membrane as the microcapsule wall.

Regarding photosensitive microcapsules that can be used in the production of photosensitive materials, Japanese Patent Publication No. sho s 1-11556, sho 61-11557, sho 61-53871, sho 6
No. 1-531172, No. 61-53873, No. 61-
No. 53874, No. 61-53875, No. 61-538
No. 77, No. 61-53878, which is described in the winter specification.

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

As above! A photosensitive material is produced by applying a coating solution for a photosensitive layer produced by IW 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 is used after being subjected to a development process at the same time as imagewise exposure or after imagewise exposure.

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

The photosensitive material is developed at the same time as the above-mentioned imagewise exposure or after the imagewise exposure.
Development processing using a developer described in Publication No. 49 etc. may be performed. Furthermore, as mentioned above, since the method described in Japanese Patent Application Laid-open No. 61-69062, which involves heat development processing, is a dry process. , it has the advantage of being easy to operate and can be processed in a short time. Therefore, the development process for 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.Also, as in the image forming method described in JP-A-62-210461, the amount of oxygen present in the photosensitive layer can be controlled. The heating temperature is generally 80°C to 200°C, preferably 100°C to 16°C.
It is 0°C. The heating time is 1 second to 5 minutes, preferably 5 seconds to 1 minute.

Note that instead of including the base or base precursor in the photosensitive material as described in ##, the base or base precursor may be added while the base or base precursor is added to the photosensitive layer or development processing may be carried out immediately after the addition. As a method, a sheet containing a base or a base precursor (
The method using a base sheet) is the easiest and preferable.
An image forming method using the above base sheet is described in JP-A-63-32546.

The photosensitive material can be subjected to a heat development process as described above to polymerize the polymerizable compound in the area where the silver halide latent image is formed.

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

When the photosensitive material is constructed like the photosensitive material described in JP-A No. 62-209444 mentioned above, the photosensitive material subjected to in-process processing is pressurized to destroy the microcapsules and cause a coloring reaction. Color images can be formed on photosensitive materials by bringing different types of substances into contact.

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

The image-receiving material will be explained below. The general image forming method using an image-receiving material or an image-receiving layer is described in 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 as in the image-receiving material described in the above publication, and 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 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, as in the image-receiving material described in JP-A No. 62-209454, a polymer with low acid tolerance may be used as the binder.

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 be constituted as an aggregate of thermoplastic compound fine particles. The image-receiving layer 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-mentioned thermoplastic compound is not particularly limited, and known plastic resins ( (plastic), wax, etc. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200°C or less. Regarding image-receiving materials having an image-receiving layer, Japanese Patent Application Laid-Open No. 62-28
There is a description in No. 0071 and 62-280739 this winter gazette.

In image formation using an image-receiving material, the image-receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator,
The color image forming material is transferred together with the unpolymerized polymerizable compound as described below. Therefore, for the purpose of smooth progress of the curing process (fixing process) of the unpolymerized polymerizable compound, a photopolymerization initiator nest or a thermal polymerization initiator can be added to the image-receiving layer. Regarding an image receiving material having an image receiving layer containing an agent, see JP-A-62-161149,
Image-receiving materials having an image-receiving layer containing a thermal polymerization initiator are described in Japanese Patent No. 62-210444.

Dyes or pigments can be included in the image-receiving layer for the purpose of writing characters, symbols, frames, etc. in one layer, or for the purpose of making the background of an image a specific color. A dye or an R material 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. A variety of substances can be used, but it is best to reduce the staining density of the dye or pigment (e.g. f1 reflection density 1 or less), or an image-receiving layer containing a dye or pigment that has the property of decolorizing by heating or light irradiation. The image-receiving material having the above-mentioned image receiving material is described in Japanese Patent Application Laid-Open No. 62-251741.

Furthermore, when adding a white pigment such as titanium dioxide or neurolium sulfate to the image-receiving layer, the image-receiving layer may be used as a white reflective layer.
It can be made alil. When the image-receiving layer functions as a white reflective layer, the white pigment is preferably used in an amount of Log to LOOg per tg of the thermoplastic compound.

When the dye or ImJl agent mentioned above is contained in the image-receiving layer, it may be contained uniformly or unevenly distributed in some areas.For example, the support described below may be made of a light-transmitting material. By incorporating the above-mentioned white pigment into a part of the image-receiving layer, a part of the reflected image can be made into a projected image. 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 layers depending on the above-mentioned function, and the thickness of the image-receiving layer is preferably 1 to 100 μm, and preferably 1 to 20 μm. is even more preferable).

It should be noted that a protective layer II may be further provided on the image-receiving layer, a layer made of aggregates of fine particles of a thermoplastic compound may be further provided on the image-receiving layer, and a layer of a thermoplastic compound may be further provided on the image-receiving layer. An image receiving material provided with a layer made of aggregates of fine particles is described in JP-A-62-210460.

Furthermore, an adhesive or a layer containing an adhesive and a release paper may be laminated in a single manner on the surface of the support opposite to the side on which the image-receiving layer is provided. Regarding image-receiving materials, Japanese Patent Application Laid-Open No. 63-2564 by the present applicant
There is a description in Publication No. 7.

The recording material of the present invention is developed as described above, and
By pressing the above image-receiving materials in a stacked state,
The unpolymerized polymerizable compound can be transferred to an image-receiving material to obtain a polymer image on the image-receiving material. Regarding the above-mentioned pressurizing means, various conventionally known methods can be used.

Further, in the case a 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 the image on the image-receiving material as described above, the image-receiving material may be heated as in the method of copying and forming the image in Japanese Patent 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.

The recording material of the present invention is a photosensitive material for black and white or color photography and printing, a printing photosensitive material, a printing plate, an X-ray photosensitive material, a medical photosensitive material (for example, ultrasonic diagnosis @ CRT photosensitive material), a combinator. It has many uses, such as photosensitive materials for graphic notebooks and copying machines.

The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited thereto.

[Example 1] Preparation of silver halide emulsion Gelatin θg and 23.1 g of potassium bromide were dissolved in 31 g of water, heated with to'ci, and while stirring, 744 g of silver nitrate was dissolved in 200 ml of water. Added over 70 minutes. Then add 3.3g of potassium iodide to 100r of water.
The solution dissolved in rll was added for 2 minutes. After adjusting the pH of the silver iodobromide emulsion obtained in this way, allowing it to settle and removing excess salt, the pH was adjusted to t, oKy4, and the yield decreased to 0.
0 g of silver iodobromide emulsion was obtained.

Preparation of benzotriazole silver emulsion 22 g of gelatin and 3.2 g of benzotriazole are mixed with 3 parts of water.
000ml. This solution was stirred while maintaining the temperature at ψ0°C, and a solution of 17 g of silver nitrate dissolved in 100 ml of water was added over 2 minutes. Excess salt was precipitated and removed by adjusting the pH of the resulting emulsion. Then the pH was adjusted to 6.
30 to obtain a benzotriazole silver emulsion. The yield of emulsion was 4toog.

Preparation of Photosensitive Composition In 100 g of trimethylolpropane triacrylate, 0.40 g of the following copolymer and 6.00 g of Pergus Script Red 1-4-B (manufactured by Ciba Geigy) were dissolved. To the above solution ir, oog, l, /'-azobis(/-
cyclohexanecarbonitrile)s, oog, reducing agent (1) of the present invention (1) J, 7Fg in methylene chloride/, trg
A solution dissolved in was added.

Silver halide emulsion prepared as described above in the above solution! ,
ff4g1&benzo) I) Azole silver emulsion J, J
jll and use a homogenizer every minute/! 00
At 0 rotations! The mixture was stirred for a minute to obtain a photosensitive composition.

(°′su”-) a-i3 Microcapsule liquid p4 Isopan (Kuraray ■) /r, 4% aqueous solution 10, J-
1g of pectin, 2. rde polyaqueous solution←r.

vI4 to pH ψ, Q using lOs sulfuric acid.
The above photosensitive composition was added to the prepared aqueous solution and stirred for 2 minutes at 7000 rpm using a homogenizer to emulsify the above photosensitive composition in the aqueous solvent.

To this aqueous emulsion 7λ,jg, a urea 4Aθ% aqueous solution J',
JJg, resorcinol//#% aqueous solution 2rJg, formalin 37cm aqueous solution r, ztg, ammonium sulfate 1.7
Add 2.7ψg of 4% aqueous solution one by one and add to' while stirring.
Heating was continued for 2 hours at c. After that, the pH was adjusted to 7.2 using a 10% aqueous sodium hydroxide solution, and 30.196% sodium hydrogen sulfite aqueous solutions J, j, 2j were added.
A microcapsule liquid was prepared.

Preparation of recording material Microcapsule liquid lo, og prepared as above
, Emmalex NP-4 (made by E1 emulsion ■)
iot4 aqueous solution/, Og, the following base precursor (a)
/ (7% by weight (water/ethanol = !0/!0 volume ratio) 6.2←g of a finely dispersed solution was added and applied onto polyethylene terephthalate with a thickness of 100 pm using a coach-in blonde of ◆ψO. A recording material (A') according to the present invention was prepared by drying at 2j0c.

(Base precursor (a)) [Example 2] In place of the reducing agent (1), z, and 7Pg used in the preparation of the photosensitive composition of Example 1, the reducing agent (co) of the present invention was substituted for D.
A recording material (B) according to the present invention was prepared in the same manner as in Example 1 except that , t#g was used.

[Example J]

In place of the reducing agent (1) z and 7Pg used in the preparation of the photosensitive composition of Example/b, the reducing agent (j) of the present invention (j),
A recording material (C) according to the present invention was prepared in the same manner as in Example 1, except that 22 g of the sample was used.

[Example 1] Reducing agent (1) used in the preparation of the photosensitive composition of Example 1! , 7Pg in place of the reducing agent (φ) 3.
A recording material (D) according to the present invention was produced in the same manner as in Example 1, except that tg was used.

〔Example! ]

The reducing agent (t) 2# of the present invention was used in place of the reducing agent (/L 2.72 g) used in the preparation of the photosensitive composition of Example 1.
! A recording material (E) according to the present invention was prepared in the same manner as in Example except that fl was used.

[Example 6] Reducing agent (lφ)φ of the present invention was used in place of 2.72 g of reducing agent (1) used in the preparation of the photosensitive composition in Example/.
,/! A recording material (F) according to the present invention was produced in the same manner as in Example 1 except that g was used.

[Example 7] In place of 2.7 Pg of the reducing agent (1) used in the preparation of the photosensitive composition of Example 1, the reducing agent (/A)/ of the present invention was used.
A recording material (G) according to the present invention was prepared in the same manner as in Example/, except that , rPg was used.

[Example r]

Reducing agent (1) used in the preparation of the photosensitive composition of Example/! , 7? The reducing agent of the present invention (/F)2 instead of g
．． /! A recording material (H) according to the present invention was produced in the same manner as in Example 1 except that FZ was used.

[Comparative example/]

Example 1 except that the following reducing agent (b) and iig were used in place of 2.75 g of reducing agent (1) used in the IA photosensitive composition of Example 1. Recording material (I) according to the present invention was produced in the same manner.

[Comparative Example 2] The following reducing agent (C) λ was used instead of 2.72 g of the reducing agent (1) used in the illumination of the photosensitive composition in Example/.
A recording material (J) according to the present invention was prepared in the same manner as in Example/, except that , trg was used.

[Comparative Example 3] In place of the reducing agent (1)-2,7Pg used in the preparation of the photosensitive composition of Example 1, the following reducing agent (d) 7.
A recording material (K) according to the present invention was prepared in the same manner as in Example 1 except that 7rg was used.

[Comparative example φ]

In place of the reducing agent (1) J, 72 g used in the preparation of the photosensitive composition in Example/, the following reducing agent (e) #, /
A recording material (L) according to the present invention was produced in the same manner as in Example 1 except that 4 g was used.

(Reducing agent (b)) (Reducing agent (C)) (Reducing agent (d)) (Reducing agent (e)) 4<Q% of sodium hexametaphosphate in 721 g of water
Add the aqueous solution//fl, and then 3. ! - 3 grams of zinc di-alpha-methylbenzylsalicylate and! ! Mix r2g of polycalcium carbonate slurry.

Dispersion was performed using a mixer. Disperse the liquid with a Dyno Mill disperser, and for 200g of the obtained liquid! 0% SDR latex 6gk and 1% polyvinyl alcohol rryH were added and mixed uniformly. The basis weight of this mixed liquid is J-ta g/m.
An image receiving material was prepared by uniformly applying the mixture onto the paper No. 2 to a wet film thickness of 30 μm and drying it.

Evaluation of Recording Materials Each of the recording materials obtained in Examples/~t and Comparative Example 1-← was imagewise exposed for 1 second at λOO lux using a tungsten bulb, and then placed on a hot plate heated to lzo 0c. Heat with button for 10 seconds, then press button for 20 seconds. Next, each photosensitive material was layered with the image receiving material 3.
The density of the magenta positive color image obtained on the image-receiving material was measured using a Macbeth reflection densitometer after passing through a 70 kg 7 cm 2 pressure roller.

Further, the density of the magenta positive color image obtained on the image-receiving material was measured using a Macbeth reflection densitometer by performing the same processing except that the above-mentioned exposure processing was not performed.

The above measurement results are shown in the first raw sample column below.

In Table 7, rDmaxJ is the reflection density (corresponding to the exposed area) when exposure processing is performed, and r
Dmin J is the reflection density when no exposure processing is performed (
(corresponds to the unexposed area).

Next, the storage stability of each sample was evaluated. Example/-4
Each recording material obtained in Comparative Example/~Da was
After being stored for r days under moist heat conditions of 0°C and 277% humidity, the same treatment as for the raw sample was performed. The above measurement results are shown in the column of the middle leg moist heat sample in Table 1 below.

As is clear from the results shown in Table 1, the recording material using the reducing agent according to the present invention provides a good positive image with high contrast (S/N ratio) in a very short time and is stable in storage. It can be seen that the quality is also excellent.

[Example 7] Gelatin aqueous solution (gelatin/4g in 1600ml of water)
and sodium chloride 0. To this, an aqueous solution containing 7/fl of potassium bromide was added, adjusted to 1) HJ, 2 with /N sulfuric acid, and kept warm at 0C).
rJ and a silver nitrate aqueous solution (o,ry moles of silver nitrate dissolved in JOOml of water) were simultaneously added at equal flow rates over jO minutes. Seven minutes after this addition was completed, the following 7% methanol solution of sensitizing dye (1) was prepared! IJml was added, and from 71 minutes after the addition, 100ml of an aqueous solution containing potassium iodide λ, g and a silver nitrate aqueous solution (0.0/1 mole of silver nitrate dissolved in 100ml of water) were added at equal flow rates over 1 minute. Added. To this emulsion, add 1.2 g of polyisobutylene (monosodium co-maleate) to precipitate it, wash with water to desalt it, add 4 g of gelatin to dissolve, and add thiosulfuric acid. t
In addition, chemical sensitization was performed for 71 minutes to produce a monodisperse/φ-hedral silver iodobromide emulsion (A-/
) 7000g was prepared.

(Sensitizing dye (1)) N(C2H5)3 Gelatin aqueous solution (20 g of gelatin in 1100 ml of water
and sodium chloride 0. 200 ml of an aqueous solution containing 7/g of potassium bromide and a silver nitrate aqueous solution (0.6 g of silver nitrate in 200 ml of water). (dissolved rotamol) was simultaneously added at equal flow rates over a period of 30 minutes. Seven minutes after this addition was completed, ψrml of a /% methanol solution of the following sensitizing dye (co) was added, and 10 minutes after the addition of the sensitizing dye, 100 ml of an aqueous solution containing 2.2 g of potassium iodide and a silver nitrate aqueous solution were added. (09071 mol of silver nitrate dissolved in 700 ml of water) was added simultaneously over a period of 1 minute. To this emulsion, 2 g of poly(imbutylene-monosodium co-maleate) was added, precipitated, washed with water and desalted, 111 g of gelatin was added and dissolved, and further 0.7 mg of sodium thiosulfate was added. ,
Chemical sensitization was carried out at 60°C for lj minutes, and the average particle size was Q.

/Jμm monodisperse/tetrahedral silver iodobromide emulsion (A-J)io
oog was prepared.

(Sensitizing dye (2)) Gelatin aqueous solution (add 20 g of gelatin and 0.1 g of sodium chloride in 1 mL of water, pHJ with /N sulfuric acid,
200 ml of an aqueous solution containing 7/g of potassium bromide and a silver nitrate aqueous solution (0.2 moles of silver nitrate dissolved in 200 ml of water) were added simultaneously for 30 minutes. Added at flow rate.

Seven minutes after this addition is complete, use the following sensitizing dye (3).
0. ! After addition of the sensitizing dye, 100 ml of an aqueous solution containing 3.46 g of potassium iodide and a silver nitrate aqueous solution (1 θθ ml of water) were added.
0.02λg of silver nitrate dissolved in the solution) was added at a constant flow rate over 1 minute. To this emulsion, poly(imbutylene-monosodium co-maleate) was added to Jg, sedimented, washed with water, desalted, gelatin 1
Add and dissolve Oil, and then add sodium thiosulfate o,
Add ajmH! Chemical sensitization was carried out at 0C for 20 minutes.
1000 g of a monodisperse/tetrahedral silver iodobromide emulsion (A-3) having an average grain size of 0.73 μm was prepared.

(Sensitizing dye (3)) The following polymerizable compound (Karayat RrAou, manufactured by Nippon Kayakuhin → 4Jg, 0.77g of the following copolymer, p-)
Luenesulfonamide o, stg.

The following yellow image-forming substances! g was dissolved.

To the above solution were added 2.20 g of the reducing agent (1) of the present invention, 0.02 g of the development inhibitor release precursor described below, and the photopolymerization initiator (Irgacure 4 j / ) described below.

Ciba Geigy Co., Ltd. 11 4t, 7/g, 0.01 g of the following antifoggant, Emarex NP-r (manufactured by Nippon Emulsion ■), rgTh, and 20 g of methylene chloride were added to form a homogeneous solution.

A 10% aqueous solution of potassium bromide was added to 11 g of the above silver halide emulsion (A-7)/! ml of a solution of the following development accelerator in methoxy-2-methylpropanol. jml and stirred for 1 minute. Furthermore, polyvinylpyrrolidone (K-/j, manufactured by Wako Tsumugiku ■)
ml of the multi-aqueous solution was added and stirred for 1 minute. Add this mixed solution containing the silver halide emulsion to the above homogeneous solution and use a homogenizer at 1 too many revolutions per minute.
After stirring for a minute, a photosensitive composition (B-/) consisting of W10 emulsion was obtained.

(Polymerizable compound) (Copolymer) (Yellow image forming substance) (Photopolymerization initiator) (Development inhibitor release precursor) (Antifoggant) (Development accelerator) CH2cH2SH Creation of image recording material Photosensitive microcapsule liquid (C -/)/4g% (C-
2) Il,! g, (C-j), 1 g, 1 base pre-strength dispersion, rg% sorbitol, 2096
Aqueous solution ymt and log6 aqueous solution of starch 10ml
l was mixed. In addition, the following surfactants! 11 ml of the multi-aqueous solution and water were added to make the total amount 744 g to prepare a coating liquid for an image recording material.

Apply this coating solution on colored coated paper with basis weight toH/m2z
An image recording material (M) was prepared by coating at a ratio of oH and drying at about to0c.

(Surfactant) [Example io] Reducing agent (1) used in the preparation of the photosensitive composition of Example 22. Reducing agent (co)ji of the present invention instead of POg
A recording material (N) according to the present invention was produced in the same manner as in Example 2, except that 7 g was used.

〔Example//〕

Reducing agent (/) used in the preparation of the photosensitive composition of Example 22. Reducing agent (J) of the present invention instead of yog
A recording material (0) according to the present invention was prepared in the same manner as in Example 7 except that , ←/g was used.

[Example/λ]

Example? Reducing agent (1) used in the preparation of the photosensitive composition 2. The reducing agent (μ)g of the present invention instead of YOg,
A recording material (P) according to the present invention was produced in the same manner as in Example 7 except that /jg was used.

[Example/3] Reducing agent (1) used in the preparation of the photosensitive composition in Example, ? , the reducing agent (r) of the present invention instead of ROG!
A recording material (Q) according to the present invention was prepared in the same manner as in Example 1, except that 1 g of .

[Example/G]

The reducing agent (1) λ used in the preparation of the photosensitive composition of Example 2, the reducing agent of the present invention (/44) in place of POg
! A recording material (R) according to the present invention was prepared in the same manner as in Example except that , j/g was used.

〔Example/! ]

The reducing agent (/4) of the present invention was used instead of the reducing agent (1) x, yQg used in the preparation of the photosensitive composition of Example 2.
A recording material <S> according to the present invention was prepared in the same manner as in the example except that 26 g of the sample was used.

[Example/j) Example? The reducing agent (Il) J of the present invention was used in place of the reducing agent (1) used in the preparation of the photosensitive composition.
A recording material (T) according to the present invention was prepared in the same manner as in the example except that 13 g of the sample was used.

[Comparative example! ]

Reducing agent (1) used in the preparation of the photosensitive composition of Example 22. The above reducing agent (b) J, 1
A recording material (U) according to the present invention was prepared in the same manner as in Example except that 5'g was used.

[Comparative Example 2] The above reducing agent (C) was used in place of 2,70 g of the reducing agent (/,) used in the preparation of the photosensitive composition in Example.
A recording material (V) according to the present invention was prepared in the same manner as in Example except that 2.7ffg was used.

[Comparative Example 7] Reducing agent (1) used in the preparation of the photosensitive composition in Example 2. The above reducing agent (d) 1 instead of dioy
．． A recording material (W) according to the present invention was produced in the same manner as in Example 2 except that rtg was used.

[Comparative example r]

In place of the reducing agent (1) J and P7g used in the preparation of the photosensitive composition of Example 2, the reducing agent (e) Il,
A recording material (X) according to the present invention was prepared in the same manner as in Example 2 except that jJg was used.

Each image recording material (M) to (X) was passed through a continuous gray filter whose transmission density was continuously changing from 0 to 3.01 using a halogen lamp.

After imagewise exposure for 1 second at 2000 lux, /! ! Heat development was performed at 0C.

Then, using a halogen lamp, %! After uniform exposure at 10,000 lux for 30 seconds, each image recording material was overlapped with the image receiving material, and in this state was passed through a pressure roller of jo o Kg/cm2. For each hue (yellow, magenta, and cyan) of the positive color image obtained on each image-receiving material, the maximum density (Dmax) Th and minimum density (Dmin) were measured using a Macbeth reflection densitometer. The measurement results are shown in Table 3.

Table 3 (Immediately after production) Each image recording material was stored separately for r days under the conditions of 0° C., 1 relative humidity and 10° C., and then subjected to image forming treatment in the same manner as above, and the resulting images were evaluated. The measurement results are shown in Table 2.

Table 1 (after storage for r days) As is clear from the results shown in Table 3, the image recording method of the present invention gave very clear images.

Furthermore, as is clear from the results shown in Table 1, the image recording materials (M) to (T) containing the reducing agent represented by the above-mentioned formula CI) retain clear images even after storage under harsh conditions. give.

Claims (2)

[Claims] (1) At least a photosensitive silver halide, a polymerizable compound, a thermal or photopolymerization initiator and the following general formula [
A recording material having a photosensitive layer containing a reducing agent represented by [I] or [II]. General formula [I] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. In the expression, R^2 to R^6 are hydrogen atoms,
Halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, acyloxy group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, alkoxy group, aryloxy group,
Represents a monovalent organic group of sulfonyl group, sulfamoyl group, sulfenyl group, sulfinyl group, amino group, acylamino group, alkoxycarbonylamino group, carbamoylamino group, sulfonylamino group or sulfamoylamino group, R^2~R ^6 may be the same or different, and any two may be connected to form a ring. Incidentally, the reducing agent represented by the general formula [I] or [II] may be linked at any position to form a multimer. Further, it may form a salt. (2) At least a photosensitive silver halide, a polymerizable compound, a thermal or photopolymerization initiator and the following general formula [
I ] or [II] A recording material having a photosensitive layer containing a reducing agent can be exposed to light at the same time as image exposure, or by heating after image exposure, or by further uniformly irradiating light after heating. A recording method for forming a polymer image by polymerizing a polymerizable compound. General formula [I] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. In the expression, R^2 to R^6 are hydrogen atoms,
Halogen atom, alkyl group, aryl group, heterocyclic group, acyl group, acyloxy group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxy group, aryloxy group, sulfonyl group, sulfamoyl group, sulfenyl group, Represents a monovalent organic group of sulfinyl group, amino group, acylamino group, alkoxycarbonylamino group, carbamoylamino group, sulfonylamino group or sulfamoylamino group, and R^2 to R^6 may be the same or different. or any two may be connected to form a ring. Incidentally, the reducing agent represented by the general formula [I] may be linked at any position to form a multimer. Further, it may form a salt.