JPS63306439A - Thermally developable photosensitive material - Google Patents

Abstract

PURPOSE:To improve the aging stability by holding at least photosensitive silver halide, a reducing agent or a precursor thereof, a binder and a specified compd. on a support. CONSTITUTION:At least photosensitive silver halide, a reducing agent or a precursor thereof, a binder and a compd. represented by formula I are held on a support. In formula I, R1 is a substituent providing diffusion resistance to the compd. represented by formula I, M<n+> is a hydrogen ion, a metal ion or the like, n is an integer of 1-4 and the substituent R1 is 8-40C straight or branched chain alkyl, alkenyl or the like. When the resulting photosensitive material is used, an image having high max. density and low min. density is obtd. in a short time. The photosensitive material has superior aging stability.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention relates to a heat-developable photosensitive material that forms an image by heating.

(Prior art) Photography using silver halide has traditionally been the most widely used method because it has superior photographic properties such as sensitivity and tone adjustment compared to other photographic methods, such as electrophotography and diazo photography. I've been exposed to it. In recent years, image-forming processing methods for photosensitive materials using silver halide have been changed from the conventional wet processing using dyeing liquid, etc. to dry processing using heating, etc., making it possible to obtain images easily and quickly. technology has been developed.

Heat-developable photosensitive materials are well known in the technical field, and for more information on heat-developable photosensitive materials and their processes, please refer to Tatoba Fundamentals of Photographic Engineering (1979, published by Corona Publishing), pages 113 and 111, Eiji, published in January 1971. Information #O11, Nebletts, Handbook of Photography and Professional Photography, 7th Edition
fPhotography and Reorogr
aphy 7thEd,) Van Nostrand Reinhold Kanno Rnie (Van No5tra
nd Reinhold Company) 32-3
Page 3, U.S. Patent No. J,/jJ, 904c, No. J, 30
/, No. 471, No. 3゜392.0-0, No. J, 4!
No. 17.07j, British Patent No. 1. /31.101, No. 1. /67゜777 issue and Research Disclosure magazine IP71 in monthly issue y~tz<-ji(RD-/7
θ code).

For example, Research Disclosure Magazine/Re7! Year! Monthly issue! Gu~!
l Eigi (RD-/buri tbu issue), same/974 da month issue 30~! - Easy (RD-/Reference μ33), US Patent No. 3. Derr, tri, same μ, da≦3.072, same, ≠7 noon, t47, same μ, Hiro71. Octopus No. 7, same da,
! No. 07,710, 44. ! No. 60,444, II
, 44/rJ.

It has been proposed in No. 14L, etc. Both of these produce or release dyes by heating to form an image-like distribution of the dye, and are characterized by the ability to obtain the image-like distribution of the dye in a short period of time.

(Problems to be Solved by the Present Invention) However, the heat-developable photosensitive material must contain a reducing agent for development, which causes a problem in stability over time. In other words, stability over time refers to the stability of a photosensitive material during storage before thermal development processing. In order to improve stability over time, reducing agent precursors have been proposed that do not themselves have reducing properties but exhibit reducing properties under the action of nucleophiles or heat. For example, JP-A-1JI7Jt, J7-μ02 noon! No., U.S. Patent No. ≠, J30,617, U.S. Pat. However, converting the reducing agent into a precursor has the drawbacks of prolonging the development time and increasing the development temperature. It is an object of the present invention to provide a photothermographic material which can obtain a long image bond in a short time and has excellent stability over time.

(Disclosure of invention) These objects have been achieved by the invention described below.

That is, the present invention is a heat-developable photosensitive material characterized by containing on a support at least photosensitive silver halide, a reducing agent or its precursor, a binder, and a compound represented by the following pattern (■). .

General formula CI] (R1-Coo°)Mn0 Here, R1 represents a substituent that provides diffusion resistance to the compound of general formula [I), Mne represents a hydrogen ion, a metal ion, or an ammonium ion, and n teeth! -Represents the integer of Buddha.

First, the compound represented by the general formula (IF) used in the present invention will be explained.

ff formula CI] (Rt -COOe) MnΦR1 represents a substituent that provides diffusion resistance to the compound of general formula CI), Mne represents a hydrogen ion, a metal ion, or an ammonium ion, and n is an integer from 7 to μ. represents.

The group represented by R1 that imparts diffusion resistance to the compound of general formula [I] has a total carbon number of t to μO1, preferably lλ to 32, and a straight or branched alkyl group (for example, a methyl group, an ethyl group, n-progyl group, n-butyl group, 1so
-butyl group, a-methyl group, n-heptyl group, n-
Nonyl group% n-undecyl group, n-tridecyl group, etc.)
, alkenyl group (e.g. allyl group, decenyl group, dodecenyl group, oleyl group, etc.), cycloalkyl group (e.g. cyclopropyl group, cyclo means methyl group, cyclohexyl group, norbornyl group, etc.), alkynyl group C Example 1-Bapro-
Lygyl group equivalent aralkyl group (e.g. benzyl group, phenethyl group, etc.), cycloalkenyl group (e.g. jc-hacyclopentenyl group, cyclohexenyl group, etc.), aryl group (e.g. phenyl group, α-naphthyl group, β-su7) chill group, etc.)
or a heterocyclic group (i.e. a nitrogen atom as a heteroatom,
A 3- to 7-membered monocyclic or condensed heterocyclic group having at least 7 oxygen atoms or sulfur atoms as ring constituents, such as -1pyridyl group, derpyridyl group, λ-quinolyl group , -monofuryl group, cochenyl group,
≠-pyrazolyl group, μm imidazolyl group, etc.),
These are KM so that the total carbon number is in the range of r to 140.
, and the number of substituents may be seven or more. (However, among these groups, those having 2 or more carbon atoms may be unsubstituted.) Examples of substituents for these groups include halogen atoms (e.g., fluorine atoms, chlorine atoms,
bromine atom, iodine atom, etc.), nitro group, cyano group, hydroxy group, carboxy group, sulfo group, mercapto group, alkoxy group (e.g. methoxy group, ethoxy group, dodecyloxy group, etc.), acyloxy group (e.g. phenoxy group,
Co, 4A-di-tart-intylphenoxy group %J
tert-butyl-4-hydroxyphenoxy group, 3
-interdecylphenoxy group, -1cr
t-inchylphenoxy group, cocyanophenoxy group,
e-tcrt-octylphenoxy group, dodecyloxyphenoxy group, etc.), alkylthio groups (e.g., methylthio group, ethylthio group, dodecylthio group, etc.), arylthio groups (e.g., phenylthio group, dodecylthio group, dodecylthio group, etc.) groups), alkylsulfonyl groups (methylsulfonyl group, benzylsulfonyl group, dodecylsulfonyl group, etc.), alkylsulfonyl tsc such as phenylsulfonyl group, p-)lylsulfonyl group, ≠-dotecylphenylsulfonyl group, μm
Dodecyloxyphenylsulfonyl group 1, carbonamide group (e.g. acedoyl amide group, benzamide group, N-phenylacetamide group, tetradecanamide group, etc.), sulfonamide group (e.g. methylsulfonamide group, phenylsulfonamide group, p-tolyl) sulfonamide group,
hexadecylsulfonamide group, etc.), amino group (e.g. amino group, dimethylamino group, pyrrolidyl group, biyridyl group, dodecylamino group, anilino group, etc.), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, N -dodecylcarbamoyl group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, dodecyloxycarbonyl ts, etc.), aryloxycarbonyl group (e.g. phenoxycarbonyl group sp -t 6
r@-butylphenoxycarboel group, etc.), acyloxy group (e.g. acetoxy group, etc.), sulfamoyl group (
For example, sulfamoyl group, dimethylsulfamoyl group,
dimethylcarbamoyl group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), imide group (e.g., succinimide group, etc.), ureido group (e.g., 3,3-dimethylureido group, etc.), alkoxycarbonylamino group (e.g., ethoxy carbonylamino group, etc.), aryl group (e.g. phenyl group, p-)lyl group, p-methoxyphenyl group, α
-su7tyl group, β-naphthyl group, etc.) and heterocyclic groups (such as ld/-imidazolyl group, l-pyrazolyl group, cobiridyl group, μm pyridyl group, coquinolyl group, -furyl group, λ-chenyl group, benzotriazolyl group, phthalimide group, etc.).

When R1 is an aryl group, a heterocyclic group, or an aralkyl group, substituents for these groups include, in addition to the above substituents, an alkyl group (e.g., methyl group, ethyl group, 1so-propyl group, tert-butyl group, tert-butyl group, tert-butyl group, tert-butyl group, -pentyl group, te
rt-hexyl group, /, /, J.

3-tetramethylbutyl group, etc.), alkenyl groups (e.g., allyl group, hexenyl group, oleyl group, etc.), alkyl groups (e.g., propargyl group, etc.), and cycloalkyl groups (e.g., propargyl group, etc.).
Examples include cycloalkyl group, cyclopentyl group, cyclohexyl group, etc.).

R1 of the compound represented by the general formula (1) is preferably an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group, and an alkyl group substituted with a substituted phenoxy group or a carbonamide group is preferable. Alternatively, an aryl group substituted with an alkoxy group is preferable.

Mne is an ion of group 1 of the periodic table (e.g. He, Na0
．． ni', Cse, etc.), 1st &o(oy(tae For example, Mg, (a!e, Ba2e, etc.), group ■e3e O(oni/(71:, tbaFe2e, , Co2
e.

Co3Φ, Ni"Φ, etc.), and ammonium ions (expressed as Ra-N-Rs), preferably ions of group 1, group 2 of the periodic table, and ammonium ions. Theal.% likes it.
L, ,<HHe, Nae, Ke, and NH4e, with the most preferred h being He.

Here, R2, R3, R4% R5 are hydrogen atoms, alkyl groups (e.g. methyl group, ethyl group, t-butyl group, etc.),
Substituted alkyl groups, aralkyl groups (e.g. benzyl group,
phenethyl group), substituted aralkyl group, aryl group (
For example, phenyl group, naphthyl group, etc.) and substituted aryl group, the number of carbon atoms from R2 to R5 does not exceed 20, and a ring may be formed between R2 and R5, and they may be the same or different. It's okay.

Here, fR substituents of alkyl groups, aralkyl groups, and aryl groups include nitro group, hydroxyl group, cyano group, sulfo group,
Alkoxy groups (e.g. methoxy groups), 71J-ruoxy groups (e.g. phenoxy groups), acyloxy groups (e.g. acetoxy groups), carbonamide groups (e.g. acetamido groups), sulfonamide groups (e.g. methylsulfonamide groups), sulfamoyl groups (e.g. methylsulfamoyl group), halogen atom (e.g. fluorine, chlorine, nitrogen), carboxy group, carbamoyl group (e.g. methylcarbamoyl group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, etc.), sulfonyl group (e.g. methylsulfonyl group) ) is exposed. When there are two or more of these substituents, they may be the same or different.

(t) CaB6 engineering (t) CsHlt (person-μ) C17)135COOeNH,” (A-7) (A-r) C15H31COOH (A-to) (A-7/) (A-/4') H35C18- CB-COOH CH2-C00H (A-ij) (11)Hzs C12-CH-C0OHCH2-C0
0H (A-/A) (A-/r) (A-/?) (A-Jo) (t) C5HII (t) CsHu (A-λμ) CH3CH3 (A-J j ) (A-J4) C Person-27) (A-kot) (t)C5H11COOH (t)CBH17 (A-jO) (t)Cs H11 (A-33) (A-3da) (A-3t) 0OH (A-jj) The compound of the present invention is contained in any of the emulsion layer, intermediate layer, protective layer, etc., but it is particularly preferably contained in the same layer as the reducing agent or its precursor.

The compound of the present invention is used in a weight ratio of 0.0/-100 times, preferably o, or
- 0 times, more preferably 007 to 1 times.

The compound of the present invention can be used alone in the constituent layers of a heat-developable photosensitive material, or can be used as a solvent for other oil-soluble additives or dissolved in a known high-boiling organic solvent together with other soluble additives. You can also do it.

That is, the compound of the present invention exists as an oil dispersion in the hydrophilic colloid constituting the layer.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Alternatively, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide may be used.

Specifically, U.S. Pat. No. 4,500,626, column 50;
Research Disclosure Magazine, June 1978 issue, pages 9-10 (RD17029), JP-A-61-10724
No. 0, No. 60-22517 + No. 3, No. 60-22826
Any of the silver halide emulsions described in No. 7 etc. can be used.

The silver halide emulsion used in the present invention may be of the surface latent image type where the latent image is mainly formed on the grain surface, or the internal latent image type where the latent image is formed inside the grain. It may be a so-called core-shell emulsion in which the grain surface layer has different phases. Further, in the present invention, a direct reversal emulsion can be used in which a positive image is obtained by combining an internal latent image type emulsion with a nucleating agent and/or an optical coupler.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing bicyclic compound (JP-A-58-126526, JP-A-5B-215644).

The coating amount of the photosensitive silver halide used in the present invention ranges from 11 mg silver equivalent to 10 fj 7 m''.

In the present invention, along with photosensitive silver halide, 8!
Metal salts can also be used together as oxidizing agents.

In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

All of the above! Organic compounds that can be used to form the silver salt oxidizing agent include those described in JP-A-61-107240 (1).
0) *Lower left column ~ (11) Page upper left column, U.S. Patent 4,500
．． There are compounds described in columns 52 to 53 of No. 626. Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in Japanese Patent Application No. 113235/1982, and silver acetylene described in Japanese Patent Application No. 90089/1982. Organic silver salts of 21!1 or more may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50H to 10H/- in terms of silver.
2 is appropriate.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex 70 cyanine dyes, holopolar cyanine dyes,
Included are hemicyanine dyes, styryl dyes and hemiosonol dyes.

Specifically, Japanese Patent Publication Nos. 59-180550 and 60-1
No. 40335, Research φ Disclosure Magazine 197
Sensitizing dyes described in June 1988 issue, pages 12-13 (RDI7029), Japanese Patent Application Laid-Open No. 111239/1980, Japanese Patent Application No. 1983
Examples include heat-decolorizable sensitizing dyes described in Japanese Patent No. 172,967 and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization (for example, as described in US Pat. , No. 933, 390, ゛ 3,635,
No. 721, No. 3,743.510, No. 3,615,6
No. 13, No. 3,615.641, No. 3,617,29
No. 5, as described in No. 3,635,721).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and wS4,225,666.

The amount added is generally about 10-e to 10''2 moles per mole of silver halide.

The reducing agent used in the heat-developable photosensitive material of the present invention includes, in addition to those generally known as reducing agents, a dye-donating substance (DRR compound) having reducing properties, which will be described later. Also included are reducing agent precursors that do not themselves have reducing properties but develop reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include U.S. Pat.
No. 500,626, tA49-50 columns, 4°483.
No. 914, columns 30-31, JP-A-60-140335
No. (l) to (18) pages, JP-A-60-12843
No. 8, No. 60-128436, No. 60-128439
No. 60-128437 and the like can be used. Also, JP-A-56-138,736, JP-A No. 57-
Reducing agent precursors such as those described in US Pat. No. 40,245 and US Pat. No. 4,330,617 can also be used.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 01 to 20 mol, particularly preferably 01 to 10 mol.

In the present invention, when a compound of the general formula (CII) described below is used as a dye-donating compound, the reducing agent is a compound represented by the following general formula (LI) or (Lll) (
This will be referred to as the "Electronic 4-Yong" (hereinafter referred to as the ``Denshi 4 Yong'')7. ,5,
. 'R' In the formula, A□ and A2 each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophilic reagent.

Here, the nucleophilic reagents include anionic reagents such as OHe, Roe (R; alkyl group, aryl group, etc.), hydroxamic acid anions 8032e, secondary amines, hydrazine, hydroxylamines, etc. Examples include compounds with lone pairs of electrons such as alcohols and thiols.

Preferred examples of AI and A2 include a hydrogen atom, an acyl group,
Alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, dialkylphosphoryl group, dialkylphosphoryl group, or JP-A No. 7037, same! Turco 010! 80, A2 may be bonded to R1, R2, R3 and R4 to form a ring, if possible. Also, A, A2 may be the same or different.

R1, R2, R3 and R4 are each a hydrogen atom, an alkyl group (optionally substituted alkyl group, e.g. methyl group, ethyl group, n-butyl group, cyclohexyl group, n-octyl group, allyl i, 5ec-octyl group) , tert-
Octyl group, n-dodecyl/L4. n- is an tadecyl group,
n-hexadecyl group, tert-octadecyl group, 3-
Hetesadecanoylaminophenylmethyl group, Hiro-hexadecylsulfonylaminophenylmethyl group, λ-ethoxycarbonylethyl group, 3-carboxypropyl group, N
-ethylhexadecylsulfonylaminomethyl group, N-
methyldodecylsulfonylamine ethyl group); aryl group (optionally substituted aryl group, such as phenyl group, 3-hexadecyloxyphenylene/+4.j-methoxyphenyl group, 3-sulfophenyl group, !-chlorophenyl group) , 2-rupoxyphenyl group, 3-dodecanoylaminophenyl group, etc.); alkylthio group (optionally substituted alkylthio group, such as n-butylthio group,
methylthio group, tert-octylthio group, n-dodecylthio group, co-hydroxyethylthio group, n-hexadecylthio group, 3-ethoxycarbonylpropiothio group, etc.); arylthio group (optionally substituted arylthio group, e.g. phenylthio group, ≠-chlorophenylthio group, 2-n-octyloxy-5-t-butylphenylthio group, Hiro-dodecyloxyphenylthio group, ≠-hexadecanoylaminophenylthio group, etc.); sulfonyl group (optionally substituted) Aryl or alkylsulfonyl groups such as methanesulfonyl group, butanesulfonyl Lp-
) luenesulfonyl group, cudodecyloxyphenylsulfonyl group, Hiro-acetylaminophenylsulfonyl group); sulfo group; halogen atom (e.g. fluorine atom,
chlorine atom, bromine atom, iodine atom); cyano group; carbamoyl group (carbamoyl group that may be substituted, such as methylcarbamoyl group, diethylcarbamoyl group, 3-
(-2, 'A-sheet t-pentylphenyloxy)propylcarbamoyl group, cyclohexylcarbamoyl group,
di-n-octylcarbamoyl group, etc.); sulfamoyl group (optionally substituted sulfamoyl group; for example, diethylsulfamoyl group, di-n-octylsulfamoyl group, n-hexadecylsulfamoyl group, J- is
o-hexadekylaminophenylsulfamoyl group); 7-mido group (optionally substituted amide group, acetamido group, 1so-butyroylamino group, Hiro-tetradecyloxyphenylbenzamide group, 3- (xadecamylaminobenzamide group, etc.); imide group (optionally substituted imide group, such as cono-phosphate imide group, 3-laurylcono-phosphate group, phthalimide group, etc.); carboxyl group; sulfonamide group ( A sulfonamide group that may be substituted, such as a methanesulfonamide group, an octane sulfonamide group, a hexadeca/sulfo/amide group,
benzenesulfonamide group, toluenesulfonamide group, μm lauryloxybenzenesulfonamide group, etc.)
represents.

However, the total carbon number of R1-R4 is r or more. Further, in general formula (Ll), R1 and R2 and/or R3 and R4, and in general formula (LII), R1 and R2, R2 and R3, and/or R3 and R4 bond to each other to form a saturated or unsaturated It may form a ring.

Among the electron donors represented by the general formula (Li3 or [Ln), those in which at least two of R1 to R4 are substituents other than hydrogen atoms are preferred.

Particularly preferred compounds are those in which at least one of R1 and R2 and at least one of R3 and R4 are substituents other than hydrogen atoms.

It is represented by the general formula (Lr) or (Lll) below and is not a filter.

H (♂) H NHS O2C16H3a(n) (80H H (Jfi (t, tr)) The amount of electron donor used has a wide range, but is preferably 0.01 mole per mole of positive dye-donating substance. 〜jQmol,
A particularly preferred range is 0.1 mol to j mol.

Also, o, ooi moles per mole of silver halide! mol, preferably 0.07 mol to 5 mol.

In a preferred embodiment of the invention, the electron donor is used together with an electron transfer agent or a transfer agent precursor.

The electron transfer agent is a compound that is oxidized by silver halide and whose oxidized form has the ability to cross-oxidize the electron donor, and is preferably mobile.

Electron transfer agents include alkyl-substituted hydroquinones such as hydroquinone, t-butylhydroquinone, co-, j-dimethylhydroquinone, catechols, pyrogallol, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and alkoxy-substituted hydroquinones such as methoxyhydroquinone. and polyhydroxybenzene derivatives such as methylhydroxynaphthalene.

Furthermore, hydroxylamine series such as methyl gallate, ascorbic acid, ascorbic acid derivatives, N, N'-di (2-ethoxyethyl) hydroxylamine, /-
Pyrazolidones such as phenyl-3-pyrazolidone, ≠-methyl-t-hydroxymethyl-7-phenyl-3-pyrazolidone, p-aminophenol, p-methylaminephenol, p-dimethylaminephenol, p-piharicino Aminophenol, ≠-dimethylamine-2,6
-Amine phenols such as cymethoxyphenol, N-
) f rule - phenylene diamine, N, N.

Phenylenecyamines such as N', N'-tetramethyl-p-phenylenecyamine, gougethylaminocho, and O-dimethoxyaniline; reductones such as pyrodinohexose reductone and pyrodinohexose reductone;
Examples include hydroxytetronic acids, and in the present invention, compounds represented by the following general formula [X] are particularly useful.

In the formula, R represents an aryl group. R11, R12, R13
and R14 represent a hydrogen atom, an alkyl group, or an aryl group, and these may be the same or different.

Examples of the aryl group represented by R in the general formula [X] include phenyl group, naphthyl group, tolyl group, and xylyl group. These groups may be substituted. For example, norogen atoms (chlorine atoms, bromine atoms, etc.),
Amino group, alkoxy group, aryloxy group, hydroxyl group,
Aryl group, carbonamide group, sulfonamide group, plucyloxy group, benzoyloxy group, ureido group, carbamate group, carbamoyloxy group, carbonate group, carboxy group, alkyl group (methyl group, ethyl group, propyl group, etc.) It may also be an aryl group substituted with, etc.

The alkyl group represented by R11, R12, R13 and R14 in general formula [X] is an alkyl group having carbon number/-10 (
For example, methyl group, ethyl group, propyl group, butyl group, etc.)
and these alkyl groups may be substituted with hydroxyl groups, amino groups, etc. Further, as the aryl group, phenyl group, naphthyl group, xylyl group, tolyl group, etc. can be used. These aryl groups include halogen atoms (chlorine atoms, bromine atoms, etc.), alkyl groups (methyl group, ethyl group, propyl group, etc.), hydroxyl groups, alkyl groups,
It may be substituted with an oxy group (methoxy group, ethoxy group, etc.). R11, R12, R13 and R14 of the present invention are.

Hydrogen atom, alkyl group with carbon number/~io, carbon number/-1
A 0-substituted alkyl group and an aryl group are preferred, and a hydrogen atom, a methyl group, and a hydroxymethyl group are more preferred.

Specific examples of the compound represented by general formula (X) are shown below.

C11゜ I CI+2011 ! I ■ I C11゜ C.It.

■ χ−20 ■ 1! υ! 1 +1 The electron transfer agent precursor used in the present invention does not have a developing effect during the storage of the photosensitive material before use, but may be treated with an appropriate activator (e.g., base, nucleophile, etc.) or heating. It is a compound that can release an electron transfer agent for the first time.

In particular, the electron transfer agent precursor used in the present invention has no function as an electron transfer agent before development because the reactive functional group of the electron transfer agent is blocked with a blocking group, but under alkaline conditions Alternatively, since the blocking group is cleaved by heating, it can function as an electron transfer agent.

Examples of the electron transfer agent precursor used in the present invention include 2- and 3-acyl derivatives of l-phenyl-3-pyrazolidinone, coaminoalkyl or hydroxylalkyl derivatives, hydroquinone, metal salts such as catechol (lead,
cadmium, calcium, barium, etc.), halogenated acyl derivatives of hydroquinone, oxazine and bisoxazine derivatives of hydroquinone, lactone type electron transfer agent precursor, I-idokuquinone pro-II form having a 4c-class ammonium group, cyclohexyl-λ- En-7, ≠-
In addition to dione-capable compounds, compounds that release simitron transfer agents through electron transfer reactions, compounds that release electron transfer agents through intramolecular nucleophilic substitution reactions, electron transfer agent precursors blocked with 7-thallide groups, indomethyl Examples include group-blocked electron transfer agent precursors.

The electron transfer agent precursor used in the present invention is a known compound, for example, U.S. Pat. Ri♂r No. 3, 2 Riyo, 77g, No. 3. ≠Otsu 2, 21, 1.
No. 3. ! It! O4 No. 3. tl! r, ≠
No. 3, No. 3. Otsu! 0.7≠ri issue, same No. 1, 20ri,
rro No. 11-. 330. t/No. 7, same No. ≠, 3
10. No. t/co, British Patent No. 1, No. Q23.70/,
Same No. 1゜23/, No. 130, No. 1, 21♂, No. 2 Hiro, No. 1, 3 Hiro 6. ri No. 20, JP-A-57-≠029j
No. 61-//No. 37, same! r-//ltO issue, same j
Tar/7J'≠5 No., J Tar/12 Hiromu Ri No., same!
The developer precursor described in 1r2ti-to and the like can be used.

In particular, the Tokukai Showa Jter I'yr≠Jr issue, the same Jter/12+
Hirori issue, same! Tar/J', 2≠! /- as stated in No. O etc.
Precursors of phenyl-3-pyrazolidinone are preferred.

The electron transfer agent or its precursor used in the present invention can be used within a certain concentration range. A useful concentration range is from 0.00/molar to 0.0/molar, with a particularly useful concentration range being from 0.00/molar to 1/molar.

In the present invention, it is advantageous to use silver as the III imaging material. Also, when silver ions are reduced to silver under wet conditions, it contains a compound that generates or releases a mobile dye in response to or inversely to this reaction, i.e., a dye-donating substance. You can also do it.

Examples of dye-donating substances that can be used in the present invention include:
Compounds that form pigments by oxidative coupling reactions (
couplers).

The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. Specific examples of developers and couplers are "The Theory Opza 7 Years Old Tographic Process" by James.
4th edition (T, H.

James “The Theory of the
PhotographicProcess''')2
91-334g, and pages 354-361, JP-A-1983
-123533, 58-149046, 58-
No. 149047, No. 59-111148, No. 59-1
No. 24399, No. 59-174835, No. 59-23
No. 1539, No. 59-231540, No. 60-295
It is described in detail in No. 0, No. 60-2951, No. 60-14242, No. 60-23474, No. 6O-(36249), etc.

In addition, dye silver compounds combining organic silver salts and dyes (Research Disclosure Magazine, May 1978 issue, 54-
58 pages, etc.), azo dyes used in heat-developable silver dye bleaching methods (U.S. Patent No. 4,235,957, Research Disclosure Magazine, April 1976 issue, pages 30-32, etc.)
, leuco dye (U.S. Pat. No. 3,985,565, 4)
, 022.617, etc.) can also be used.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (CI).

CDye - Correspondingly or inversely to the photosensitive silver salt having (Dye- X)n Represents a group that has the property of causing a difference in diffusivity with Y, n represents 1 or 2, and when n is 2, two Dy
e−X may be the same or 6 different.

As a specific example of the dye-donating substance represented by the general formula (CI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in U.S. Patent No. 3,134,76.
No. 4, No. 3,362,819, No. 3,597,2
No. 00, No. 3,544,545, No. 3,482.
It is described in No. 972, etc.

In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in US Pat. It is described in No. 111.628 of 1973.

Furthermore, as described in JP-A-59-185333, a donor-acceptor reaction occurs in the presence of a base and releases a diffusible dye, but when it reacts with an oxidized form of a reducing agent, dye release does not substantially occur. Non-diffusible compounds (LDA compounds) can also be used.

Also, a coupler that has a diffusible dye as a leaving group and releases the diffusible dye by reaction with the oxidized form of a reducing agent (
DDR coupler) is patented in British Patent No. 1゜330.524, Japanese Patent Publication No. 1983-39,165, and British Patent No. 3,443.
, No. 940, etc., and is preferably used in the present invention.

In addition, dye-releasing compounds (DR
R compounds) have also been devised and are particularly advantageously used in the present invention. A typical example is U.S. Patent No. 3.928.312
No. 4,053,312, No. 4,055,42
No. 8, No. 4.33 (No. 3,322, JP-A-59-6)
No. 5839, No. 59-69839, No. 53-3819
No. 51-104゜343, Research Disclosure Magazine No. 17465, U.S. Patent No. 3,725,06
No. 2, No. 3,728,113, No. 3,443,9
No. 39, JP-A-58-116,537, JP-A No. 57-17
9840, US Pat. No. 4,500=626, and the like. A specific example of this type of dye-donating substance is the aforementioned U.S. Patent No. 4.500,6.
No. 26) No. 226-m448 D, No. 11, among which compounds (1) to (3), (10) to (13), and (16) to (
19), (28) to (30), (33) to (35), (
38) to (40) and (42) to (64) are preferred. Also, (21) Masato upper column of JP-A No. 61-124941~
(23) Shinshin The compounds described in the above column are also useful.

In addition, the DRR compound is made into an oxidized form without dye release ability and allowed to coexist with a reducing agent or its precursor, and after development,
A method has also been devised in which a diffusible dye is released by reduction using a reducing agent that remains unoxidized, and a specific example of a dye-donating substance used in this method is disclosed in JP-A-53-110,827.
No. 54-130.927, No. 5G-164,34
No. 2, No. 53-35,533.

Japanese Patent Application No. 61-88625, No. 61-87721, No. 62-34954, and No. 62-34953 disclose dye-donating substances that release diffusible dyes by a similar mechanism.
Compounds are described in which the residual reducing agent causes the N--X bond (where Xl represents an oxygen, sulfur or nitrogen atom) to undergo rM and release a diffusible dye.

This compound is preferably represented by the following general formula (CII).

General Formula (CIO) In the above general formula (Cnl), EAG represents a group that accepts or takes electrons from a reducing substance. X represents a nitrogen atom, an oxygen atom or a sulfur atom. R1 and R2 each represent a substituent other than a hydrogen atom.

When R1 or R2 is bonded to +Tirn e +T-D y e, R1 or R2 represents a simple bond or a divalent substituent, respectively. Also R1 and R2
and may be combined with each other to form a ring.

Time represents a group that releases Dye through a subsequent reaction without causing cleavage of the N-X bond in the formula;
ye represents a diffusible dye.

t represents an integer of Q or l.

Further, in the formula, a solid line represents a bond, and a broken line represents a bond at least one of them.

Among the compounds represented by the general formula (CII), compounds represented by the following general formula (CI[I) are preferred.

General Formula (CIII) In the formula, R3 represents a nitrogen atom and an atomic group necessary for bonding with X to form a 3- to ♂-membered monocycle or fused heterocycle.

The meanings of the other formulas are the same as those described for general formula (CII).

As for EAG, patent application No. 1, Showa 4/-1,1' A 26 No. 1
Mention may be made of the groups described as fC.

More specific examples of EAG include aryl groups substituted with at least one electron-withdrawing group (e.g., hi-nitrophenyl group, 2-nitro-g N-methyl-N-octadecylsulfamoylphenyl group, J-N, N-dimethylsulfamoyl-Hiro-nitrophenyl group, Kocyano-Hiro-octadecylsulfonylphenyl group, J, ≠-
Dinitrophenyl group, 2. II, l, -tricyanophenyl group, Konitro≠-N-methyl-N-octadecylcarbamoylphenyl group, Konitro 5-octylthiophenyl group, Co, Hiro-dimethanesulfonylphenyl group, 3et-dinitrophenyl group, 2-ri o o-4C
- Nitrow 1 methylphenyl group, Kornitrow 3. !
-dimethyl-Hiro-tetradecylsulfonylphenyl group,
2. Hiro-dinitrophel group, λ-ethylcarbamoyl-Hiro-nitrophenyl group, 2. ≠-bisdodecylsulfonyl-j-trifluoromethylphenyl group, co.

3, ta, t, b--: tafluorophenyl group, 2-
acetyl-μm nitrophenyl group, !-nitro 2-hyricyl group, j
-N-hexadecylcarbamoyl-2-pyridyl group, ≠
-pyridyl group, 3. j-dicyano-2-pyridyl group, j
-dodecylsulfonyl-copyridyl group,! -cyano-2-pyrazyl group, Hiro-nitrothiophen-2-yl group,
! -nitro/, 2-dimethylimidazol-ψ-yl group, 3. j-diacetyl-2-pyridyl group, /-dodecyl-! -lupamoylpyridinium-2-yl group, etc.)
, substituted or unsubstituted quinone groups (e.g.
Penzoquinone-koyl group! ',! , t-1limethyl-/, Hiro-penzoquinon-2-yl group, 3-methyl-l
, Hiro-naphthoquinone-koyl group, 3,6-dimether-j-hexadecylthio-/l≠-benzoquinone-λ-yl group, j-pentadecyl-/, 2-benzoquinone-Hiro-
yl group, etc.) or one or more of the above-mentioned vinyllobes, groups such as nitroalkanes, α-diketo compounds, and the like can be mentioned.

Among the compounds represented by the general formula ([I]), a compound represented by the following general formula (CIV) can be mentioned as an example showing more satisfactory characteristics.

General formula (CIV).

EAG, Time, t, and Dye are as described above. Xi represents a divalent linking group, particularly preferably -C- or -5O2-.

R4 and R5 each represent a hydrogen atom or a substitutable group, but may also be bonded to each other to form a saturated or unsaturated carbocyclic or heterocyclic group.

Preferred examples of R4 include a hydrogen atom, a substituted or unsubstituted alkyl group (methyl group, ethyl group, t-butyl group, octadecyl group, 7enethyl group, carboxymethyl group, etc.), a substituted or unsubstituted noaryl group (phenyl group, etc.) group, 3-nitrophenyl group, Hiro-methoxyphenyl group, μ
m-acetylaminophenyl group, ≠-methanesulfonylphenyl group, 2,≠-dimethylphenyl group, ≠-tetradecyl group, etc.), substituted or unsubstituted heterocyclic groups (2-pyridyl group, cofuryl group, 3-pyridyl group, etc.) -d) R5
Preferred examples include a hydrogen atom, a substituted or unsubstituted alkyl group (methyl group, hydroxymethyl group, -〇 H
2-(Time+7-Dye group, etc.) substituted or unsubstituted aryl group (phenyl group, Tei-chlorophenyl group, 2-methylphenyl group, unsubstituted heterocyclic group (Hiro-pyridyl group, etc.), and R4 and Examples of R5 forming a ring to form a condensed ring include the following.In addition, here, in the condensation, 1%-Ti me+T-D y
e will be explained in detail.

Time represents a group that releases Dye through a subsequent reaction by causing cleavage of the N-Xi bond. t is 0
or / represents.

Various groups represented by T im e are known, for example, JP-A-4/-/1972 Hiroshi ≠, pages (j) to (6), ! , /-23t include the groups described in 'A<ir> pages to (/4=) pages.

Examples of positive response type compounds among the dye-providing compounds used in the present invention are listed below.

5O2 2≠ , AVPCH3 (-''12H25 The amount of the dye-providing compound used is arbitrary, but it is usually 0.0
5 mmol/m” (preferably 0.1 mmol/m2)
It is used in the range of ~3 mmol/ug2.

Hydrophobic additives such as the dye-providing compounds described above and the image-forming accelerators described below are disclosed in U.S. Pat.
They can be incorporated into the layers of the photosensitive element by known methods such as those described in No. 7. In this case, JP-A-59-
No. 83154, No. 59-178451, No. 59-17
No. 8452, No. 59-178453, No. 59-178
No. 454, No. 59-178455, No. 59-1784
A high boiling point organic solvent such as that described in No. 57 may be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of high boiling point organic solvent depends on the dye-donating substance 1fj used.
10 g or less, preferably 5 g or less.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic substances into hydrophilic colloids. For example, JP-A-59-
The surfactants listed on pages (37) to (38) of No. 157636 can be used.

In the present invention, a compound that activates development and simultaneously stabilizes the image can be used in the heat-developable photosensitive material. For specific compounds preferably used, see U.S. Patent No. 4.
, 500,626, columns 51-52.

Various anticapri agents or photographic stabilizers can be used in the present invention. For example, research
Disclosure magazine December 1978 issue No. 24-25
Azoles and avi>dans as described above, +yrIg nitrogen-containing carboxylic acids and phosphorus Il as described in No. 59-168442! or JP-A-59-111636
Norcapto compound and its metal salt described in No. 1, patent application No. 1983
Acetylene compounds described in No. 0-228 Coro No. 7 are used for falsification.

In the present invention, the heat-developable photosensitive material may contain a toning agent if necessary. Specific examples of effective toning agents include compounds described in JP-A-4/-/$7 JaS (Komude) Shinshin, upper column to lower left column.

In the present invention, a development inhibitor or its precursor can be used. % of the above-mentioned oxidized DRR compound or the general formula (C
When using the dye-providing compound II), the general formula (
It is preferable to use a positive development inhibitor release agent precursor in which Dye of Cπ) is replaced by a development inhibitor group (AP)K. Regarding Jin's positive development inhibitor precursor, a patent application was filed in 1983.
71 ko r741! ! It is written in the number etc. Addition of these development inhibitors or development inhibitor precursors further reduces fog and further improves the ability to discriminate.

The amount of the development inhibitor or development inhibitor precursor added is preferably about 1 x 10-5 to 10 mol, particularly about 1 x 10-3 to 7 mol, per 1 mol of silver. Also, dye-donating compound / -% /
I/per 1xio-" ~ 1xio"*le, #to/X1
The amount is preferably about 0-10 moles.

Examples of development inhibitors (λF) include compounds having a mercapto group bonded to a heterocycle, such as substituted or unsubstituted mercaptoazoles (specifically /-phenyl-!-mercaptotetrazole, t-(g -carboxyphenyl)-7-mercaptotetrazole, /-(J-
Hydroxyphenyl)-! - mercaptotetrazole,
/-(sulfophenyl)-! -Mercaptotetrazole, 1-(3-sulfophel)-! -Mercaptotetrazole, /-(S-sul7amoylphenyl)-!
-Mercaptotetrazole, /-(3-hexanoylaminophenyl)-! -Mercaptotetrazole, l-ethyl-! -mercaptotetrazole, /-(J-carboquine, ethyl)-1-mercaptotetrazole, -methylthio-yo-mercapto-7,3,≠-thiadiazole, λ-(2-carpoquinlethio)-j-mercazotole /, J, Hiro-theadiazole, 3-methyl-≠-
Phenyl! -mercapto/, 2,4L-triazole, 2-(2-dimethylamineethylthio)-yo-mercapto-/, 3. It-thiasiasol, /-(p-n
-hexylcarbamoylphenyl)-comelcabutoimidazole, 3-acetylamino-gumethyl-! °−
Mercapto/, J, 4Z-triazole, λ-mercaptobenzoxazole, comelcabutobenzimidazole, λ-mercaptobenzothiazole, comelcabuto-6-nitro-/, 3-benzoxazole, 1-
(/-naphthyl)-yo-mercaptotetrazole, cophenylu! - Mercer f'to-y.

3, ≠-oxadiazole, 1-(3-(J-methylureido)phenyl)-yo-mercaptotetrasol, t
-(≠-nitrophenyl)-t-mercaptotetrazole, 1-(2-ethylhexanoylamine)-2-mercaptobenzimidazole, etc.), substituted or unsubstituted mercaptoazaindenes (specifically, 2-mercaptobenzimidazole, etc.), -Methyl-≠-Mercapto/, J, Ja, 7-Tetrazaindene, 6-Methyl-!-Benzyl-Hiro-Mercapto/.

! ,! a, 7-chitrazaindene, o-phenyl, -μ
m-mercaptotetrazaindene, ≠, O-dimethyl-2
-mercapto-/, 3.3a, 7-tetrazaindene, etc.), substituted or unsubstituted mercaptopyrimidines (
Specific examples include 2-mercaptopyrimidine, 2-mercapto-≠-dumethyl-6-hydroxypyrimidine, comerkabuto≠-propylpyrimidine, etc.). Petrocyclic compounds capable of producing iminosilver, such as substituted or unsubstituted benzotriazoles (specifically, benzotriazole, !-2) o benzotrianol, ! -Methylbenzotriazole,! , O-dichloropenzotriazole, r--7'' lomobenzotriazole, j-methoxybenzotriazole, !-acetylaminobenzotriazole, j-n-butylbenzotriazole, !-dichlorobenzotriazole, !, 6-dimethylbenzotriazole, Hiro, j, 4,7-tetrachlorobenzotriazole, etc.), substituted or unsubstituted indazoles (specifically indazole, !-ditroindazole, 3-nido/dazole, 3-Kurorou!
- Nitrointasol, 3-cyanoindazole, 3-
n-butylcarbamoyl intersol, j-nitro 3
-methanesulfonylindazole, etc.), substituted or unsubstituted benzimidazoles (specifically, !-nitropenzimidazole, ≠-nitrobenzimidazole, j, G-diclobenzimidazole, t-cyano-
(6-chlorobenzimidazole, j-trifluoromethyl-6-chloropenzimino"sol, etc.).In addition, development inhibitors can be used as 1→-gin→ → After being released from the i-mono-oxidation-reduction mother nucleus, it becomes a compound that has development inhibition, and even if it changes into a compound that has substantially no or significantly reduced development inhibition. good.

Specifically [/-(J-phenoxycarbonylphenyl)
-yo-mercaptotetrazole, /-(4L-phenoxycarbonylphenyl)r-mercaptotetrazole,
/-(3-maleinimidophenyl)-mercaptotetrazole,! -(phenoxycarbonyl)benzotriazole,! -(p-cyanophenoxycarbonyl)benzotriazole, λ-phenoxycarbonylmethylthio-termercap)-/, 3.41-thiadiazole,
! -nitro 3-phenoxylphonylindazole, j-phenoxycarbonyl-2-mercaptobenzimidazole, j-(2,3-dichloropropyloxycarbonyl)benzotriazoleopenzyloxyluponylbensotriazole, 1-( Butylcarbamoylmethoxycarbonyl)benztriazole,! −()
)oxycarbonylmethoxycarbonyl)bensitol)azole /-(g-benzoyloxyphenyl)-yo-
Mercaptotetrazole, j-(,2-methanesulfonylethoxycarbonyl)-λ-mercaptohenzothiazole, /-(Hiro-<2-chloroethoxycarbonyl)
phenyl)-comelcabutoimidazole, u-[J-
(thiophene-choylcarbonyl)furobylcothio-
Yoichi mercapto/, J, ψ-thiadiazole,
! -cinnamoylaminobenztriazole, /-(J
-vinylphenyl)-mercaptotetrazole, j-succinimidomethylbenzotriazole, j-(≠-succinimidophenyl)-! -Mercapto/, j, 4! -Oxadiazole, 3(≠-(i/
C/, 2-inchazole-3-oxil-t,t-dioxy-2-yl)phenyl)-yo-mercapto-≠-
Methyl/, 2. μ-triazole, 6-fethoxycarbonyl-comelkabutobenzoxazole, etc.
It will be done.

These development inhibitors have a site (-8H) that causes development inhibition.
(S atom of imino group, N atom of imino group, etc.) to Time or R1, R2, R3 or EAG.

Specific examples of the development inhibitor precursor will be shown below.

AF-/ AF-2 AF-J AF-Hiro AF-j AF-1 AF-7 AF-f' AF-ta AF-10 AF-// AF-/3 CONHC16H33 Using 3yX colors of yellow, magenta, and cyan In order to obtain a wide range of colors in the chromaticity diagram, a light-sensitive element having at least three silver halide emulsion layers, each with a different color range, may be used. Examples include a combination of three layers, a back-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each of these photosensitive layers may be divided into one or more layers as necessary.

If necessary, various additives known for heat-developable photosensitive materials and layers other than the photosensitive layer, such as protective layers, interlayers, antistatic layers, antihalation layers, and dye fixing elements, can be easily peeled off. It can have a release layer, a matte layer, etc. For various additives, see Research Disclosure magazine, 1971, Monthly issue, pages 9-1! Member, Japanese Patent Application Publication No. 1973
-Plastic molds, matting agents, sharpness improving dyes, antihalation dyes, surfactants, fluorescent whitening agents, anti-slip agents, and antioxidants described in No. 412j6.

There are additives such as anti-fading agents.

In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent to prevent color fading and color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving sensitivity.

The image receiving element (hereinafter referred to as dye fixing element) may be provided with auxiliary layers such as a protective layer, a peeling layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective layer. One or more of the above layers may include hydrophilic heat solvents, plasticizers, anti-fade agents,
UV absorbers, slip agents, matting agents, antioxidants, dispersed vinyl compounds for increasing dimensional stability, surfactants, fluorescent whitening agents, etc. may be included. In addition, especially in a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable for the dye fixing element to contain a base and/or a base precursor as described below in order to improve the storage stability of the photosensitive element. . Specific examples of these additives are described on pages (24c) to (32) of JP-A-112-112J.

Thermal development: An image formation accelerator can be used in the photosensitive element and/or the dye fixing element of the photosensitive material. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents; accelerating reactions such as generation of Ω dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes; and photosensitive material layers. Physicochemical functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, and silver. It is also classified as a compound that interacts with silver ions. However, these groups of substances generally have multiple functions and usually have some of the above-mentioned promoting effects. For details on these, see Japanese Patent Application Laid-open No. 1983
-Ta 3≠Yo No. 1.

There are various other methods of generating bases, and the compounds used in these methods are all useful as base precursors. For example, JP-A-60-, /6-ri 5rs-t
i); A method of generating a base by mixing a poorly soluble metal compound described above and a compound (referred to as a complex-forming compound) that can undergo a complex-forming reaction with a metal ion constituting the poorly soluble metal compound; There is a method of generating a base by electrolysis, which is described in JP-A No. 4 O-Jjλu, issue '/.

The former method is particularly effective. Examples of poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. Regarding complex-forming compounds, for example, N.E. Martell, R.M. Smith (A.E., Martell, R.M.
, Sm1th) co-author, “Critical Stability.
Constance (Critical 5 tabilit)
y Con5tants) J, Volumes 1 and 5, Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri, and tetracarboxylic acids, as well as 7-osulfono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, compounds with substituents such as phosphino), hydroxamic acids,
Examples include salts of polyacrylates, polyphosphoric acids, etc., with alkali metals, guanidines, amidines, μ-class ammonium salts, and the like.

It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive element and the dye-fixing element separately.

Thermal development---Various development stoppers can be used in the photosensitive element and/or dye fixing element of the photosensitive material in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development. .

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors that undergo a substitution reaction with a coexisting base when heated (for example, JP-A-Sho tO-10
No. 1137, same to-/Takota 3rd issue, same 6Q-ko J (
1) /JJ No. 1.0-230/, 3≠ etc.).

Compounds that release mercapto compounds upon heating are also useful; for example, JP-A-Sho&/-17♂j/No.
/μ72 Hirohiro issue, 6/-/217 Rihiro issue, same t/-/
r! No. 71A3, same &/-/J'203? No. 4/-
/r! 74# issue, same J/-/, Hiroj 3rd issue, same 4/-/
Il'! This is a compound described in Koori No. 6/-J'JtJ2.

A hydrophilic binder can be used for the photosensitive element and/or dye fixing element of the heat-developable photosensitive material. Hydrophilic binders are typically transparent or translucent, such as proteins such as gelatin and gelatin derivatives, cellulose derivatives, starch,
These include natural substances such as polysaccharide compounds such as gum arabic, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. Dispersed vinyl compounds, which are used in latex form and increase the dimensional stability of the photographic material, can also be used.

These binders can be used alone or in combination.

In the present invention, the binder is 1rrL2adashiλ・0g
The following coating amount is suitable, preferably 10 g or less, more preferably 7 g or less.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is less than or equal to solvent/CC to binder/g, preferably O1
! (support) or less, more preferably 0.3 CC or less.

The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and/or dye fixing element may contain an inorganic or organic hardening agent.

Specific examples of hardening agents are given in JP-A/-/1772≠≠ (,
1) to (2) pages and Tokkai Shojter/! ;7A3 No. Otsu No. (
Examples include those described on page 3Lr), and these can be used alone or in combination.

Further, in order to promote dye transfer, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature may be incorporated into the photosensitive element or dye fixing element. The hydrophilic thermal solvent may be incorporated into either the photosensitive element or the dye fixing element, or may be incorporated into both. The built-in layer may also be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but the dye fixing layer and/or
Alternatively, it is preferable to incorporate it into a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be contained in the photosensitive element and/or the dye fixing element.

The support used in the photosensitive element and/or dye fixing element is one that can withstand the processing temperatures. Common supports include glass, paper, polymer films, metals and their analogs;
-/Hiroshi 72≠Those described as a support on page 2 can be used.

The photosensitive element and/or the dye fixing element may have a conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements. As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder. Materials that can be used in these methods include those described in JP-A No. 61-22133 and the like.

Coating methods for the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, pack layer, dye fixing layer and other layers are described in U.S. Pat.
No. J of J26! The methods described in columns ~j-j can be applied.

Radiation, including visible light, can be used as a light source for imagewise exposure to record an image on the photosensitive element. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (LEDs), etc.
Reference No. 44 and US Patent No. 44,! The light sources described in column jA of No. 00.4J4 can be used.

The heat development and dye transfer steps may be performed independently or simultaneously. Further, it may be continuous in the sense that transfer is performed following development in one step.

For example, (1) after imagewise exposing and heating the photosensitive element,
There are two methods: (2) a method in which the dye-fixing elements are stacked and heated if necessary to transfer the mobile dye to the dye-fixing element; and (2) a photosensitive element is imagewise exposed, and the dye-fixing elements are stacked and heated.

The methods (1) and (2) above can be carried out in the substantial absence of water or in the presence of a trace amount of water.

The heating temperature in the heat development process can be developed at about jO'c to about 2 toC, but it is particularly useful to set the heating temperature to about ro 0c to about /f'('. When heating in the presence of a trace amount of water, The upper limit of the heating temperature is below the boiling point.When the transfer process is performed after the heat development process, the heating temperature in the transfer process can range from the temperature in the heat development process to room temperature;
006 or higher and about 100C higher than the temperature in the heat development process
It is more preferable to lower the temperature.

A preferred image forming method involves heating in the presence of a trace amount of water and a base and/or a base precursor' after or simultaneously with image exposure, and at the same time as development, the diffusible dye produced in the area inversely corresponding to the silver image is converted into a dye. It is transferred to a fixed layer. According to this method, the production or release reaction of the diffusible dye proceeds extremely quickly, and the movement of the diffusible dye to the dye fixed layer also proceeds rapidly, so that a high-temperature color image can be obtained in a short time.

The amount of water used in this embodiment is at least 0.1 times, preferably 0.1 times or more, the weight of the total coating film of the light-sensitive element and the dye fixing element, and the amount of the solvent is equivalent to the maximum swelling volume of the total coating film. A small amount of less than the weight (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film) may be sufficient.

The state of the film during swelling is unstable, and depending on the conditions, there is a risk of local bleeding.To avoid this, use water equivalent to the volume at maximum swelling of the total coating film thickness of the photosensitive element and dye fixing element. It is preferable that the amount is less than or equal to . Specifically, F) 1g per square meter of the total area of the photosensitive element and dye fixing element.
A range of -10 g, particularly -35 g, more preferably 3 g-cojg is preferred.

The base and/or base precursor used in this embodiment can be incorporated into both the photosensitive element and the dye fixing element. It can also be supplied dissolved in water.

In the above embodiment, the image forming reaction system contains, as a base precursor, a basic metal compound that is sparingly soluble in water and a compound that can undergo a complex formation reaction with metal ions constituting the sparingly soluble metal compound using water as a medium; It is preferable to raise the pH of the system by reaction of these two compounds during heating. Here, the image reaction system means a region where an image forming reaction occurs. Specifically, layers belonging to both the photosensitive element and the dye fixing element can be mentioned. If two or more layers are present, any of the layers may be used.

The poorly soluble metal compound and the complex forming compound need to be added at least in separate layers in order to prevent them from reacting before the development process. For example, in a so-called monosheet material in which a photosensitive element and a dye-fixing element are provided on the same support, it is preferable that the above-mentioned two additive layers be separate layers, with one or more layers interposed between them. Furthermore, a particularly preferred embodiment is one in which the poorly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. For example, it is preferable to contain the poorly soluble metal compound in the photosensitive element and the complex-forming compound in a dye fixing element having a support separate from the photosensitive element. The complex-forming compound may be supplied by being dissolved in the coexisting water. Hardly soluble metal compounds are covered by Tokukai Sho! It is desirable to contain it as a fine particle dispersion prepared by the method described in J3-10.27 JJ, etc., and the average particle size is preferably 50 microns or less, particularly preferably j microns or less. . The poorly soluble metal compound may be added to any layer of the photosensitive element, such as the photosensitive layer, intermediate layer, or protective layer.
It may be added in two or more layers.

The amount of a poorly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the type of compound, the particle size of the poorly soluble metal compound, the rate of complex formation reaction, etc. It is appropriate to use it in an amount of 6,014 weight percent or less, and more preferably a range of 0,0 weight percent to 6,014 percent by weight is useful.

In addition, when the complex-forming compound is dissolved in water and supplied, the amount of F) from 0.003 mol to jmol/liter
.

In particular, a concentration of O, Ojmol to 2 mol is preferred. Further, in the present invention, the content of the complex-forming compound in the reaction system is preferably 1/10 to 100 times, particularly t//o to 20 times, in molar ratio to the content of the poorly soluble compound.

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, there is a method described on page (2z) of JP-A-4/-/'t72≠≠.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, etc. are used.
There is a means described in pages (colo) to (27) of No. 1724A≠. Alternatively, a layer of conductive material such as graphite, carbon black, metal, etc. may be applied to the photosensitive element and/or the dye fixing element, and the conductive layer may be heated directly by passing an electric current through the layer. .

The pressure conditions and method of applying pressure when overlapping the photosensitive element and the dye fixing element and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 11-117.
The method described on page (27) of No. 21A can be applied.

Any of a variety of heat development apparatuses can be used to process heat-developable color photosensitive materials. For example, Tokukai Shoj Turf 52≠7
No., same jter/77jlA7, same! 1? -/l'/J
! ! No. 60-11'? J No. 1, Jitsugan Showa 60-//4
The devices described in No. 73≠ etc. are preferably used.

Example/ The method of preparing the emulsion for the first layer will be described.

A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 10,100 O of water and keeping it warm at 7!0 C) is mixed with 1 p00 ml of an aqueous solution containing sodium chloride and potassium bromide and a nitric acid aqueous solution (100 ml of water).
0,052 mol of silver nitrate dissolved in nl) was simultaneously added at an equal flow rate over ≠0 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine rO molar ratio) with an average grain size of 0°3Jμ was prepared.

After washing with water and desalting, chemical sensitization was carried out at 0c by adding Hiroshi-hydroxy-6-methyl-/,3.3a,7-tetrazaindene 2011I9 to sodium thiosulfate. The yield of emulsion was 1.00 g.

Next, we will discuss how to prepare the emulsion for the third layer.

A well-stirred gelatin aqueous solution (containing 201 g of gelatin and 3 t of sodium chloride in 1,000 m of water, 7j"ClI
C) 400 m of an aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (400 m of water)
1) and the following dye solution (I) were simultaneously added at equal flow rates over 4 AO minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine to
Mol S) was prepared.

Sodium thiosulfate after washing with water and desalting! ■Tobi-1 hydroxy-4-methyl/, j, Ja,? -Tetrazaindene 2
Chemical sensitization was carried out to"c by adding 0M9. The yield of the emulsion was toot.

Dye solution (I) Methanol μ00x1 Next, we will describe how to prepare the emulsion for the third layer.

A well-stirred gelatin aqueous solution (gelatin 20f and ammonium dissolved in water 1000°C and kept at 30°C), K aqueous solution containing potassium iodide and potassium bromide 1ooo- and a silver nitrate aqueous solution (water/ 000mK
One mole of silver nitrate (dissolved) was added at the same time while keeping the KpA constant. In this way the average particle size O
0! A monodisperse octahedral silver iodobromide emulsion (iodine!molar) of μ was prepared.

After washing with water and desalting, gold and sulfur sensitization was performed by adding chloroauric acid (salt hydrate) and 2f of sodium thiosulfate. The yield of the emulsion was 4/4.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

The yellow dye-donating substance (ri7) is ivy, the electron donor (reducing agent) (//) is 9f, and tricyclohexyl phosphate is 5P? Weigh, cyclohexanone 411
1 d was added and dissolved by heating for about to" cK to form a homogeneous solution. This solution and 104 solution of lime-processed gelatin 1 oo
f and sodium dodecylbenzenesulfonate/I
After stirring and mixing with f, 10 minutes with a homogenizer.
Dispersion was performed at 10,000 rpm. This dispersion is called a yellow dye-providing substance dispersion.

Dispersions of magenta and cyan dye-providing substances are similar to dispersions of yellow dye-providing substances.

It was made using a magenta dye-providing substance <at> or a cyan dye-providing substance (data).

From these K, color photosensitive material 1 with multilayer structure shown in Table
I made 0/.

Furthermore, the compound of the present invention (
A-2), (A-1'), (A-t) and (A-J4)
Ten color photosensitive materials, IOJ%lOμ and ioz, having the same structure as photosensitive material 101 were prepared, except that the same weight of each was used.

In addition, a color photosensitive material IOT was prepared in the same manner using a dye-donating substance prepared by removing the high-boiling point solvent and an electron-donating gelatin dispersion, but aggregates of the coloring material were generated in the coating film of Photosensitive Material 101. .

Next, we will discuss how to prepare the dye fixing material.

Gelatin jj? , mordant 130 with the following structure? and guanidine picolinate were dissolved in 1 sooxt of water and placed on a paper support laminated with polyethylene! After coating to a wet film thickness of μm, it was dried.

On top of the mordant, add 3 t of gelatin and 1 t of hardener. Corbis(vinylsulfonylacetamido)ethane/, 0! t to I
A dye fixing material was prepared by applying a solution dissolved in 00 nl of water to a wet film thickness of 77 μm and drying.

The above multi-layered color photosensitive material iol is made of 1ozK tungsten using a sphere, and the concentration of B%G is continuously changed.
, 2000 through R and gray color separation filters
Exposure was made for 7 seconds at lux.

/jml/m on the emulsion side of this exposed color photosensitive material
Water from step 2 was supplied using a wire purr, and then the dye fixing material and the membrane surface were overlapped so that they were in contact with each other.

The temperature of the water-absorbed film was adjusted to rroc, and the film was heated for 10 seconds using a heat roller. Next, when the dye-fixing material is peeled off from the light-sensitive material, clear colors of blue, green, red, and gray corresponding to the B, G, R, and gray color separation filters are obtained on the dye-fixing material.

Table 2 shows the results of measuring the maximum density (1) max ) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part.

Also, these color photosensitive materials are gt'c, relative humidity t
Table 2 also shows the results of storing the cells under the ON condition for one week and then treating them in the same manner.

It has been found that the use of the compounds of the present invention improves the stability of photosensitive materials over time.

Example - A photosensitive material 0/ was prepared by sequentially coating the following layers on a transparent polyethylene terephthalate support.

(I) The back layer (It) containing ra) The middle layer (III) containing J, A green-sensitive layer (W) containing a green-sensitive layer (W) containing a WI layer containing a green-sensitive layer (W) containing a green-sensitive layer (W) containing the present invention in place of the tri(cyclohexyl) phosphate used in the (I) fourth layer, (III) layer, and (V) MK in the light-sensitive material Koi. Compound (A-ri, (A-6
), (A, -3o) and (A-Jj) were used, but the photosensitive material koi had the same structure as the photosensitive material koi.
203, -〇4! And Ko0! It was created.

Dye-donating substance (Y-/) C4Hg(t) (M-/) (C-/) The method for preparing the internal latent type emulsion is shown below.

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were mixed with an aqueous gelatin solution containing potassium bromide (gelatin j O
f, potassium bromide t? A silver bromide emulsion was obtained by simultaneously mixing the two components (containing the above-mentioned components) at 7!0C for 60 minutes without vigorous stirring. The pAg during addition was kept at r, r.

Before precipitation (before co-mixing) O1 per mole of silver was added as a halogenated steel solvent to the aqueous K-gelatin solution.

When the precipitation was completed, octahedral silver bromide crystals with a uniform grain size and an average grain size of 0.0 and r.mu.m were produced.

Next, per mole of silver, sodium thiosulfate (J hydrate) μ, rWIy and ferric acid (μ hydrate) K, μ■ were added to the silver bromide particles and heated at 7!0C for to minutes. Chemical sensitization treatment was performed. To the core silver bromide emulsion chemically sensitized in this way, an aqueous solution of potassium bromide and silver nitrate was added at 4A at the same pAg as when forming the core grains! The core/shell emulsion is precipitated by simultaneous mixing and addition over a period of 1 minute, and hydrogen peroxide is added as an oxidizing agent at 1 mole per mole of the complex. 2 plus 7!0C! After heating for a minute, the mixture was washed with water to obtain an octahedral silver bromide emulsion with an average grain size of 1 μm.

Next, this internal latent scratch type core/shell silver bromide emulsion was treated with sodium thiosulfate (!hydrate) at 0°7, tWl! per mole of silver.
and poly(N-vinylpyrrolidoy)x.

A cape was added and heated with TOOC for 60 minutes to chemically sensitize the particle surface.

Note that 0.3 tmol of silver was added to form particles in the core portion, and 0.3 μmol of silver was added to form particles in the shell portion.

゛The following sensitizing dye S- was added to this internal latent scratch type emulsion when preparing the coating solution.
/ (0, jlaP/m2') and S-co(l.

0ki7m2') was added.

S-/ (CH2)3 SOa H-N(C2H5)3S-2 Preparation An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of silver latin over 10 minutes at 7j0C with vigorous stirring to form an average grain. An octahedral monodispersed silver bromide emulsion with a diameter of 00 μm was obtained.

Chemical sensitization treatment was carried out by adding jj9 thiosulfuric acid (JJ hydrate) and chloroauric acid (C4C hydrate) per mole of silver to this emulsion, and heating at 77"C for 10 minutes. Using the nonabromide chain particles as a core, potassium bromide and silver nitrate were further added for a minute in the same precipitation environment as when the core particles were formed, resulting in monodispersed octahedral particles with an average particle size of 0.7 μm. A core/shell silver bromide emulsion was obtained.

After washing and desalting, 7 mol of silver was added to the emulsion, i and z, respectively.
A chemical sensitization treatment was carried out by adding txq amount of thiosulfuric acid (IJ) and chloroauric acid (dahydrate) and heating at tooC for 60 minutes to obtain an internal latent scratch type emulsion.

When used for a green sensitive layer, the following sensitizing colors ass-J (0, utrq/m2) and S-u (0,3119/m2) were added to this emulsion when preparing a coating solution.

When used for a red-sensitive layer, the following sensitizing dye B-z (o, arrq/m2) was added to this emulsion when preparing a coating solution.

S- The dye fixing material used in Example I was used.

After applying my-like exposure to the above photosensitive material through a wedge,
Water was supplied to the light-sensitive material at a rate of 1 ko/m2 by spraying, and after overlapping with a dye-fixing material, the entire surface of the light-sensitive material was exposed to white light of 2 lux for 10 seconds from the transparent support side. This was passed between heated rollers so that the temperature of the film was rooCK, heated for -0 seconds, and then the dye-fixing material was peeled off from the light-sensitive material, and a clear positive color image was obtained. Ta.

The results obtained by sensitometry are shown in Table 3.

Table 3 also shows the results of storing these photosensitive materials for one week under the conditions of azoc and 60% relative humidity and then processing them in the same manner.
Shown below.

It has been found that the use of the compounds of the present invention improves the stability of photosensitive materials over time.

Example 3 Using the same emulsion, dye-donating substance, and electron donor as in color photosensitive material 10/ of Example 1, a color photosensitive material 301 having a multilayer structure as shown in Table μ was prepared.

The organic silver salt emulsion was prepared as follows.

Gelatin-02 and μmm acetylaminophenylpropiol! , ri2 to 0. /% sodium hydroxide aqueous solution/
000- and ethanol solution. This solution was kept at 4t00C and stirred. Silver nitrate μ,
! A solution of 2 dissolved in water was added over 1 minute. Excess salt was then removed by sedimentation. then p)
Match 1 to 6.3 and yield JOO? An organic silver salt dispersion was obtained.

Furthermore, the high boiling point solvent ax l used in photosensitive material 301! 30 color photosensitive materials having the same structure as photosensitive material 30 were prepared except that O weight was replaced with the compound (A-t) of the present invention.

Next, we will discuss how to make the dye fixing material.

Poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (the ratio of methyl acrylate and vinylindylammonium chloride is l21) lOf is dissolved in co00- water, and 10
4. Mixed uniformly with 100f of lime-treated gelatin. A hardening agent was added to this mixed solution, and the mixture was coated and dried to a wet film thickness of 0 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed, to obtain a dye fixing material.

After exposure in the same manner as in Example I, the film was heated uniformly for 20 seconds on a heat block heated to a trooc.

After supplying 20d1m2 of water to the membrane surface of the dye fixing material,
Layer the heat-treated photosensitive material so that the film surface is in contact with the photosensitive material, heat it for 1 second on a ROOC heat block, and then peel off the dye fixing material from the photosensitive material. It was done. Its photographic properties are shown in Table j.

In addition, these color photosensitive materials are subjected to uzoc, relative humidity t
After being stored for one week under OES conditions, the samples were treated in the same manner and the results are also shown in Table J.

It has been found that the use of the compound of the present invention improves the stability of light-sensitive materials over time.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Showa era? R/MU old

Claims (1)

[Claims] At least a photosensitive silver halide, a reducing agent or its precursor, a binder, and the following general formula [
A heat-developable photosensitive material comprising a compound represented by I. General formula [I] (R_1-COO^■)_nM^n^■
Here, R_1 represents a substituent that imparts diffusion resistance to the compound of general formula [I], M^n^■ represents a hydrogen ion, metal ion, or ammonium ion, and n is 1
Represents an integer from ~4.