JPS63304242A - Thermally developable color photosensitive material - Google Patents

Abstract

PURPOSE:To enable the conversion of an image of light in the infrared region into a dye image by heating, by using silver halide sensitive to light in the infrared region, a reducing agent, a binder and a dye providing substance which releases or forms a dye by coupling with the oxidized product of the reducing agent. CONSTITUTION:At least silver halide sensitive to light in the infrared region, a reducing agent, a binder and a dye providing substance which release or forms a dye by coupling with the oxidized product of the reducing agent are held on a support. Concretely a silver halide emulsion can be used as the silver halide. The silver halide emulsion may be any of surface latent image type and internal latent image type emulsions. A latent image is chiefly formed on the surfaces of particles in case of the surface latent image type emulsion and in particles in case of the internal latent image type emulsion. A mobile dye image corresponding to an image of light in the infrared region can be formed by heating.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a heat-developable color photosensitive material containing a dye-providing substance that reacts with photosensitive silver halide upon heating to release or form a dye. The present invention particularly relates to a method for preserving a dye image by transferring dyes released by heating to a dye fixing layer. (Prior art and its problems) Regarding the method of obtaining a color image by heat development,
Many methods have been proposed. For a method of forming a color image by the combination of an oxidized developer and a coupler, U.S. Pat. J/, Co.R6 uses a p-phinidine diamine reducing agent and a 7-enolic or activated methylene coupler, U.S. Pat. toλ,ziP
Issue and Research Disclosure Magazine 7! Year? U.S. Pat. This method has the disadvantage that a reduced silver image and a color image are simultaneously generated in the exposed area after expansion and heat development, resulting in a one-color image becoming cloudy. or remove only the pigment from other layers,
For example, a method has been proposed in which the image is transferred to a sheet lacking an image-receiving layer. Furthermore, in order to achieve development in a relatively short time, high density and low density, the mobile dye is imagewise released onto the mobile dye by heating, and the mobile dye is transferred to a solvent such as water. A method for transferring to a dye fixing element with a mordant, a method for transferring to a dye fixing element using a high boiling point organic solvent, a method for transferring to a dye fixing element using a hydrophilic hot solvent built into the dye fixing element, a method for transferring a mobile dye to a dye fixing element. is thermally diffusible or sublimable, and a method has been proposed in which the dye is transferred to a dye-receiving element such as a support. (U.S. Patent No. ≠, 4A≦
No. 3.07, No. 17744.167, No. 4
! l≠7r, No. 717, same No. 3,! No. 07.310, No. u, soo, txt, No. 1I-, 4ctJ. No. 21; European Patent Publication No. 210,640,'! '! Kaisho! r-/$204A6, same II-/≠? Ohiro No. 7,
same! ? -l! HatUO issue, same jP-/Ha14A! Same issue! Tar/410! No., same jter/r01411, same 15'-74r4'JP, same! Chi7711132
No., JP-774nJJ No., same! P-/7ulJII
No. jF-/7113! issue. U.S. Patent No. 3, No. PF, No. 110, etc. The present invention further improves the heat-developable color photosensitive material, imparts the photosensitive silver halide with the ability to be sensitive to light in the infrared region of 70 nm or more, particularly 7 nm or more, and It is intended to visualize images. (Object of the Invention) The object of the present invention is to provide a new photosensitive material that can convert an optical image in the infrared region into a dye image by heating. An object of the present invention is to provide a new method for forming a mobile dye image in the infrared region by moving a mobile hydrophilic dye released by heating to a dye fixing layer. The present invention provides a new method for obtaining a dye image corresponding to the present invention. (Structure of the Invention) The present invention provides a new method for obtaining a dye image corresponding to This is achieved by a light-sensitive material carrying a dye-donating substance that releases or forms a dye through a coupling reaction with an oxidized form of a reducing agent.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, Fi, U.S. Patent No. 200, + Coro No.! 0
Column, Research Disclosure Magazine/? Is 71 the month? Buy ~10 pages (RD/70F), special request Shozv-xat
Zzi issue, 60-22! /No. 71, same t O-1 cor.
Any of the silver halide emulsions described in No.-67 and the like can be used. The silver halide emulsion used in the present invention may be a surface type emulsion in which a latent image is mainly formed on the surface of the grains, or an internal latent image type emulsion in which a latent image is formed inside the grains. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a direct reversal emulsion can also be used in which an internal latent image type emulsion is combined with a nucleating agent and/or a photocasolase. Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. for emulsions for conventional light-sensitive materials can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A Sho! I-/2t! No. 26, Ibid.! T-2/744 (No. 44)). The coating amount of the photosensitive silver halide is in the range of 1 to /Ot/rrL2 in terms of silver.The silver halide that is sensitive to the infrared region is an infrared sensitizing dye, preferably the following: It can be obtained by color sensitization with sensitizing dyes of the general formulas (A) to (L) of the general formula (AI), where R1 and R2 may be the same or different, each alkyl M (preferably number of carbon atoms/
-r, e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, etc.), substituted alkyl group (substituents such as carboxy group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, etc.) atom 1. bromine atom, etc.), hydroxyl, alkoxycarbonyl, (up to r carbon atoms, e.g. methoxycarbonyl group,
Ethoxylated fonyl group, benzyloxycarbonyl group, etc.), alkoxy! I (7 or less carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, butoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, p-)lyloxy group, etc.), acyloxy group (
3 or less carbon atoms, e.g. acetyloxy group, propionyloxy group, etc.), acyl group (up to 3 carbon atoms, e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group,
N,N-dimethylcarbazoyl group, morpholinocarbazoyl group, piperidinocarbamoyl group), sulfamoyl J (e.g. sulfasoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), Aryl slow (e.g. phenyl group, p-hydroxyphenyl group, p-carboxyphenyl, p-sulfophenyl group, α
-naphthyl, etc.) substituted with a π alkyl group (number of carbon atoms below). However, one or more of these substituents may be substituted with alkyl MKt in combination. ). In the general formula (A), -fYx, Yz are oxygen atoms, sulfur atoms, selenium atoms, =N-Rs (Rs is the number of carbon atoms! , carboxyl group, sulfo group, alkoxy group, etc.), or π is an allyl group] or -CH=CH-. In the general formula (A), zlz2 is unsubstituted, and zlz2 is substituted, and π is a benzene ring or naphthyl. Examples of substituents representing atomic groups necessary to form a ring include lower alkyl groups such as methyl groups, halogen atoms, phenyl groups, hydroxyl groups, alkoxy r with carbon number/~Hiro, carboxyl groups, alkoxycarbonyl groups, alkyl sulfur groups, etc. There are famoyl groups, alkylcarbamoyl groups, acyl groups, cyano groups, trifluoromethyl groups, nitro groups, etc. Nitrogen-containing rings made of Yl-Zl, Y2 to Z2 include thiazole nuclear systems [e.g. benzothiazole,
μm Chlorbenzothiazole%! -Chlorpenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, ≠-methylbenzothiazole, j-methylbenzothiazole, t-methylbenzothiazole,! −
Pro-7benzothiazole, t-bromopentthiazole, j-:r-tohenzothiazole,! -Phenylbenzothiazole,! -methoxybenzothiazole, 6-methylbenzothiazole,! -Ethoxybenzothiazole,! -Carboxybenzothiazole,! -2, Toxycarbonylpenzothiazole, j-゛Phenethylbenzothiazole,! -Fluoropentthiazole,! -trifluoromethylbenzothiazole,! ,'6-dimethylbenzothiazole,! -Hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, Hiro-phenylbenzothiazole, natuto [co, /-d)thiazole, naphtho (/, 2-dl thiazole, naph) (J, J-
d) Thiazole,! -meth xinaf) [/, J-d]
Thiazole, 7-nitoxynaphtho[co,/-d]thiazole, l-methoxynaphtho[co,/-d)thiazole,
! -methoxynaphtho [co, J-d) thiazole, etc.],
Zelenazole nuclear system [e.g. penzoselenazole,! -Chlorpenzozelenazole nucleus,! -Methoxybenzozelenazole,! -Methylbenzozelenazole,! -hydroxypenzoselenazole, natu[,2,/-d]zelenazole, natu[/,2-d]zelenazole, etc.], oxazole nuclear systems [e.g. benzoxazole, ! -Chlorbenzoxazole! -Methylbenzoxazole,! -Brombenzoxazole,! -Fluorobenzoxazole,! -Phenylbenzoxazole,! −
Methoxyhenzoxazole, j-) + 1 fluorobenzoxazole,! -hydroxybenzoxazole,
! -Chlorboxybenzoxazole, 4-methylbenzoxazole, 6-chlorobenzoxazole, t
-Methoxybenzoxazole, -Hydroxybenzoxazole,! , ≦-dimethylbenzoxazole,
44.4-dimethylpenzoxazole,! -ethoxybenzoxazole, naphtho [co, /-dl oxazole, naph) [/, J-d] oxazole, naphtho [2,
3-d] oxazole, etc.], quinoline nucleus [e.g. 2-
Kinoline, 3-Me fight Luko Kinoline! -Dimethyl-coquinoline, 6-methyl-coquinoline, ? -fluoro-2-quinoline, t-methoxy-λ-quinoline, t-hydroxy-quoquinoline, r-chloro-quoquinoline,
r-fluoro-hiro-quinoline, etc.], J, J-dialkyl isodorenine nuclei (e.g., 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-cyanoindorenine, 3.3-dimethyl-j-
Methoxyindolenine, 3,3-dimethyl-! -Methylindolenine, J, J-di-tiru! -chlorindolenine, etc.), imidazole cores (e.g., l-methylbenzimidazole, /-ethylbenzimidazole, l-
Methyl-y-chlorobenzimidazole, l-ethyl-
Yo-chlorobenzimidazole, l-methyl-! , 6-
Dichlorobenzimidazole, l-ethyl-3,6-dichlorobenzimidazole, l-alkyl-! -Methoxybenzimidazole, l-methyl-! -cyanobenzimidazole, l-ethyl-! -cytenopenzimidazole, /-methyl-j-fluoropenzimitazole, l-ekylu! -fluorobenzimitasole, l-
Phenyl! . t-dichlorobenzimidazole, l-allyl-! ,6
-dichlorobenzimidazole, l-allyl-! -Chlorbenzimidazole, l-722hensoimitasol, l-phenyl-j゛-chlorobenzimidazole,
l-methyl-! -Trifluoromethylbenzimidazole, l-ethyl-! - triple olometribenzimidazole, l-technical lunaft [l, code d] imidazole, etc.). In general formula (A), Y3 is! Represents the atomic group necessary to form a complete or six-membered carbon ring. General formula (In Al, ml represents 1 or -1, 1 Xi represents an acid residue, m2 represents O''! 7c represents 1, and when the dye has a betaine structure, it is O. Ll, R2 are methine Substituted methine groups represent substituted methyl groups. Substituted methine groups include lower alkyl groups with carbon number/-j, lower alkoxy groups, and aryl groups (this aryl group has a halogen atom, carbon number l-≠ τh*h transitions number of carbons/
~The alkoxy group, sulfo group, carboxy group, etc. of
Examples include π-methine substituted with an aralkyl group (benzyl group, etc.). General formula (B1 In the formula, Y3 and Y4 have the same meanings as Yl and Y2, R6 and R7 have the same meanings as R1 and R2, z3 and z4 have the same meanings as Zl and Z2, and X2 has the same meaning as X, ms has the same meaning as m2. General formula (C) In the formula, Z5 is the atom *1r*υ required to complete the μm quinoline nucleus and coquinoline nucleus. Z6 is zl, z , p represents O or l. m4 represents ko or 3. Y5 has the same meaning as Yl and Y2, υ, R8 and R9 have the same meaning as R1 and Rz, and X3 has the same meaning as R1 and Rz. It has the same meaning as xl, ms has the same meaning as m2, and L3 and L4 have the same meaning as Ll and L2. General formula (D) In the formula, Z8, ZgitZ1%Z2 and f+31 significance, RI
G, R11 have the same meaning as R1, R, Y8 has the same meaning as Y3, X4 has the same meaning as Xl, ms has the same meaning as m2, Y6 and Y7 have the same meaning, It has the same meaning as Y. 1R12,R
13 represents an alkyl group having 1 carbon atoms, and 13 represents a phenyl group. General formula (E) RIO Rima χ has the same meaning as ZxodZt, z2 in the formula. Y9 has the same meaning as Yl and Y2. Yll is oxygen atom, borosilicate atom, selenium atom, =N-Rt
s (R16 has the same meaning as R cost). R14 has the same meaning as R1 and R2; R15 represents a phenyl group and a pyridyl group in addition to the group having the same meaning as R1 and R2; YIO has the same meaning as Y3; m7 has the same meaning as ml; 69, L5 , L6 have the same meaning as Ll and L2. General formula (F) In the formula, Zlo, y9. Yl o, Yl1%R14°R15
The work m7 is the general formula (E) and direction: 1! It is righteousness. General formula (G1, where Zll, Z 1 zu Z 1%Z 2 and IJHir
9 F), YIZ, Yl4 have the same meanings as Yl and Y2, and R17 and R19 have the same meanings as R1 and R2. R18 represents a lower alkyl group having less than 100 carbon atoms or allyl M. Yls has the same meaning as Y3, X5 has the same meaning as Xl, and m7 has the same meaning as m2. General formula (H) Z1 in the formula! , zl4 is synonymous with zl, z2 p. Yl5, Yl6 have the same meaning as Yl, Y2, R21,
R22 has the same meaning as R1 and R2, and 1'izo is R1
11 has the same meaning, X6 has the same meaning as xi, and m8 has the same meaning as m2. General formula (J) Yl7 has the same meaning as Y3, Ylg has the same meaning as Yl・Y2, zl5 has the same meaning as Zz, zl6 has the same meaning as Z1%Z2 wars, a, R23, R24
has the same meaning as R1 and R2, and R2H is RXa and 111
1), has the same meaning as ql"tp, X7 has the same meaning as Xl, and m9 has the same meaning as m2. General formula (K) In the formula, Z1? and Zls have the same meaning as Zz and Z2. Significance teashi, Yl9,
yzo has the same meaning as Yl, Y2, R26, R27 has the same meaning as R,, R, R28 has the same meaning as R11l, X8 has the same meaning as Xl, mlo has the same meaning as m2. R7 has the same meaning as LX%L2. General formula (L) In the formula, zl9 and Zzo are Zx, Z 2 J knee direction Mtlkteh
F), Y21. Y22 has the same meaning as Yl, Y2, R
29・R30 has the same meaning as R1 and R2, and -R9 to L8
, LIOlIJII, Lxz, R13, R14 are L
1, L has the same meaning as 2, X9 has the same meaning as Xl, and mll has the same meaning as m2. A specific example of a sensitizing dye represented by the general formula (Al to (L)) is shown below, but the sensitizing color chart used in the present invention is not limited to this.
勺＄
41I between h@
Koshiki% ＼
＼勺
pleasure hQ between b
~λ 5 ko 7 ko r 2ri\)
勺I′i′1)） 工＄S
Mamachi ~
)b
−~ Town)
Fierce humiliation
Humiliation, S
humiliation S
S
~humiliation
Vine Kiku stick - 4 handles Kue
Mouse Mouse
These sensitizing dyes can be used singly or in combination. Along with the sensitizing dye, it is acceptable to include in the emulsion a dye that itself has no 7C spectral sensitizing effect or a substance that does not substantially absorb visible light 1C and exhibits supersensitization. For example, an aminostilbene compound Cπ substituted with a nitrogen-containing heteroartic ring 1, for example, US Patent λ, RI J3゜3RI No. 0, 3.43! , 7/MK) Aromatic organic acid formaldehyde condensates (yc, for example, US patent!, 74
A3. ! 110)) may contain cadmium salts, azaindene compounds, etc. US patent! ,t/!
r, 6/J issue, 3,6ij, Hiro 1 issue, same J, la/
7. λ? ! No. 3゜43! Particularly useful are the combinations described in t.7co.1. These sensitizing dyes are described in U.S. Pat. No. 73, No. 200,
Same J,! ! r2.34 Hiro issue, F, M, Hamer. J, Chem, soc, J Ko (/F Hiro), US Patent J, 1tt2.9711, r+m3. t'ii,b
TTR issue, British patent! ? ! , 7r4A issue, same! the law of nature! ,7
1! No. r, US Patent Co., tit, Hiroshi No. 0, British Patent Hir2゜33! Bureau, United States Patent Co,! Jt, No. 216, J. Chem, Soc,, Hiro7t2 (/ri! 2)
, Chem. Berrta tsbJ (/ri!bu) US Patent, 2
゜! 31. Tade No. 2, Mukayu! ;3! , No. 223,
Same co, sir, yso, 1st 2nd. ! 3', Tata J, J, Qen, Chem, U, S, S, R, e core
202 (luri!7), British patent! JJr, 4444F
No. 31, No. 4/-10, U.S. Patent No. 2.2!1.
21! Can be synthesized by the method described in No. t. The amount of these sensitizing dyes added is generally 1% of silver chloride.
10-8 to 1Q mol per 10-10 mol. Preferably i
o ~ lO-1 nyl. The infrared sensitizing dye used in the present invention can be directly dispersed into the emulsion. Alternatively, they can be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. Ultrasound can also be used to treat the solution. However, the method for adding this infrared sensitizing dye is described in U.S. Patent No. 3゜≠62. the law of nature? A method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion into an emulsion, as described in Specification i of No. A method of dispersing a water-insoluble dye in a water-soluble solvent without decomposition and adding the dispersion to an emulsion as described in U.S. Pat. No. 3,122, et al.
131, a method in which the dye is completely dissolved in a surfactant and the solution is added to the entire emulsion; JP-A-Sho! l-7
≠ A method of dissolving a red-shifting compound using a red-shifting compound and adding the solution to the entire emulsion as described in JP-A No. 62; For example, a method is used in which a furnace is used, such as dissolving the emulsion in an acid and adding the solution to the emulsion. Other additions to emulsions include US patent HfJ2. Riyoko, 3 Hiroko 3, 3.3 Hiroko, to!
No. 2.296.217, mtl,! ,4t2?
, rJJr No. Nato may also be used. The above-mentioned infrared sensitizing dyes may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but of course they may be dispersed during any step of the preparation of the silver halide emulsion. can do. In addition to the layer that is sensitive to the infrared region, the photosensitive material of the present invention may optionally include at least one layer that is sensitive to other spectral regions. You may have one. Sensitizing dyes useful for this purpose include, for example, German Patent No.
same! ,! 03.774 issue, same co, yoly, ooi issue, same co, riyoko, 3 kota issue, same 3゜6! T-ri! ri issue,
1 Tsukasa! , 672. ruri No. 7, 3.62 Hiroshi, No. 217,
Same U, O co, Hiro 3? No., Dohiro, Ohiro No. 4.172, British Patent 1.2 Hiro2゜zrr now, Special Publication Show IA4A-14A
It is described in the OJO issue and the Yoko-2 Hirohiro issue, and is π. These sensitizing dyes may be used individually or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is the U.S. patent, try,! Hiro! No., rF! 3 pieces. '? 77.2 Kota No. 3. xi hiro, 602, same 3, j
2λ, No. 012, same J,! 27.6 Hiro No. 1, same J, t/
7. Kota No. 3, same J, A col. 44L, same J,
jA4, ≠to issue, same J, 672.1? r issue, same J,
A75',! Jf No. J, 703. No. 377, 3. xi Hiroshi, No. 602, 3. ? 37, ♂
No. 6, same≠, No. 014.707, British Patent/, 341
17. itI issue, i, to7. to3, special public show≠3
- No. P3≦, No. jJ-/237j, JP-A-Shojλ-/
10. T/R issue, same j2-10? , No. 121. The dye image of the present invention includes multicolor and monochrome dye images, and the monochrome image in this case includes a monochrome image formed by a mixture of two or more types of dyes. As the reducing agent used in the photothermographic material of the present invention, those commonly used in the field of photothermographic materials can be used, such as those described in US Patent No. J, j3/. Kot No. 6, same No. 3,7/s/, 270, same No. 3゜74
4c, jJt issue specifications, Maku IJ Search Disclosure IRD) A/Co 14At% Dokuro/j10r, IJ/J/27, and JP-A-4-27/3.2-Wj Publications, etc. Examples include p-phenylenediamine-based and p-aminephenol-based developing agents, phosphoramidophenol-based and sulfonamidophenol-based developing agents, and hydrazone-based color developing agents. Mayu, U.S. Pat. No. 3,3442.799, U.S. Patent No. 3,7/9. ≠92
No., JP-A No. 344-7903, No. 344-7903
! Color developing agent precursors and the like described in No. 1, etc. can also be advantageously used. A particularly preferable reducing agent is JP-A-ShojA-/Hiroshi613.
There are anilines having -NH8OaM (here, MU represents a compound containing an alkali metal atom, an ammonium group, a nitrogen-containing organic base, or a primary nitrogen atom) at the para position described in Publication No. 3. Other reducing agents as described below can also be used. For example, phenols (such as tfp-phenylphenol, p-methoxyphenol, J, A-tert-
butyl-p-cresol, N-methyl-p-aminephenol, etc.), sulfonamide phenols [e.g. Dibromo-II
-(p-toluenesulfonamine)phenol, etc.], polyhydroxybenzenes (e.g., hydroquinone, te
rt-7” methylhydroquinone, co,6-dimethelhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.)
, naphthols [e.g. α-naphthol, β-su7thol, Hiro-aminonaphthol, ≠-methoxynaphthol, etc.], hydroxybinaphthyls and methylene bisnaphthols [e.g. l,7'-dihydroxyco, λI-binaphthyl, 4.4'-dibromo-2,λ'-dihydroxy/, l'-binaphthyl, 6.6-dinitro 2,2
'-Dihydroxy-7,7/-binaphthyl, Hiro, μ'-
dimethoxy/,//-dihydroxy-2,2'-binaphthyl, bis(2-hydroxy-7-naphthyl)methane, etc.], methylenebisphenols [e.g./,/-bis(2-hydroxy-3,!-dimethylphenyl) )−j,
J. J-) Limethylhexane, /, /-bis(2-hydroxy-3-tert-7thyl-j-methylphenyl)methane, l,l-bis(2-hydroxy-3,j-di-te
rt-butylphenyl)methane, co, t-methylenebis(λ-hydroxy-3-1 er t -)f.ruj-methylphenyl)-≠-methylphenol, α-phenyl-α, α-bis(2- Hydroxy-3,j-di-tcrt-butylphenyl)methane, α-phenyl-α
, α-bis(λ-hydroxy-J-1ert-butyl-
j-methylphenyl)methane, l,/-bis(2-hydroxy-31j-dimethylphenyl)-2-methylpro/en, i,t,j,j-tetrakis(2-hydroxy-3,j-dimethylphenyl) )-2゜Reference-: r-thyl is methane, Co, Corbis (Hiro-Hydroxy-3,j-dimethylphenyl)propane, Co. λ-bis(4cm hydroxy-3-methyl-j-1e
r t-7'tylphenyl) furonotone, co, 2-bis(ψ-hydroxy-3.!-diLert-butylphenyl) solonotone, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, etc. Examples include yohyparaphenylenediamines. More preferred compounds are compounds that release reducing agents upon heating or alkaline hydrolysis, such as those disclosed in Japanese Patent Application Laid-Open No.
No. 7323, No. j9-13111, pj? −／／
No. 1,71AO, No. zq-ire6 Hiroj, No. 1.0
-/kot, ≠39, same to-/2r, 4431, same 60-l, 4A36, same tO-/-! , 4I
It is described in No. 37. In order to obtain a positive color image by causing a dye-forming coupling reaction during thermal development, among the compounds that release a reducing agent by heating or alkaline hydrolysis, compounds represented by the following general formulas +1) to IV) are used. A color developing agent precursor is preferred. a tt4 to a R4 In the formula, 11% R2, R3 and R4 are independently hydrogen atoms,
Halogen atom, alkyl group, alkenyl group, cycloalkyl group, aralkyl group, hydroxyl group, amino group, substituted amine group, alkoxy group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryl group, carbamoyl M, a-substituted represents a carbamoyl group, sulfamoyl group, substituted sulfamoyl group, acyl group, acyloxy group or alkoxycarbonyl group, R
, and R2 or R3 and R4 may be linked to form a ring. A1 is a hydroxyl group, a hydroxyl group atom by the action of a nucleophile,
Unsubstituted or substituted alkyl, alkenyl,
cycloalkyl represents an aralkyl group, R6 and R
7 may be connected to form a heterocycle). MaN
, A, and R7) or both groups may be linked to form a heterocycle. Furthermore, when R1 to R4 are substituents other than a hydrogen atom, a halogen atom, or a hydroxyl group, they may further have n permissible substituents. Mayu, R15~R18,1
20% R21 may be linked to each other to form an alicyclic ring, an aromatic ring, a heterocyclic ring, or a combination thereof. In the general formula (1), R5 represents an unsubstituted or substituted alkyl, alkenyl, 7-chloroalkyl, aralkyl, or aryl group. Xl represents the -502- group in -0-ma9. In the general formula (II), 112 represents a cyano group, and 9 represents an unsubstituted or substituted alkylsulfonyl group or an arylsulfonyl group. In the general formula (IN), the hydrogen atom at 1119 represents a fluorine atom. n represents an integer of /-77. In general formula (IV), R26 represents an unsubstituted or substituted aryl group or a heterocyclic group. In the general formula B) VC, R53t'l represents an aryl group, substituted aryl group, heterocyclic group or substituted heterocyclic group. The compounds of general formulas (1) to (V) used in the present invention will be explained in detail below. In general formulas (1) to (V), when R4 is an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group, the number of carbon atoms is 1 to 3, and the straight chain It may be shaped or branched. Cycloalkyl group has 3 carbon atoms! and these n may have one or more substituents (including substituent atoms; the same applies hereinafter) for R1 described below, and when two or more, they may be the same or different. Good too. Typical examples of the aryl group for R1 to R4 include phenyl and naphthyl.
Ru. These rirtl may have one or more permissible substituents. RIK-permissible substituents include aliphatic groups, aryl groups, heterocyclic groups, aliphatic oxidation groups, aromatic oxy groups, acyl groups, ester groups, amide groups, 4t-s, aliphatic sulfonyl groups, and aryl groups. Examples include a sulfonyl group, a heterocyclic sulfonyl group, an aliphatic thio group, an arylthio group, a heterocyclic thio group, a hydroxyl group, a cyano group, a carboxyl group, a sulfo group, and a nitro group. R1 to R4 are substituted amino groups, substituted carbamoyl groups, or 7'? The permissible substituents for the -d-substituted sulfamoyl group have the same meanings as the permissible substituents for R1 above. However, in the case of a hydroxyl group precursor, it is a group that provides a hydroxyl group by the action of a nucleophile. Here HlO as the nucleophile
Ho, 0Re (Ttnyryv*ru group fx etc.), 503
Examples include anionic reagents such as 2e, and compounds having lone pairs of electrons such as λ-class amines, hydrazines, hydroxylamines, alcohols, and thiols. Preferred examples of A include hydroxyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, dialkylphosphoryloxy group, diarylphosphoryloxy group, and dialkyl group. Examples include an amino group (the alkyl group may be substituted), a pyrrolidino group, a piperidino group, a morpholino group, and R1,
Preferred examples of R25R3% R4 are hydrogen atoms,
- Examples include a rogene atom, an alkyl group, an alkoxy group, an acylamino group, an aryl group, a carbamoyl group, a substituted carbamoyl group, and the like. Preferred examples of R5 in general formula (1) include an alkyl group,
Examples include a cycloalkyl group, an aralkyl group, an aryl group, etc., which may be further substituted with a permissible substituent. Preferred examples of R12 in general formula (II) include methanesulfonyl group, benzenesulfonyl group, p-chlorophenylsulfonyl group, λ,j-dichlorophenylsulfonyl L, m-nitrophenylsulfonyl group, l-Natsutaraysulfonyl group, and hiscyano group. Examples include groups. 1119 in general formula (III) represents a hydrogen atom or a fluorine atom. Represents an integer from n-frame/ to 17. R26 in general formula (fV) is an unsubstituted or substituted aryl group (preferably 6 to 20 carbon atoms, such as phenyl group, α-su7tyl group, β-naphthyl group, p-tolyl group, o-chlorophenyl group) , p-chlorophenyl group, 21
≠-dichlorophenyl group, 2, ≠, 4-) IJ dichlorophenyl group p 70 mophenyl group, J-φ-dibromophenyl group, 2゜a, t-) 1,1 bromophenyl group,
p-cyanophenyl group, p-methanesulfonylphenyl group, p-(/-furobylsulfonyl)phenyl group, m-
Nitrophenyl S, t-bromo-β-naphthyl group, 2,
≠-dichloroα-su7ter group, etc.), or an unsubstituted or substituted heterocyclic group (e.g., l-pyridyl group, copyridyl group, 3-pyridyl group, coquinolyl group, gouquinolyl group, etc.) . When R26 is a substituted aryl group or a substituted heterocyclic group, the permissible substituents are the same as the permissible substituents for R1 above. R2
Preferred examples of 6 include phenyl group, substituted phenyl group,
Examples include naphthyl group, substituted naphthyl group, pyridyl group, and substituted pyridyl group. Preferred examples of R33 in general formula (V) include a frame, phenyl group, p-chlorophenyl group, p-nitrophenyl group, o
-hydroxyphenyl group, p-hydroxyphenyl group,
Co-hydroxy-7-naphthyl group, /-hydroxy-conaphther group, ≠-hydroxy-/-naphthyl group, furyl group, chenyl group, pyridyl group, etc.
These may further be substituted with a permissible substituent on R1. Represented by general formulas (1) to (V) below

Preferred specific examples of compounds are shown below, but the present invention is not limited thereto. -i ■-2 -J ■-μ α -z /'/ rl rl (l r 1-i. C3117 (iso) 1, -// rl 1-/ko α C/ (Z 1-/ Ko 1- /yo I-/A r r α -1t 1-/? ■-koλ ■-ko3 I-λ≠ α 1-j I-kot CON(CH3)2 I-2! ■-29 α NHCOC7H1s ■ -37 α 0NHa The compound of general formula 11) used in the present invention can be prepared by a known method, for example, New Experimental Chemistry!
ll] p/≠91~/Hiroq7 (tq71) (Maruzen) and obtained by using sulfonyl incyanates and the amines. [-/ ■-ko r [i-J α ■-Hiroshi α 1-z n-+ n-r d-q α 1-i. ■-ii [[-1ko[[-t3 11-t ≠ α 1-tz Cε n-1f. α・ -1t (Z ■-2O NHCOC17H35 ■-col l-2- 11-x3 r ■-λμ ■--t ■-27 ■-λ1 11-J? n-3゜α-it α ■-32 The compound of general formula (n) used in the present invention can be prepared by known methods such as addition reaction between β-substituted ethanols and phenyl isocyanates, condensation reaction between β-substituted ethanols and urethanes, etc. -t α -x l fi-s r ■-μ -s ■-t I[1-7 α ■-r III -9 ■-/9 ■-ko0 ■-ko/■ -Coco■-Co3 ■-26 α General formula (III)H used in the present invention can be easily obtained by a known method, that is, by fluoroacylating anilines with a suitable acylating agent. -J α ■-1 -r ■-tp (l ■-10 α (e IV-// ■-/ko■-/3 ■-i μ r ■-/! r fV-iA IV-/7 α - tr ■-79 ■-λ3 ■-2μ ■-Coj IV-24 ■-Core ■-2! ■-Co9 ■-jO ■-31 Known compounds of general formula (IV) used in the present invention For example, it can be synthesized by the condensation reaction of anilines and chloroformates or carbonate esters.V-7 ■-r LT V-/- α y-/3 α V-/ Hiro V-/! V-/A ■-77 H ■-/9 α V-koO ■-ko/ ■-23 V-λμ ■-2! α (Z -Xa ■-27 α -2r 0g ■- 29 The compound of general formula (V) used in the present invention can be easily obtained by a known method, that is, by a condensation reaction of anilines and aldehydes. These reducing agents may be used alone or in combination of two kinds. The above combination can also be used.The amount of the reducing agent used depends on the type of photosensitive silver halide used, the type of organic acid silver salt, the type of other additives, etc., but usually The reducing agent or its precursor used in the present invention can be incorporated into the photosensitive material by many methods. It can be introduced by dissolving it in a hydrophobic oil and emulsifying it as an oil-in-water dispersion in water or in a hydrophilic colloid solution, or by dissolving it in a water-miscible solvent according to a method commonly known as the oil protection method. Alternatively, the compound may be added in the form of fine particles to water or a hydrophilic colloid solution, or the compound in a solid state may be introduced into water or a hydrophilic binder using a ball mill or the like. The reducing agent or color developing agent precursor represented by the general formulas +1) to (V) used in the present invention may be added to any layer constituting the heat-developable color photosensitive material. For example, photosensitive silver halide emulsion layer, hydrophilic colloid layer,
The middle class and others are being attacked. It is particularly preferable to add the dye-donating substance to a layer containing gold. The dye-donating substance used in the present invention is a compound that causes total formation or release of a diffusible dye through a coupling reaction with an oxidant formed by the reducing agent reducing silver halide. . As one example, JP-A-Sho II-/Hirori Ovt issue,
Coupler having a hydrophobic pallast group in the leaving group as described in J.
Coupler in which a leaving group is linked to the polymer main chain as described in No. 7, etc.; 2ri No. 10, Mukai 60-Coco 2zaj
o issue, same 7/-, j7ri≠3, same A/-jri 33
A, A/-A//37, A/-4//II,
Same J/-/xrtia issue, r+51A/-21031/
No. 3,370. Rij No. 2, 31≠51,1
Contains polymer couplers described in No. 20, ≠, oro, No. 1, μ, λ/j, No. 5, Tei, 4A09, No. 3, IA, ≠ Jj, No. 363, etc. f′Lru.Also,
British Patent No. 1,330,5211, Special Publication No. 111-3
9/61 issue, JP-A-17-/1r47! ! No., j7-2
Colored couplers containing all dye components in the leaving group described in No. 07230, No. 61-72λ17, etc. are also useful in the present invention. Couplers preferably used in the present invention include active methylene and active methine compounds, phenols, naphthols, pyrazolidone compounds, pyrazoloazoles and condensed pyrazoloazole compounds, and particularly preferred couplers are represented by the following general formula (M). ~IXMI). Raa-CCH-CNt
X)37R38 N==N In the above formula, Raa R37, R38, Ra9 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an aryl group, an alkoxy group, aryloxy group, acyl group, acylamino group, alkoxyalkyl group, aryloxyalkyl group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, alkylamino group, arylamino group, acyloxy group, alkoxyalkyl group, These substituents are selected from substituted ureido groups, cyano groups, and heterocyclic residues, and these substituents further include alkyl groups, alkoxy groups, halogen atoms,
Hydroxyl group, carboxyl group, sulfo group, 7-ano group, nitro group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, aryl group, aryloxy group, aralkyl group may be substituted with a group or an acyl group. X represents a hydrogen atom or a coupling-off group, and examples of the coupling-off group include a halogen atom, an acyloxy group, a sulfonyloxy group,
Representative examples include alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkoxycarbonyloxy groups, dialkylcarbamoyloxy groups, imido groups, N-heterocyclic residues, and pyridinium groups. In addition, R36, R37, R38, R39 are preferably ballast groups that provide diffusion resistance, and even if these groups are connected to the polymer main chain. good. A diffusion-resistant compound (dye-releasing coupler) that undergoes a coupling reaction with an oxidized developer to release all of the diffusible dye can also be used in the present invention. Compounds of this type include US Pat. No. 3,227. The compounds listed in No. J'10 are representative. For example, in the following formula (including those represented by A1. (■) or X■) A partial and complete cover obtained by removing Xl from the n coupler. When the dye-donating substance represented by the above formula (A1) performs a coupling reaction with the oxidized form of the developer, the bond between the linktlCoup moiety and the Coup moiety can be cleaved. Represents a group, such as azo group, azoki7 group, -〇-1-11g-, alkylidene group, -5-
In addition to 1-S-S-1NI (SO2- group, etc., the coupling-off group Xl described above is also useful. Dye represents a dye or a dye precursor. Dye n represented by the above formula (X■) Among the releasing couplers, t2Coup is preferably a phenol coupler residue, a naphthol coupler residue, or an indanone coupler residue, and Link is an oxygen atom or a nitrogen atom and C
It connects to oup. Specific examples of the dye-forming or dye-releasing couplers represented by the general formulas (■) to (XVI) include JP-A-Sho! 7
-Ir67 Hirohiro No. 73~/j pages, same jl-7921
No. 17, pages 1J to /j, t/-177 HirojI, pages 6 to l! Page, page #S10 of issue 6l-21PO4!2, page tr-r of issue jr-/2JjJ3, jt-/≠
riO≠No.6-10 pages, same jza-/4! Examples include the compounds described on page 7Ir of Ohiro No. 7. Specifically, the following compounds are listed as examples. Hsh Cs Hr l(+1 CsH+ +(11 o
h's
8α3c. OH Nishiki H OCH2CH2SC1aH3a In the present invention, an organic metal salt can also be used as an oxidizing agent together with the frame and photosensitive silver halide. In this case, it is necessary that the photosensitive silver halide and the organometallic salt be in contact with each other or close to each other at a distance of about 90 degrees. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent are described in Japanese Patent Application Laid-open No. 1072170, pages 37 to 3; There are compounds described in columns to column j3, etc. Magaku special request 1977-//
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in No. 3.231, and
Acetylene silver described in No. 2≠20 Guda is also useful. Organic silver salts or more may be used in combination. To the above organic silver salt, 1 molar amount of photosensitive silver halide,
0.0/ to 10 mol, preferably 0°0/ to 1
Moles can also be used together. Photosensitivity 1 Silver halide and education 1! ! ! The appropriate amount of coating for silver is between 01119 m2 and 1097 m2 according to Ginkakusan. The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. Dyes that may be used include cyanide dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioquinol dyes. Specifically, the Japanese Patent Publication No. 40-/
≠03Jj issue, Research Disclosure magazine/ri7
The sensitizing dyes described in the June 2006 issue, pages 1-13 (RD/70 pages), and the sensitizing dyes described in JP-A-Sho t. Examples include heat-decolorizing sensitizing dyes described in Japanese Patent Application No. 1973-23 and Japanese Patent Application No. 67-1979. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used especially for the purpose of 5-strong color sensitization. . Along with sensitizing dyes, dyes that themselves do not have a spectral sensitizing action or substances that do not substantially absorb visible light;
It is also possible to include a substance exhibiting supersensitization in the emulsion (for example, U.S. Pat.
No. 1frJJ, t/j, No. 613, 3,6/j. 6φ/No., same J, t/7. λri No. 3, 3,631.7
- those listed in item 7). These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
! , No. m, No. 1. It may be carried out before or after nucleation of silver halide grains according to λλj, No. 446. The amount added is generally about 7 moles of silver halide to 10-8 to 10 moles. The dye-donating compounds described above and hydrophobic additives such as bond formation promoters described below are described in U.S. Pat.
They can be incorporated into the layers of the photosensitive element by known methods such as the method described in No. 7. In this case, JP-A No. 131117, JP-A No. 131117, JP-A No. 71171, JP-/7rlljJ, 1?
-/71u14L issue, same 39-/71!44itj issue, same 1? -171%! If necessary, add a high boiling point organic solvent as described in No. 7, etc.
It can be used in combination with a low boiling point organic solvent. The amount of high boiling point organic solvent is IO for the dye-donating substance/f used? It is preferably below If. Magi special public Shozi-iyrzJ, special public Shoj/-j Tataμ
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, the following surfactants listed in Nos. 37 to 31 of JP-A No. 7436 may be used. In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. Specific compounds preferably used are described in U.S. Patent Nos.
o, t26 issue j/~! It is written in the column. In the present invention, photographic stabilizers can be used as antifoggants. For example, research
Disclosure magazine 127 December issue No. λj
Azoles and azaindenes described in JP-A No. 4117, Nitrogen-containing carbon modified compounds and phosphoric acids, or mercapto compounds and their metal salts described in JP-A No. 111tJt, Acetylene compounds described in Japanese Patent Application No. 60-Coco 1247 are used. The light-sensitive material used in the present invention may optionally contain a development inhibitor and other processing aids in order to improve photographic performance. For example, US Patent No. 2. ≠27. The benzotriazole derivatives (e.g., benzotriazole, j-methyl-benzotriazole, !-chlorobenzotriazole) described in No. 17 of
It has a low intensity and gives good photographic performance. These processing aids may be added to the water supplied during thermal development, or may be added to the dye fixing element. It is also preferable to incorporate these as precursors into a photosensitive element or a dye fixing element. In the present invention, the photosensitive element may contain an image toning agent if necessary. Specific examples of effective toning agents include the compounds described in JP-A/-/≠72μ≠, page 3 of λ-3. Using the three primary colors yellow, magenta, and cyan to obtain a wide range of colors in the chromaticity diagram, at least three different layers are used, each with a combination of light-sensitive layers in the color range, a green-sensitive layer, and a green-sensitive layer. There are combinations of red-sensitive layers and infrared-sensitive layers. This
Each of the photosensitive layers may be divided into two or more layers, if necessary. The photosensitive element used in the present invention may optionally contain various additives known for use in heat-developable photosensitive elements and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, and a layer. It can have a preventive layer, a release layer for facilitating peeling from the dye fixing element, a matte layer, and the like. For various additives, see Research Tisfroger Magazine 127r.
June issue page~l! Plasticizers, matting agents, sharpness-improving dyes, antihalation dyes, surfactants, fluorescent brighteners, anti-slip agents, oxidation agents, etc., as described in JP-A No. 6, JP-A-Sho+/-RR Co., Ltd. There are additives such as inhibitors and anti-fading agents. In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. You may also add mordants and ultraviolet absorbers to this protective layer. The protective layer and the intermediate layer may each be composed of 1" Lλ layer or more. The protective layer and the intermediate layer may also contain an anti-fading agent, an ultraviolet absorber, and a white pigment such as titanium difluoride. A white pigment can be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving the sensitivity. Placement of color photosensitive materials,
When the oxidized form of the reducing agent formed in each photosensitive layer moves between layers and causes a coupling reaction with a dye-donating substance in another photosensitive layer, a problem of one-color turbidity (r@@ intercolor mixing) occurs. In order to prevent this, it is useful to place an intermediate layer made of a hydrophilic binder between each photosensitive layer and to add a non-diffusible reducing agent to this intermediate layer. This non-diffusible reducing agent functions to return the oxidized form of the reducing agent (currently herbal medicine) that has migrated from the photosensitive layer back to the reduced form. That is, in a preferred embodiment of the present invention, at least a silver halide emulsion, a reducing agent, and a dye donor that releases or forms a diffusible dye by coupling reaction with a reducing agent and an oxidized form of the reducing agent is provided on a support. At least two photosensitive layers (of which l is an infrared-sensitive layer) each containing a photosensitive substance and having photosensitivity in different spectral regions, and an infrared-sensitive layer between the photosensitive layers. A heat-developable color photosensitive material having an intermediate layer containing an existing and non-diffusible reducing agent is used. Examples of the non-diffusible reducing agent used in the present invention include compounds represented by the following general formulas (CI) to (CXEK). OH General formula (CF/) OH General formula + CV) Q)1 t3 General formula (C■) R4 "General formula (C■) General formula (C■) l NH302R5 H tl General formula (X■) H Of( NH8O2R5 In the formula, R1, R2s R3, R4, R7, and R8 may be the same or different, and include a hydrogen atom; a halogen atom (e.g., a chlorine atom, a bromine atom, etc.); an aliphatic group (e.g., an alkyl group with a carbon number of l to (e.g. methyl group, ethyl group,
n-propyl group, isopropyl group, n-butyl group, te
rt-butyl group, n-pentyl L n-decyl group, t
ert-decyl group, n-dodecyl group, 5ec-dodecyl group, tert-dodecyl L n-pentadecyl group, 5
ec-d ntadecyl group, 1erL-d ntadecyl group s
Straight chain or branched alkyl groups such as 5ec-oftadecyl group and tert-octadecyl group), substituted alkyl groups having 1 to 1 carbon atoms [substituents include halogen atoms, hydroxyl groups, alkoxy groups, substituted amino groups (alkyl or aryl sulfamoyl group, alkyl or arylcarbamoyl group), and cyano group. 2-hydroxyethyl group, 3-methoxypropyl group, 3
-〇-butylsulfamoylpropyl group, etc.)], alkenyl group having 3 to 2 carbon atoms (for example, allyl group, etc.)
, 7-chloroalkyl group (e.g. evacyclohexyl group, etc.) of carbon eat-/2%; Aralkyl group having 7 to 7 carbon atoms (e.g. (endyl group, phenethyl group, Hiro-methylphenylethyl group, etc.) 1; aryl group (e.g. phenyl group, hydroxy group, alkyl or arylsulfonyl group, etc.): Alkoxy group, for example, an optionally substituted alkoxy group having 1 to 7 carbon atoms (for example, methoxy group, ethoxy group,
n-butoxy group, n-dodecyloxy group, etc.);
Aryloxy group, for example, an optionally substituted aryloxy group having 6 to 2 carbon atoms (for example, phenoxy group, <<-
n-butoxyphenyloxy group, etc.): alkylthio group, e.g. carbon I! i/~ here optionally substituted alkylthio group (e.g. methylthio group, ethylthio group, n-hanthylthio group, n-dodecylthio group, n- is tadecylthio group%j-chloroynthylthio group, etc.); arylthio group, For example, an optionally substituted arylthio group having 6 to λ carbon atoms (e.g. phenylthio group, 4A-nitrophenylthio group): a sulfonyl group, e.g. 7 to 3 carbon atoms
o alkyl or arylsulfonyl group (e.g. rhodesylsulfonyl group etc.); acyl group, e.g. carbon number λ
~J1717) Acyl group (e.g. stearoyl group)
; Carbamoyl group, e.g., carbamoyl group having 2 to 3 carbon atoms (e.g., co#j-di(1)amylphenokylethylcarbamoyl group); Ester group, e.g., t has 2 to 3 carbon atoms;
Ester group of Q (eg, p-(t)octylbenzyloxycarbonyl group): represents a sulfamoyl group, for example, a sulfamoyl group having 1 to 30 carbon atoms (eg, octadecylsulfamoyl group, etc.). Furthermore, R1 and 12% R3 and R4s are of the general formula (C1l), (CV), (CV), (CV), (CVK
), (CK) to (CX■)K, R2 and R3 may jointly form a condensed ring, preferably a j to 7-membered ring (for example, cyclo means a methane ring, a cyclohexane ring, a cyclohexadiene ring, ring, norbornene ring, etc.). 115 s us' is an aliphatic group (for example, an alkyl group with 1 carbon atoms (for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, n-decyl group% n-dodecyl group) groups, straight-chain and branched alkyl groups such as i6-teryl groups), substituted alkyl groups having 1 to 1 carbon atoms [those having 1/I-eugen atoms (chlorine atoms or bromine atoms) as substituents, such as -1 Ryloloethyl group sx
-Bromoethyl group % J-Chloropropyl group, Hiro-bromobutyl group, dichloromethyl group, etc.; those with hydroxy groups, such as co-hydroxyethyl, 3-hydroxypropyl group, ≠-hydroxy-butyl group, 6-hydroxyhexyl group, etc. those with sulfonyl groups, such as ethanesulfonylmethyl M, n-butylsulfonylethyl group, preylsulfonylbutyl group; alkoxy group (e.g. methoxy) group, ethoxy group, n-butoxy group, n-
hexyloxy group, etc.), such as methoxymethyl group, methoxyethyl group, ethoxyethyl group, n-butoxyethyl group, n-hexyloxoethyl group, etc.; ethylthio group, n-hexylthio group, etc.), such as methylthiomethyl group, methylthioether group, J-ethylthiopropyl group, rhohexylthioethyl group, etc.; or substituted amino group, such as <4 −
(N,N-dimethylamino)butyl group,! -acetamidopentyl group, Hiro-methylsulfonylaminobutyl group,
Anilinomethyl group, etc.]; Schiff's alkyl group (e.g., cyclohexyl, etc.): For example, an aralkyl group having 7 to λ carbon atoms and optionally all substituents (e.g., benzyl group, ≠-methylbenzyl group, ≠-chlorobenzyl group, phenethyl group, methylphenylethyl group), substituted amine group (e.g. alkyl group having 1-coQ carbon atoms or teryl group), mono- or di-substituted t'LfI-amine group (e.g. dipropyl (amino group, etc.)), or aryl groups, such as phenyl groups and substituted phenyl groups (as substituents), those having a rogene atom (e.g., chlorine atom, bromine atom), such as Hiro-chlorophenyl group, μm bromophenyl group, J
-Chlorophenyl group, etc.: Those having a hydroxyl group, such as low hydroxyphenyl group, ≠-hydroxyphenyl group, J, t-dihydroxyphenyl group: Those having an optionally substituted alkyl group, e.g. V-methylphenyl group, a-1-propylphenyl group, ll-n-
dodecylphenyl group, Cokelower μm methylphenyl group, Hiro-/lff-romethylphenyl group, J, t-dihydro-Hiro-alkylphenyl group; optionally substituted alkoxyhexyl, etc.); for example, carbon number 7-2 Aralkyl groups which may have all substituents include benzyl group, Hiro-methylbenzyl group, Hiro-chlorobenzyl group, phenethyl group, Hiro-methylphenylethyl group, etc.), substituted amine groups (for example, carbon number / -20 alkyl or aryl groups, or di-substituted amino groups (e.g., dipropylamino), and haaryl groups, such as phenyl and substituted phenyl groups (substituents include halogen atoms, e.g. chlorine atom, bromine atom), such as ≠-chlorophenyl group, μm bromophenyl group, 2-
Chlorophenyl group, etc.: those having a hydroxy group, such as a co-hydroxy-7 phenyl group, a chloro-hydroxy phenyl group, 2. s-dihydroxyphenyl group, etc.; those with an alkyl group that may be substituted, such as evergomethylphenyl group, ≠-1-propylphenyl group, un-)"decylphenyl group, J-chloro-Hiro-methyl Phenyl group, $
-chloromethylphenyl group, 2. j-dihydroxy-Hiro-alkylphenyl group, etc.; those with alkoxy which may be substituted, such as ≠-methoxyphenyl group, ≠-
Ethoxyphenyltssp-n-propoxyphenyl group, Komethyl-Hiroshi-methoxyphenyl group, 3-methoxyphenyl group, ≠-n-on methyloxophenyl group, ≠-
n-Dodecyloxophenyl group s 3 n 'Those with an optionally substituted alkylthio group, such as s 3 n 'ntadecyloxophenyl group, such as ≠-methylthiophenyl group, Hiro-ethylthiophenyl group, *-n-butylthiophenyl group , 3-n-hexylthiophenyl group, 3-n-decylthio-phenyl group, etc.; those having an alkoxycarbonyl group, such as μm methoxycarbonylphenyl group,
Cou-ethoxy group, luponyl-co-chlorophenyl group, etc.;
Those having a carboxy group, such as a goo-carboxyphenyl group; those having a carbamoyl group, such as a goo-carbamoylphenyl group. Hiro-methylaminocarbonylphenyl group, λ-chloro4<-(N,N-diethylaminocarbonyl)phenyl group, etc.: Substituted amine group (as a substituent, an alkyl group,
Those having an aralkyl group, )'enyl group, an acyl group derived from a carboxylic acid or a sulfonic acid (each of these substituents may be further substituted) 1 For example, a goomethylaminophenyl group, a 4'- (N, N-'; ethylaminophenyl group % Hiro-(N-ethyl-N-benzyl, mino) phenyl group, guacetamidophenyl group, ≠-methanesulfonylaminophenyl group, 3-n-heptanoylaminophenyl group , j-phenylsulfonylaminophenyl group, etc.: Those with a nitro group, such as ≠-nitrophenyl group, μm nitro-methylphenyl group, Cochrochloride-nitrophenyl group, etc. Those with a nitro group, such as Hiro-cyano Phenyl group, etc.; those with acyl group, such as Hiro-acetylphenyl group, comethyl-Hiro-
acetylphenyl group, μm benzoylphenyl group;
Those having a sulfonyl group, such as ≠-methanesulfonylphenyl group%2-chloro-Hiro-ethanesulfonylphenyl group, cuphenylsulfonylphenyl group, 3-(λ,
j-dihydroxy-μmtert- is methylphenyl)
Sulfonylphenyl group; Those having a sulfamoyl group, such as 3-sulfamoylphenyl group, J-1n-
butylaminosulfonyl) phenyl &, 2-chloro4
4-phenylaminosulfonylphenyl group, etc.; and those with sulfo groups, such as μm sulfophenyl group, i-chloro-! -Sulfophenyl group (JeFit). Preferably, R5 does not contain a dye residue or its precursor. R6 represents an aryl group (the details of the aryl group are the same as R5). In molecules represented by general formulas (C1) to +CXIX), the total number of carbon atoms in R1 to R8 is preferably at least 2 or more to make the compound non-diffusible, but more preferably It is 30 from io. Specific examples of non-diffusible reducing agents are listed below, but the present invention is not limited to these. C-+21 011 H C-(!31 C-(6) C-(71 C-(8) t-C5H1□ C-(9) H C-03 ft)CsHtx C-Q!19 mae C-αη H H C-090H C-■ c-2υ 1l C-■ il COOC1gH37(n) CONHC128C00C1 H CONH(CH,)30C14)I2. (n) C-(g) C-(foundation) H C-plane0[4 T1 a (?-Gll C-(4υ C-(43 tt3) lo-1 mole to IQ-7 mole per 1rrL2, preferably 10
-2 mol to 10-5 mol. In the present invention, the dye fixing element is one that is capable of fixing the f'L9 mobile dye released by development. To fix the dye, use polymer mordant or Tokukaisho! The use of dye-receptive polymers such as those described in No. 7-7, t≠sr, produces color. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation group, etc., and preferably other hydrophilic polymers (gelatin, etc.). etc.). Regarding polymers containing one unit of vinyl monomer having a tertiary amino group, JP-A No. 3, No. 1.0
Specific examples of polymers containing one vinyl monomer unit having a tertiary imidazole group include JP-A-40-//rr3a and to-ixx
yai issue, U.S. Patent No. 212.30! No., No.
iiz, i2≠ issue, same number 3. /≠r, written in oti issue, etc. Preferred specific examples of polymers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent No. 2,0
rjp, No. 10/No. 2,0ri3゜017/No. 1. J Rihiro, Ri No. 61, US Patent No. 11. /21t, 3
No. 16, No. 1I, //! , /2≠ issue, same issue≠, Cocoa, 133 issue, same issue, 4LjO, cocoμ issue, JP-A 1-21. It has been published in the Kolambda issue, etc. Other preferred specific examples of polymers containing one vinyl monomer unit having quaternary ammonium group include US Pat. No. 3,702.620, US Pat. ? 11,2P No.1. It is described in JP-A-17134, JP-40-404143, JP-A No. 60-l Kokota≠θ, JP-A No. 1pO-/2-Tag λ, and JP-A No. 60-KO3J/3-Hiroshi. The polymer mordant can be made to function as a dye fixing element by being mixed with pin darts such as gelatin and coated integrally with the photosensitive element, or by coating it on a support separate from the photosensitive element. The polymer particularly preferably used in the present invention is composed of a heat-resistant organic polymer substance having a glass transition temperature of 00c or more and 00c or less. There are many points that are not clear regarding the mechanism by which the dye released from the dye-donating substance used in the present invention enters the polymer. In general,
It is believed that at processing temperatures above the glass transition point, the thermal motion of the polymer chains becomes large, and as a result, the dye can enter the gaps between the chain molecules. This method,
By using a layer made of an organic polymer substance with a glass transition temperature of μo O (' or more and less than 2100 C) as a dye fixing layer, the dye can be distinguished from the dye donating substance used in the present invention, and only one dye can be fixed. It is possible to form a clear image that penetrates into the layer. Examples of the organic polymer material used in the present invention include the following.
, tooo polystyrene, polystyrene derivatives with substituents having a carbon number of μ or less, polyacetals such as polyvinyl 7-chlorohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral, Polyvinyl chloride, chlorinated polyethylene, polytrichloride butylene, polyacrylonitrile, poly N, N-dimethylallylamide, p-
7 anophenyl group, interchlorophenyl group and 2.
Polyacrylates with dichlorophenyl groups, polyacrylic chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, polytert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly -2-cyano-
Polyesters such as ethyl methacrylate and polyethylene terephthalate, polysulfone, bisphenol A
Polycarbonate, polycarbonates, polyanhydrides, polyamides and cellulose acetates,
are mentioned. Maku, Bolimano Ndobukku 2nd edition G.I. Brandlap, E.H. Inmerg)
(J, Brandrup, E, H, Im
mergut) - John Wiley & 5on
s The glass transition temperature listed in the publication
As mentioned above, synthetic polymers and remers having O0C or less are also useful. These polymeric substances may be used alone or in combination, or a plurality of them may be combined to form a copolymer. These polymers may also serve as a support applied to the photographic element described below, or may form a layer independent of the support. For example, these polymers can be used as a support for the photosensitive material of the present invention, and this support can also function as a dye fixing layer, or these polymers can be used as a support independently of the photosensitive material. It can also be used as a dye fixing layer of a dye fixing material, and the support of the dye fixing material can also function as a dye fixing layer. The dye fixing element can be provided with auxiliary layers such as a protective layer, a release 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 the present invention, an image formation accelerator can be used in the photosensitive element and/or the dye fixing element. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, generating dyes from dye-donating substances, accelerating reactions such as decomposition of dyes or releasing diffusible dyes, and photosensitizing agents. It has functions such as promoting the movement of dye from the material layer to the dye fixed layer, and from a physicochemical function, the base friends described below are base precursors, nucleophilic compounds, high-boiling organic solvents (oil), and thermal solvents. ,
It is classified as a surfactant, a compound that interacts with silver or silver ions, etc. However, the group of substances generally has multiple functions and usually has some of the above-mentioned promoting effects. For details on these, see JP-A-61-
No. 231711, pages 67-7/n. Various development stoppers can be used in the photosensitive element and/or dye fixing element of the present invention. The term "development stopper" used here refers to the ability to quickly neutralize a base after proper development, or react with the base to reduce the base concentration in the film.
The t-stopping compound is a compound that interacts with silver and silver salts to completely inhibit development. Specifically, an acid precursor that releases acid upon heating;
Examples of electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating include nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, JP-A-60-1
No. 011137, to-19, 2-3, pto-
No. 23013, No. 3 is a compound described in No. 23013, No. 3, etc.). Compounds that release mercapto compounds are also useful;
For example, JP-A No. 47-67rj1, t/-/Hiro7ha1
No. 4/-/ko $5'! / issue, same t/-/13717
No. 3, No. 4/-/I Koo3, No. 4/-/II Ha No. 1, No. 4/-/I, No. 3, No. 4/-/It! 11
No. 70, 4/-! There is a compound described in No. J63. A hydrophilic binder can be used for the photosensitive element and/or dye fixing element of the present invention. Typical hydrophilic binders include transparent or translucent hydrophilic binders, such as gelatin, gelatin derivatives, cellulose derivatives, starch, etc.
These include natural materials such as polysaccharides such as gum arabic, and synthetically polymerized materials 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 coating amount of the binder is 1rrL2A9C02 or less, preferably toy or less, more preferably 7f 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/f, preferably 0.
, jOc below 1. More preferably, the amount is 0.7cc or less. The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and/or dye fixing element of the present invention may contain an inorganic or organic hardening agent. Specific examples of hardening agents can be found in JP-A-1986/-/177λ Reference μ, page 5 to page 5! Examples include those described on page 31 of JP-A No. 2003/077736, and these can be used alone or in combination. In addition to promoting dye transfer, a method can also be adopted in which a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature is placed inside 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 layer to be incorporated may also be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. (9) 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 of the present invention is one that can withstand processing temperatures. Common supports include glass, paper, cast coated paper, synthetic paper, heavy theta film, metals and their analogs. The supports described in JP-A-4/-/4LL1244≠, pages 1 to 6, can be used. In the present invention, the method for coating the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, pack layer, dye fixing layer, and other layers is described in US Pat. No. 11-1+ of U.S. Pat.
The method described in the column can be applied. In the image forming method of the present invention in which a diffusible dye is formed in one image and transferred to a dye fixing element, various process patterns are used, examples of which are shown below. l) A photographic material in which a photosensitive element and a dye fixing element are laminated,
A method of forming an image in l steps by heating. 2) A method in which a photosensitive material and a dye-fixing material are stacked, heated and the entire image is formed in one step. 3) A method in which an image is formed in 1 steps by supplying a small amount of water and then heating it in the method of 1) and 2). 4) A method in which a photographic material in which a photosensitive element and a dye fixing element are laminated is heated and developed, and then heated again to form an image in two steps. 5) A method for forming an image according to method 4), which comprises supplying a transfer solvent after heat development. 6) A method in which a photosensitive material is heat-developed and then a dye-fixing material is layered and heated to form an image. 7) In the method of 6), a transfer solvent is supplied to the photosensitive material and/or dye fixing material after development. A method of stacking the two and heating them to form an image. The above method is just an example, and various variations are possible, and the present invention is not limited to the above method. The bases used in the present invention are well known among base precursors. A base or base precursor is a compound or adduct having a nucleophilic group that can make the system basic and activate development, and is extremely effective in increasing the maximum density and accelerating and speeding up development. In particular, when compounds represented by general formulas tl) to (V) are used in the present invention, since these are precursors of developing agents, the developing activity is inhibited by removing the a-binding groups from the precursors. A base is essential during heat development for the purpose of expression. That is, in the 1Ikl image forming method of the present invention, the light-sensitive material is preferably heat-developed in the presence of a base or a base precursor. Specifically, the base precursor may be added to the photosensitive material in advance, or it may be supplied from the outside during the heating phenomenon (for example, it may be dissolved in water and supplied), or it may be supplied from the dye fixing material. (Can be supplied in a diffused manner). In the present invention, 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, and then heated. Sometimes, it is also possible to use a method in which the p T-I i of the yarn is increased by a reaction between these two compounds. By image reaction system is meant here the area in which the image forming method takes place. Specifically, layers belonging to both the photosensitive element and the dye fixing element are 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 must be added to at least separate layers in order to prevent them from reacting before the development process. For example, in a so-called monochrome material in which a light-sensitive element and a dye-fixing element are provided on the same support, it is preferable to separate the additive layers of the two and further interpose layers of /# or more in between. Good. A more preferable form is one in which the poorly soluble metallized adduct and the complex-forming compound are each contained in nine layers 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 after being dissolved in water to be coexisting. Hardly soluble metal compounds are covered by Tokukai Sho! t-/7
μt3O issue, same! It is preferable to contain it as a fine particle dispersion prepared by the method described in Japanese Patent No. J-102733, etc., and the average particle size thereof is preferably 30 microns or less, particularly 5 microns or less. The poorly soluble metal compound may be added to layers such as the photosensitive layer, intermediate layer, and protective layer of the photosensitive element.
It may be added by dividing into more than one layer. The amount of a poorly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the compounding process, particle size of the poorly soluble metal compound, complex formation reaction rate, etc. It is appropriate to use less than 30 e-cents by weight, and more preferably from 0.0 to 10 e-cents by weight. (9) When the complex-forming compound is dissolved in water and supplied, the amount ranges from 0.00 jmol to jmol/liter.
ls especially 0. (The concentration is preferably 7 Jmol or Jmol. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is set at a molar ratio of 1 to the content of the poorly soluble metal compound.
7100 times to 100 times, particularly preferably 1710 times to 20 times. Examples of poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. For complex-forming compounds, e.g.
E.Martill, R.M. Smith (A,E,Ma
Rtell, R, M, Sm1th), [Critical Stability Constances]
5ability Con5tants) J Volumes D to 5, Plenum Press
s). Specifically, aminocarboxylic acids, imidinoacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di-tri, tetracarboxylic acids, and also phos-7-ono, hydroxy, oxo,
Compounds with substituent groups such as esters, amides, alkoxy, mercapto, alkylthio, and 7-osphine), alkali metals such as hydroxamic acids, polyacrylates, polyphosphorus, guanidines, amidines, or Fi
Examples include salts with μ-class ammonium salts and the like. Examples of the base of the present invention include inorganic bases such as alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphoric acids, borates, carbonates, quinolates, metaborates: Ammonium hydroxide; hydroxide of double alkylammonium; hydroxide of other metals, etc.N1 Organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines) ; Aromatic amines (N-alkyl substituted aromatic amines, N
-Hydroxylalkyl-substituted aromatic amines and bis(p-(dialkylamine)phenylcomethanes), heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines, especially those with a pKa of 2
The above are preferred. Salts of the above-mentioned organic bases and weak acids, such as carbonates, bicarbonates, borates, secondary and tertiary phosphorus salts, quinolates, acetates, metaborates, etc., are also preferably used. In addition to these compounds, the compounds described in JP-A No. 2003-120003 are also preferably used. In addition to the above-mentioned base precursors, salts of organic acids and bases that decompose by decarboxylation upon heating, and decompose by reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, and K-Tucmann rearrangement, release amines. Preferably used are compounds that release bases by causing some kind of reaction when heated, such as chemical adducts, and compounds that generate bases by electrolysis or the like. A preferred base precursor of the former type, which forms a base by heating, is British Patent No. 2P! , 2≠No. 2, etc., and the salt of trichloroacetic acid described in U.S. Pat. Salts of α-sulfonylacetic acids as described in JP-A No. 010, ≠ No. 20, salts of propiolic acids as described in JP-A No. , with a thermally decomposable acid using an alkali metal or an alkaline earth metal in addition to an organic base as the base component (Japanese Patent Application Laid-open No. 5237), and with a pyrolyzable acid using a Rossen rearrangement! JP-A-Sho IF-/!, which produces nitrile by heating the hydroxame carbamates described in ``Itr Hiro≠θ''. Examples include aldoxime carbamates described in No. 7637. Other British Patent No. 2
2r, P≠j, U.S. Patent No. 3. Koio, rip issue, JP OJ J 4.21, British Patent No. 2,07
The base precursors described in ≠to, etc. are also useful. 'Compounds that generate bases by electrolysis include the following: For example, electrolysis of various fatty acid salts can be cited as a typical method using electrolytically oxidized gold. Through this reaction, carbon salts of organic bases such as alkali metals, guanidines, amidines, etc. can be obtained extremely efficiently. In addition, methods using electrolytic reduction include the production of amines by reduction of nitro and nitroso compounds; the production of amines by reduction of nitriles; dinitro compounds, azo compounds,
Examples include the production of p-aminophenols, p-phenylenediamines, and hydrazines by reduction of azoxy compounds and the like. Not only can p-amine phenols, p-phenylene diamines, and hydrazines be used as bases, but they can also be used directly as color image-forming substances. Of course, it is also possible to generate an alkaline component by electrolyzing water in the coexistence of various inorganic salts. In addition to the above, there are various methods of generating bases, and the compounds used in these methods are all useful as base precursors. For example, there is a method of generating a base by electrolysis, which is described in Japanese Patent Application Laid-Open No. 2001-23331. The base and/or base precursor can be used alone or in combination of two or more. The amount of base and/or base precursor used in the present invention can be used within a wide range. When used in a photosensitive layer and/or a dye fixing layer, it is appropriate to use the coating film in an amount of 10% by weight or less, more preferably 0.0% to 0.0% by weight. Weight percent ranges are useful. When used in the present invention dissolved in water, the concentration is preferably 0.00zmole/l to λmole/l, particularly 0.00zmole/l to λmole/l. Ojmo
Concentrations from le/l to /mole/J are preferred. These addition amounts have no direct relation to p I-1. This is because when layered with a dye fixing element, etc., the base etc. may migrate to other layers. In the present invention, a conventionally known method can be used as a heating method for transfer. For example, the photosensitive material may be brought into contact with a hot plate such as a hot plate or a drum, or may be transported using a heat roller. ! It is also possible to use air heated to a high temperature, or to heat by high frequency heating or a laser beam. Depending on the photosensitive material, it can also be heated using an infrared heater. Furthermore, it is also possible to apply a method of heating using eddy currents generated by electromagnetic induction. Alternatively, a liquid that is inert to the photosensitive material, such as a fluorine-based liquid, may be heated in a heated bath. Furthermore, the photosensitive material may be heated by providing a heat source separate from the heating means described above. For example, a layer of conductive particles such as carbon black or graphite may be incorporated into a photosensitive material and/or a dye fixing material, and the Joule heat generated when electricity is applied may be utilized. There are various patterns for heat-developing photosensitive materials.
Turns can be applied. The most common method is heating at a constant temperature, but depending on the characteristics of the photosensitive material, multi-step heating, such as a method of heating at high temperature for a short time and then gradually lowering the temperature completely, may be effective. If the photosensitive material is susceptible to air oxidation during heating, it is effective to replace the deaeration chamber around the heating section with an inert gas. The surface of the photosensitive material may be brought into direct contact with the heated portion or may be exposed to air. When developing the surface of a photosensitive material on the air side, it is effective to attach a cover to prevent moisture and volatile components from evaporating from the photosensitive material and to keep the material warm. In the present invention, when electrical heating is employed as the developing means, the transparent or opaque heating element can be made as a resistance heating element using conventionally known techniques. The heating temperature is suitably between ro 0c and 2ro0c, and the particularly preferable range varies depending on the form of development and transfer. For example, in the case of pattern 2) mentioned above, if a next base precursor is used to activate the development, the preferred temperature range is the temperature required to activate the base precursor and the released NFT dye. Determined by the temperature required for diffusion, usually 10o0c or more
Particularly preferably the range is /lo'c or more and 1ro0c or less. If water is involved in the developing process, the temperature must be below the boiling point of water (
especially! 00CI: ), 1 oz or less) is preferable. The temperature required for dye diffusion also varies depending on the type of transfer.
Generally, when using sublimation diffusion of a dye, a high temperature is required, 0-200'C, and when using a hot solvent such as urea as a carrier for the dye, a temperature higher than the melting point of the hot solvent is required, for example, t0'. C-710'C is preferred. Further, when an organic solvent is used, the temperature is preferably below its boiling point, and when using dimethylformamide (DMF), the temperature is preferably below 10°C. As mentioned above, the preferred temperature for development and transfer is not constant, but can be selected in an optimal range depending on the form. The thermally developable @photosensitive material of the present invention, especially in the case of a full-color photosensitive material, is composed of a silver halide emulsion layer that is sensitive to multiple spectral regions. It is necessary to expose to light. The number of light sources for this purpose may be one type or a combination of two or more types. When selecting a light source, it goes without saying that you should choose a light source that is suitable for the sensitive wavelength of the photosensitive material, but also consider whether the image information will be transmitted via electrical signals, the processing speed of the entire system, lamp suitability, and power consumption. You can consider and choose. When image information does not go through electrical signals, for example when directly photographing a landscape or person, directly copying an original image, or exposing through a negative, it is necessary to use an exposure device such as a camera, printer, or enlarger for printing. A photocopier, an exposure device of a copying machine, etc. can be used. In this case, the two-dimensional image can be simultaneously exposed in so-called 1 shots, or can be scanned and exposed through a slit or the like. You can also enlarge or reduce the original image. In this case, a light source such as a tungsten lamp is usually used instead of a monochromatic light source such as a laser. When image information is recorded via electrical signals, the exposure device may include one light emitting diode and various lasers in combination depending on the color sensitivity of the photosensitive material.
Various types of Denozois (CR) known as image display devices
T, liquid crystal display, electroluminescent display, electrochromic display, plasma display, etc.) can also be used. In this case, the image information includes an image signal obtained from a video camera or an electronic still camera, a Nippon Television Signal Standard (NISC)
), an image signal obtained by dividing an original picture into many pixels using a scanner, etc. Density image signals stored on recording materials such as magnetic tapes and disks can be used. When exposing a color image, a combination of LEDs, lasers, fluorescent tubes, etc. is used depending on the color sensitivity of the photosensitive material, but it is also possible to use multiple combinations of the same type of LED, or to use a combination of different types. good. The color sensitivity of the photosensitive material is, for example, CG or R. IR) or (R%IR (short wave), IR (long wave)
etc., the vector area is used. The light source may also be a combination of different types, such as a combination of LED λ color and laser. As for the above-mentioned arc tube or element, a single tube or element may be used for each color for scanning exposure, or a play tube or element may be used to increase the exposure speed. Available plays include LED play, LCD shutter array,
Examples include magneto-optical element shutter arrays. The image display devices described above include those with color display such as a CRT and those with monochrome display, but a method may be adopted in which a monochrome display is combined with a filter and exposed several times. The existing λ-dimensional 111g1 display device may be used by making it one-dimensional like FOT, or may be used by dividing the 1liIi plane into several pieces and combining it with scanning. 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 JP-A-47-/$7J.
The method described in No. 444C, pages IOJ to IOA can be applied. Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A-ShojP-7HaI7, same! ? -1771 Hiro 7, same! ? -/Ir/J! J No. 60-/r? rI issue, Jitsugan Showa 60-//17! Preferably, the apparatus described in Ko No. 1 and the like is used. (Specific Embodiments of the Invention) Hereinafter, one specific embodiment of the present invention will be shown and the present invention will be explained in further detail. Example 1 A method for preparing a be/citriazole silver emulsion will be described. Gelatin 211 and benzotriazole 13. λV to water 3
Dissolved in 00-. Keep this solution at 4 cOoC and stir. A solution prepared by dissolving silver nitrate/79 in water 700 was added to this solution over a period of 2 minutes. The p)l of this benzotriazole silver emulsion was adjusted to p4. Sedimentation was performed to remove excess salt. Then the pH was adjusted to t, J
A benzo)IJ azole silver emulsion was obtained. This article describes how to make silver halide emulsions for the j-th layer and the first layer. A well-stirred gelatin aqueous solution (water ioo. d contains gelatin 209 and sodium chloride Jf, y
60g of an aqueous solution containing 0.2'?j moles each of sodium chloride and potassium bromide in
Oyptt and a silver nitrate aqueous solution (dissolved in mol of silver nitrate in water) were simultaneously added at equal flow rates over 30 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine!θmolti) having an average grain size of 0 μm was prepared. After washing with water and desalting, sodium thiosulfate! Chemical sensitization was performed at % 60°C by adding ηbi-hydroxy-6-methyl-, J, ja, 7-chitrazai/den 2019. The yield of emulsion was toot. Next, we will explain how to make a silver halide emulsion for the third layer. A well-stirred gelatin aqueous solution (water ioo. - containing 209% gelatin and 79% sodium chloride, 7%
400 yd of an aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (0.22 mol of silver nitrate dissolved in water AOOyd) were simultaneously boiled for 30 minutes in In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 10 mol %) with an average grain size of 0.3!μm was prepared. After washing with water and desalting, sodium thiosulfate!■ Reference-hydroxy-t-methyl-/, J, Ja, 7-chitrazai/de/
Chemical sensitization was carried out at to''c by adding CoOW.The yield of the emulsion was 600?Next, we will explain how to make a gelatin fraction of a dye-donating substance.Yellow dye-donating property Substance (Hardness If, interface +'l [
As J, weigh succinic acid-coethylhexyl ester sulfonic acid sodium o, zt, and triisononyl phosphate (amounts in the table), add vinegar-brewed ethyl JOd, and dissolve by heating to about 0C to form a homogeneous solution. And so. After stirring and mixing this solution and 100 t of a 3% solution of lime-treated gelatin, Ioooorpm was heated using a homogenizer for 10 minutes.
It was dispersed. This dispersion is called a yellow dye-providing substance dispersion. Magenta dye-providing substance (Cyan dye-providing substance) Magenta was prepared in exactly the same manner as the yellow dye-providing substance dispersion except that t- was used. A dispersion of a cyan dye-donating substance was prepared. By using these, a color photosensitive material (A) having a multi-member structure as shown in the first table is made.9. CD-/) (D-2) I Neat G%R1IR three-color separation filter (G is j00-600nm. R was a 600 to 700 nrn band/R filter. IR was constructed using a filter that transmits 700 nm or more), and was exposed for 1 second at ioo lux. Water of ryit/m2 is supplied to the emulsion surface of the exposed light-sensitive material using a wire parer, and then overlapping holes are formed so that the dye-fixing material and the film surface are in contact with each other. When the dye-fixing material is peeled off from the photosensitive material after heating for 30 seconds using a heat roller whose temperature is adjusted so that the temperature of the film becomes O when it absorbs water,
G on the fixed material. A clear yellow, magenta, and cyan image was obtained corresponding to the RlIR three-color separation filter. The maximum density (Dmax) and minimum density (Dmin) of each color were measured using a Macbeth reflection densitometer (RD-11?). Example - The same treatment and operation as in Example 1 were carried out except that the sensitizing dyes /, t, and 2λ mentioned in the text were used in the amounts shown in the table instead of the sensitizing dye D-j in Example 1. As a result, almost the same results as in Example 1 were obtained. Example 3 Dye-donating substance of Example 1 ((12)% instead of firmness)
(/ instead of (//), (it) instead of (l?
) was performed in exactly the same manner as in Example 1, except that the processing amount was used, and almost the same results as in Example 1 were obtained.

Claims (1)

[Claims] (1) Dye-donating property of releasing or forming a dye through a coupling reaction with at least a silver halide sensitive to infrared light on a support, a reducing agent, a binder, and an oxidized form of the reducing agent. A heat-developable color photosensitive material containing a substance.