JPS61159644A - Fixing material for coloring matter - Google Patents

Abstract

PURPOSE:To improve a muddiness of color by providing a fixing layer of a mobile coloring matter distributing so as to give an image matrix on a substrate, and by incorporating compds. shown by specific formulas to said fixed layer or its adjacent layer. CONSTITUTION:The color fixing layer which fixes the mobile coloring matter distributing so as to give the image matrix is provided on the substrate. Said color fixing layer or its adjacent layer contains one or more of compd. shown by formula I wherein R1 is an alkyl group, A is a nonmetal atom capable of forming a five or a six membered ring together with >C=C<O binding, R<2>, R<3>, and R<4> are each a cycloalkyl group, and formula II wherein R<1> is an alkyl group, R<5> is an alkoxy group and R<6> is an alkylthio group and formula III wherein R<8> is an alkyl group, R<9> is an alkenyl group and also formula IV where in R<10> is an alkenyl group, R<11> and R<12> are each a hydrogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a dye fixing material for heat-developable photography, which develops silver halide by heating under substantially moisture-free conditions. In particular, by forming a mobile dye into an image by heat development,
Regarding the material for fixing this dye.

(Prior art) Photography using silver halide has been the most widely used method since it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. has been used. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. has been developed.

Heat-developable photosensitive materials are well known in the art, and for information on heat-developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979), pages 553-555;
Video information published in April 1978, page 40, Netletts
Handbook of Photography
ncl Reprography 7th Eil,
(van No5trand ReinholclCo
page 32-34 of U.S. Pat. No. 31,529.
No. 04, No. 3,301,678, No. 3,392.02
No. 0, No. 3457; No. 075, British Patent No. 1,131,
No. 108, No. 1.167.777 and Research Disclosure Magazine June 1978 No. 9-15-! - Di (RD-17029).

Many methods have been proposed for obtaining color images. A method for forming a color image by combining an oxidized developer with a coupler is described in U.S. patents &
No. 53L286 uses p-phinidine diamine reducing agents and phenolic or activated methylene couplers, and U.S. Pat. 31.32 E., September 1975, a sulfonamidophenol reducing agent is proposed, and in US Pat. No. 402L240, a combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler is proposed.

However, this method has the disadvantage that a reduced silver image and a color image are simultaneously produced in the exposed area after thermal development, resulting in a cloudy rounded color image. To solve this problem, there is a method of removing the silver image by liquid processing or transferring only the dye to another layer, for example, a sheet having a receiver layer, but it is possible to remove the unreacted material and the dye. It has the disadvantage that it is not easy to distinguish and transfer only the dyes.

Research Disclosure Magazine May 1978 issue 54-58- also describes a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development. -jiR
D-16966. With this method, it is difficult to suppress the release of dye in areas that are not exposed to light, and a clear image cannot be obtained, so it is not a common method.

Regarding the method of forming a positive color image using a photosensitive silver dye bleaching method, for example, see Research Disclosure Magazine, April 1976 issue 30-32 Easy (RD-14
433''), December 1976 issue 14-15 of the same magazine (RD-15227), and U.S. Pat. No. 4,235,957, useful dyes and bleaching methods are described.

However, this method requires extra steps and materials, such as stacking and heating activator sheets to speed up the bleaching of the dye, and the resulting color images may not coexist during long-term storage. It had the disadvantage of being gradually reductively bleached by free silver and the like.

Further, regarding methods of forming color images using leuco dyes, for example, US Pat. No. 3,985,565 and US Pat.
It is described in No. 2617. However, this method has the drawback that it is difficult to stably place the leuco dye into the photographic material, and the material gradually becomes colored during storage.

Furthermore, the above-mentioned methods generally require a relatively long time in practice, and the resulting images have the disadvantage of only high capri and low density.

In order to improve these drawbacks, an image forming method using silver halide has been proposed in which a movable dye is formed in the form of an image and the dye is moved to a dye fixing layer. (I# 58-58543, 79247-79247, 58
-149046, 58-149047).

(Problems to be Solved by the Invention) This method has greatly improved the conventional technical problems and has made it possible to sufficiently transfer the released dye in the sensitive material layer to the dye fixing layer. There is a problem in that the transferred color image formed in the dye fixing layer has low light fastness.

An object of the present invention is to provide a photographic element for heat transfer photography which provides a transferred color image of high density and improves the light fastness of the transferred color image. The object of the present invention is to provide a fixing material that efficiently fixes dyes and has high light fastness.

(Means for solving the problem) The above object has a dye fixing layer on a support that fixes a mobile dye distributed on an image, and the dye fixing layer or a layer adjacent thereto has the following general properties. This is achieved by a dye fixing material characterized by containing at least one compound selected from the compounds represented by formulas (I) to (5).

Here, R is a hydrogen atom, preferably an alkyl group having 1 to 22 carbon atoms (e.g., methyl, ethyl, propyl, n-octyl, todecyl, hexadecyl, etc.), an acyl group (e.g., acetyl, be/noyl, intanoyl, etc.). , (24-di-tert-amylphenokyl)acetyl, etc.), sulfonyl groups (e.g., methanesulfonyl, butanesulfonyl, benzenesulfonyl, toluenesulfonyl, hexadecanesulfonyl, etc.), carbamoyl salts (e.g.,
N-methylcarbamoyls N5N-i'ethylcarbamoyl, N-r"decylcarbamoyl, N-phenylcarbamoylnato), sulfamoyl group (e.g., tbN-methylsulfamoyl, N,M-)methylsulfamoyl, N-tetradecylsulfamoyl, N-phenylsulfamoyl), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, indyloxycarbonyl, phenoxycarbonyl, etc.), 5- or 6-membered rings in trialkylsilyl represents a non-metallic atom necessary to complete the ring, and this ring may be substituted, with preferred substituents being alkyl groups (e.g. methyl, t-
butyl, cyclohexyl, octyl, dodecyl, octadecyl, etc.), alkoxy groups (e.g., methoxy, butoxy, dodecyloxy, etc.), aryl groups (e.g., phenyl), aryloxy groups (e.g., phenoxy), aralkyl groups (e.g., , benzyl, 7enethyl, etc.), aralkoxy groups (e.g., pen/zyloxy, phenethyloxy, etc.), alkenyl groups (e.g., aryol, etc.),
Examples include N-substituted amino groups (e.g., alkylamino, dialkylamino, N-alkyl-N-arylamine, pyrazino, etc.), heterocyclic groups (e.g., benzothiazolyl, indioxadiyl, etc.), and also those forming a fused ring. may be substituted by a residue. Preferred substituents for the alkyl and aryl groups mentioned above include a halogen atom, a hydroxyl group, a carboxy group, an alkoxycarbonyl group, an acyloxy group, a sulfo group, a sulfonyloxy group, and an amide group (e.g., acetamide, ethanesulfonamide, benzamyl group, etc.). ), an alkoxy group, an aryloxy group, etc.

R, R, and R each represent a hydrogen atom or an alkyl group (for example,
Methyl, t-butyl, cyclopentyl, n-octyl,
t-octyl, dodecyl, octadecyl, etc.), cycloalkyl groups (e.g., cyclohexyl group, etc.), alkoxy groups (e.g., methoxy, butoxy, dodecyloxy, etc.), aryl groups (e.g., phenyl, etc.), aryloxy groups (e.g., phenoxy) ), aralkyl groups (e.g., indyl, phenethyl, etc.), aralkoxy groups (e.g., benzyloxy, 7enethyloxy, etc.), alkenyl groups (e.g., allyl), alkenoxy groups (e.g., allyloxy, etc.), acylamino groups (e.g., acetyloxy, etc.), Amino, benzamide 9, (2,4-tert-
acylphenoxy) acetylamino, etc.), halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkylthio groups (e.g., ethylthio, dodecylthio, octadecylthio, etc.), diacylamino groups (e.g., succinimide, hydantoinyl, etc.), arylthio groups ( for example,
phenylthio, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonylnato), acyloxy group (e.g. acetyloxy, benzoyloxy, etc.), acyl group (e.g. methylcarbonyl) or sulfonamide group. They may be the same or different.

Furthermore, the compound represented by general formula (I) contains 5
or six-membered ring bisspiro compounds. Among them, the bisspiro compounds useful in the present invention have the following general formula (
It is expressed as

R% R, R, R4, R, R in general formula (I').

R3', R4' are R, R, R, in general formula (I) Ic,
It has the same meaning as R.

R, R, R and A in the general formula (I) preferably have a total of 8 or more carbon atoms and those represented by the general formula (I') have low diffusivity and are suitable for specific dye fixing materials. Hydrophilic (suitable for selectively existing in the molecule.For general purposes, the above general formula (1) preferably has a total number of carbon atoms contained in the molecule of up to about 40.
5-hydroxycoumarans and 6-human 90-oxychromans in which one of R and R3 is a hydrogen atom,
Also particularly useful are a6'-dihydroxybis-22'-spirochromans represented by the general formula (■').

More preferably, R2 of general formula (I) and (I'),
R3, R4, R'', R'', R'' are an alkyl group, an alkoxy group, an aryl group, an aryloxy group or an alkylthio group.

In the formula, R is the same as defined in general formula (I),
R is preferably a substituted or branched alkyl group having 1 to 22 carbon atoms (e.g. methyl, 1-butyl, n-octyl,
t-octyl, dodecyl, hexadecyl, etc.), alkoxy groups having 1 to 22 carbon atoms (e.g., methoxy, ethoxy, octyloxy, tetradecyloxy, etc.), alkoxycarbonyl groups (e.g., ethoxycarbonyl, etc.), arylthio groups (e.g., phenylthio, etc.) , arylsulfinyl (e.g., t, phenylsulfinyl, etc.),
Arylsulfonyl (e.g. phenylsulfonyl)
, aralkyl groups (e.g. benzyl, phenethyl, etc.),
R is preferably hydrogen atom,
Alkyl groups having 1 to 22 carbon atoms (e.g. methyl, ethyl,
t-butyl, t-octyl, n-to"decyl, n-hexadecyl, etc.), alkoxy groups having 1 to 22 carbon atoms (such as methoxy, n-butyloxy, n-octyloxy,
n-tetradecyloxy, 2-ethylhexyloxy7, etc., however, R''O-, !:R are not the same substituent), aralkyloxy group having 7 to 22 carbon atoms (
For example, benzyloxy, β-7enethyloxy, etc.
However, R"O- and R are not the same substituent)
, alkylthio groups having 1 to 22 carbon atoms (e.g. methylthio group, octylthio group, to9decylthio group, hexadecylthio group, etc.), aralkylthio groups (e.g. benzylthio group, β-phenoxythio group, etc.), Acylamino group (e.g., acetylamino group, benzamide group, etc.), acyl group having 2 to 22 carbon atoms (e.g., acetyl group, butanoyl group, benzoyl group, etc.), alkylamino group having 1 to 22 carbon atoms (e.g., methylamino group), group, ethylamino group, N,N-dimethylamino group, N-methyl-N-dodecylamino group, etc.), arylamino group having 6 to 22 carbon atoms (e.g., phenylamino group, N-phenyl-N-methylamino group, group, β-naphthylamino group, etc.), heteroacid amino (for example, R is preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, t-butyl group, t-octyl group, t-amyl group, t-hexyl group, n-hexadecyl group), arylthio group having 6 to 22 carbon atoms (e.g. phenylthio group, etc.), 1 to 22 carbon atoms alkylthio groups (e.g. methylthio group, octylthio group, dodecylthio group, octadecylthio group, etc.), 7-arylsulfonyl groups IJttf, yenylsulfonyl groups having 6 to 22 carbon atoms, etc.), arylsulfinyl groups having 6 to 22 carbon atoms (
(e.g., Ic-14 phenylsulfinyl group, etc.), aralkyl groups having 7 to 32 carbon atoms (e.g. benzol group, α- or β-phenethyl group, etc.), aryl groups having 6 to 32 carbon atoms (e.g. phenyl, α- or β-naphthyl) represents an aryldithio group having 6 to 32 carbon atoms or an aryloxy group having 6 to 22 carbon atoms. Furthermore, the substituents for R and R%R above are any substituents for R%R and H, or in the hydroxy formula, R is preferably a hydrogen atom, a straight chain or branched alkyl group having 1 to 22 carbon atoms ( For example, methyl group, ethyl group,
t-butyl group, t-octyl group, i-propyl group, t-
Pentyl group, t-hexyl group, n-octadecyl group, 3
-Methyl-3- is a methyl group, 3-ethyl-3-octyl group), an alkenyl group having 3 to 22 carbon atoms (e.g. allyl group, 1-t-butyl-1-allyl group, etc.), R is ,
Preferably, a straight chain or branched alkyl group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a t-butyl group, a t-octyl group, a 1-propyl group, a t-pentyl group, a t-hexyl group, n-octadecyl group, 3-methyl-3--!antyl group, 3-ethyl-3- is methyl group, etc.), carbon number 3
-22 alkenyl groups (eg, allyl group, 1-t-butyl-1-allyl group, etc.), and R and R may be the same or different from each other. Further, R 2 represents the same meaning as R in general formula (I).

Further, the above substituents R and R may have an -NHCO- bond within the substituent.

In the formula, R10 is an alkyl group (e.g. methyl, ethyl,
propyl, n-octyl, tert-octyl, benzyl, hexadecyl), alkenyl groups (e.g. allyl,
octenyl, oleyl), aryl groups (e.g. phenyl, naphthyl), aralkyl groups (e.g. benzyl, etc.),
A heterocyclic group (eg, tetrahydropyranyl, pyrimidyl) or R''Co.

R”802. or R20NH■. Here, R18, R19 and R20 each represent an alkyl group (e.g. methyl, ethyl, n-propyl,
butyl, n-octyl, tert-octyl, benzyl), alkenyl groups (eg allyl octenyl, oleyl), aryl groups (eg eva, phenylmethoxyphenyl, naphthyl) or heterobases (eg pyridyl, pyrimidyl). R2Z and R12 each represent a hydrogen atom, a halogen atom (e.g., oxygen, chlorine, bromine), an alkyl group (e.g., methyl, ethyl, n-7'thyl, indyl), an alkenyl group (e.g., allyl, hexenyl,
octenyl), alkoxy groups (e.g. methoxy, eth*'/, <:y)ruoxy), or alkenoxy groups (
For example, R13, R14, R15, R1'', R17 are hydrogen atoms, alkyl groups (e.g. methyl, ethyl, n-butyl, benzyl), alkenyl groups (for example, 2-proynyloxy, hexenyloxy), 2-propenyl, hexenyl, octenyl), l'c hafuryl group (
Examples, phenyl, methoxyphenyl, chlorphenyl, naphthyl).

General formula (I'), (IF') used in the present invention
(Specific examples of compounds are shown below, but are not limited to these).

I-7 Knee 12 ■'-I I'-2 Eng'-3 ■'-4 ■'-5 ■'-6 ■'-7 n-I II-2TI-5II
-6 H II-7m-8 口I-9 I-10 ■-11 2H5 TII-I I[[-2I[I
-3m-4 III-5m-6 lll-7DI-8 m-9lll-10 m-11m-12 ■-13 V-I V-2 V-3 ■-4 V-5 V-6 V-7 ■- 8 IV-9 ■-10 ■-11 ■-12 ■-13 ■-15 ■-16 ■-17 ■-18 ■-19 IV-20 Shi u3 v, jj, (iso) ■-21 ■-22 ■ -23 (1)-24 Among the compounds represented by the general formula (It), preferred from the viewpoint of the effects of the present invention are the compounds represented by the general formula (■').

Here, B represents -S-1-S-S-1-0-1.

Preferably, R21, R22% R29 and R24 each represent an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an alkylthio group, a halogen, an alkoxy group, an arylthio group, an aralkoxy group, a')k O*
'/1g, -COOR"': -NHCOR", -N
H8O□R.

-8o2R"': -0-COR- ÷CH2+YA. R2S represents a hydrogen atom, an alkyl group, or an aryl group, and R26 and R27 are each a hydrogen atom, an alkyl group, an aryl group, or are bonded to each other and are substituted. R2g represents a hydrogen atom or a methyl group. R29 represents an alkyl group or an aryl group, and R30 and R31 each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or an aralkyl group. a 5- or 6-membered group bonded to each other and having any of the above-mentioned substituents
This shows a heterocyclic ring of members. A represents an ester group or a number.

■'-1 ■'-2 ■'-4 0HOH ■'-5 ■'-6 0HOH Shi f13 Shi d3 ■'-7 ■'-8 ■'-9 Ki, -3 n'-10 ■'-11 1['-12 II'-13 II'-14 ['-15 II'-16 I['-17 m'-18 If'-19 In addition, a chroman compound or a compound represented by general formula (I) Even if only one type of compound, a phenol derivative represented by the general formula (II), a hydroquinone derivative represented by the general formula (to), or a spiroindane derivative represented by the general formula (IV) is used alone,
Alternatively, two or more types may be used in combination. Further Kt nine general formula (
Antifading agents or antioxidants other than those represented by general formulas (I) to GV) including I') and (■') may be used in combination.

Furthermore, U.S. Patent No. 236 (No. 1290, 2.41a6
No. 13, No. 2,675,314, No. 2,701,19
No. 7, No. 2.704713, No. 2.72 & 639,
2732300, 2.735765, 2.7
No. 1+1801, No. 281a028, British Patent No. 1, 3
Hydroquinone derivatives described in U.S. Pat. No. 63,921, etc., U.S. Pat.
Dan (child acid derivative, US Pat. No. 273,576) described in
p-alkoxyphenols described in U.S. Pat.
No. 50, No. 3574627, No. 4764337, JP-A No. 52-35633, No. 52-14743, No. 5
The p-oxyphenol derivatives described in No. 2-152225 and the like can also be used in dye fixing materials for heat-developable photography, and can be used as photofading inhibitors.

The photofading inhibitors represented by formulas (I) to (EV) used in the present invention are usually used in an appropriate amount of about 0.01 mol to 10 mol per mol of the dye-providing substance.

Particularly preferred is about 0.1 mol to about 5 mol.

The above-mentioned anti-fading agent can be dissolved in an aqueous solution of a hydrophilic colloid such as gelatin, or an emulsified dispersion can be prepared using a conventional oil dispersion method or solid dispersion. It can be added to the coating solution for the adjacent layer.

Adjacent layers include a water-absorbing layer (usually composed of gelatin and a hardening agent) coated between the dye-fixing layer and its support, and a protective layer for the dye-fixing material (which may also serve as a peel-promoting layer). (usually mainly composed of gelatin).

It is preferable that the dye fixing layer in the dye fixing material of the present invention contains a mordant. In this case, the mordant can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferred. Here, the polymer mordant includes a polymer containing a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing these quaternary cation groups, and the like.

Preferred specific examples of homopolymers and copolymers containing one vinyl monomer unit having a tertiary amino group include the following. The number of one monomer unit represents molten (hereinafter the same). Specific examples of homopolymers and copolymers containing one vinyl monomer unit having a tertiary imidazole group include U.S. Pat. No. 4,282,305, U.S. Pat.
&061, Japanese Patent Application No. 58-226497, No. 58-2
The following include mordant NJ described in No. 32071 and the like.

Preferred specific examples of homopolymers and copolymers containing one vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 205fi101 and 2.09&041.
No. 1.594961, U.S. Patent No. 4124386
No. 41154124, No. 4273853, No. 4
．． The following may be mentioned, including mordants described in No. 45α224, JP-A-48-23225, and the like.

ite ite In addition, preferred specific examples of homopolymers and copolymers containing one vinyl unit having a quaternary ammonium salt include U.S. Pat.
No. 88, Kaida No. 95a995, patent application 1986-1661
No. 35, No. 58-169012, No. 58-23207
The following may be mentioned, including the mordants described in No. 0, No. 58-232072, and No. 59-91620.

le et al., U.S. Patent No. 2.54 & 564, U.S. Patent No. 2.48
No. 4430, No. 31148,061, No. 375
Vinylpyridine polymers and hyphenylpyridinicum cationic polymers disclosed in Fi814 specification etc.;
U.S. Patent No. 3,625.694, U.S. Patent No. 3,85 C40
No. 96, No. 412a538, British Patent No. 1.277
Polymer mordants crosslinkable with gelatin etc. disclosed in US Pat. No. 145529,
Aqueous sol-type mordant disclosed in US Patent No. 54-126027, etc.; Water-insoluble mordant disclosed in US Patent No. 389&088: US Patent No. 4168.9
Reactive mordants capable of covalently bonding with dyes disclosed in the specification of No. 75 (Japanese Unexamined Patent Publication No. 54-137333); and US Pat. No. 3,705,690, US Pat. No. 378a855, US Pat. No. 1557.066, No. 17L147, No. 327
1.148, JP-A No. 50-71” 332, JP-A No. 53-
No. 30328, No. 52-155528, No. 53-12
No. 5, No. 53-1024.

Others: U.S. Patent No. 2675316, U.S. Patent No. 2.882
Mention may also be made of the mordants described in No. 156.

Usually, the dye fixing layer is composed of the above-mentioned mordant and a hydrophilic colloid (binder).

Gelatin is the most representative hydrophilic colloid.
Other polymer mordants such as polyvinyl alcohol can also be used in the present invention.The mixing ratio of the polymer mordant and gelatin and the amount of polymer mordant to be applied are determined by the amount of dye to be mordant, the type and composition of the polymer mordant, and the image forming process to be used. The mordant/gelatin ratio is 20/80 to 80/20 (weight ratio), which can be easily determined by a person skilled in the art depending on the
, mordant application amount is 0.2 to 1511/lr? It is preferable to use an appropriate amount, preferably 0.51 to 8.9/-. The molecular weight of the yH+)mer mordant of the present invention is L00
0~100QOOO is appropriate, especially 1 (1000~
20QOOO is preferred.

In the present invention, in order to distribute the mobile dye imagewise, the photosensitive silver halide, the binder and the photosensitive silver halide are reduced to silver under high temperature conditions by reacting or inversely to the reaction. It is preferable to use a method in which a heat-developable photosensitive material having on a support a dye-providing substance that forms or releases a diffusible dye is exposed and then heated.

Furthermore, the effects of the present invention are particularly remarkable when a method of heating is used to transfer the dye.

A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixed layer. As a dye transfer aid,
A liquid or hot solvent that can dissolve the dye to be transferred at least under heating can be used. That is, if the pigment to be transferred is a hydrophilic pigment, a hydrophilic liquid or a hydrophilic hot solvent is used, and in the case of a lipophilic pigment, an organic solvent, an oil-lipophilic hot solvent, etc. that can dissolve the pigment is used. Can be used. Further, depending on the degree of hydrophilicity or lipophilicity of the dye, suitable amounts of a hydrophilic liquid, a hydrophilic heat solvent, a lipophilic solvent, and a lipophilic heat solvent may be mixed and used. The dye transfer aid may be used by moistening the dye fixing layer and/or the photosensitive layer, preferably the dye fixing layer, with a solvent, or by incorporating it directly into the layer in advance, or by adsorbing it to the mer or crystal. Alternatively, it may be incorporated as crystal water or as microcapsules.

Hydrophilic or lipophilic solvents used as the dye transfer aid include water or basic aqueous solutions containing inorganic alkali metal salts such as caustic soda, caustic potash, and soda carbonate, methanol, ethanol, propatool, butanol, and benzyl alcohol. Monohydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, phlopylene gelicol, polyhydric alcohols such as glycerol, ethers with alcoholic OH groups such as furyl alcohol, methyl cellosolve, cellosolve, acetone, acetylacetone , methyl ethyl ketone, hexanone, cyclohexanone and other ketones, methyl acetate, ethyl acetate,
Esters such as butyl acetate, methyl benzoate, n-butyl sinate, diethylamine, dibutylamine, pyridine/
and nitrogen-containing solvents such as quinoline.

When a dye transfer aid is incorporated into a photosensitive material or/and a dye fixing material, a hydrophilic thermal solvent is used as the dye transfer aid, and by heating in the presence of the dye transfer aid, the hydrophilic dye is transferred to the dye fixing material. It can be transferred and fixed to

In the image forming method in which the dye is transferred to the fixed layer by heating in the presence of a hydrophilic hot solvent, the transfer of the mobile dye may start at the same time as the dye is released, but may occur after the dye release is completed. It's okay. Therefore, the heating for transfer may be performed after the heat development or at the same time as the heat development.

Heating for dye transfer is from 60°C to 250°C from the viewpoint of storage stability and workability of the photosensitive material, so in the present invention, it functions as a hydrophilic thermal solvent within this temperature range. You can choose one as appropriate. It goes without saying that hydrophilic thermal solvents must be able to quickly aid the movement of dyes when heated, but if we also consider the heat resistance of photosensitive materials, we need to consider the melting point required for hydrophilic thermal solvents. is 40°C to 250°C, preferably 40°C to 200°C, more preferably 40c' to 150°C.

The hydrophilic thermal solvent is a compound that is in a solid state at room temperature but turns into a liquid state when heated, and has an (inorganic/organic) value>1 and a water solubility at room temperature of 1 or more. is defined as a compound of Here, inorganic and organic are:
It is a concept for predicting the properties of compounds, and its details are described in, for example, Chemistry Region 11, p. 719 (1957). As a hydrophilic heat solvent, it is essential that the (inorganic/organic) value is 1 or more, preferably 2 or more.

On the other hand, considering the size of the molecules, it is considered preferable that there be molecules that can move on their own without inhibiting the movement of the moving dye. Therefore, the molecular weight of the hydrophilic heat solvent is preferably small, about 200 or less, and more preferably about 100 or less.

Hydrophilic thermal solvents are useful if they can substantially assist the movement of hydrophilic dyes generated by heat development to the dye fixing layer, so they can not only be included in the dye fixing layer. , can be included in photosensitive materials such as photosensitive layers,
It can be contained in both the dye fixing layer and the photosensitive layer, or an independent layer containing the hydrophilic thermal solvent can be provided in the photosensitive material or in an independent dye fixing material having a dye fixing layer. From the perspective of increasing the efficiency of dye transfer to the dye fixing layer, hydrophilic thermal solvents are suitable for dye fixing layer and/or
It is also preferable to include it in a layer adjacent to the layer.

The hydrophilic thermal solvent is usually dissolved in water and dispersed in the binder, but it can also be used dissolved in alcohols, such as methanol, ethanol, etc.

Examples of usable hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles.

Specific examples and particularly preferred examples of the hydrophilic heat solvent are disclosed in Japanese Patent Application No. 58-42092, page 149~
Mention may be made of the compounds described on page 158.

These hydrophilic heat solvents can be used alone or in combination of two or more.

The hydrophilic thermal solvent is added in an amount of 10 to 10% by weight of the total coating film thickness excluding the hydrophilic thermal solvent in the photosensitive material or dye fixing material.
300% by weight, preferably 20-200% by weight! t%,
Particularly preferably, it can be used in a range of 30 to 150% by weight.

The dye-fixing material of the present invention is used in combination with a light-sensitive material as described above, and this combination can be roughly divided into two types: one is a peelable type and the other is a non-peelable type. In the case of the former peel-off type, after image exposure or heat development, the coated surface of the photosensitive material and the coated surface of the dye-fixing material are overlapped, and after the transfer image is formed, the photosensitive material is immediately peeled off from the dye-fixing material. Ru. Depending on whether the final image is of a reflection type or a transmission type, the support for the dye-fixing material can be an opaque support or a transparent support. Further, a white reflective layer may be coated if necessary. In the case of the latter type that does not require peeling, it is necessary to interpose a white reflective layer between the photosensitive layer in the photosensitive material and the dye fixing layer in the dye fixing material. It may be coated on any of the fixing materials.

The support for the dye fixing material needs to be a transparent support.

In the present invention, a dye-fixing material having a support separate from the light-sensitive material is particularly preferred.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and cyan, the photosensitive material used in the present invention contains at least three layers of halogens each sensitive to different spectrum regions. It is necessary to have a silver oxide emulsion layer.

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different wavelength regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, and a green-sensitive emulsion layer. , a combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and an infrared-sensitive emulsion layer, a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer There are combinations of emulsion layers.

Note that the infrared light-sensitive emulsion layer herein refers to an emulsion layer that is sensitive to light of 700 nm or more, particularly 740 nm or more.

The light-sensitive material used in the present invention may have two or more layers, depending on the sensitivity of the emulsion, or a photosensitive emulsion in the same wavelength region, if necessary.

Each of the above emulsion layers and /f or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer contains a dye-donating substance that releases or forms a yellow hydrophilic dye, and a dye-donating substance that releases or forms a magenta hydrophilic dye. It is necessary to contain one of a dye-providing substance that forms and a dye-providing substance that releases or forms a cyan hydrophilic dye. In other words, each emulsion layer and/or the non-photosensitive hydrophilic colloid layer adjacent to each emulsion layer must contain dye-donating substances that release or form hydrophilic dyes of different hues. If desired, two or more of them may be mixed and used in the dye-providing substance 1 having the same hue. Particularly when the dye-providing substance is colored from the beginning, it is advantageous to contain the dye-providing substance in a layer separate from the emulsion layer.

In addition to the above-mentioned layers, the photosensitive material may be provided with auxiliary layers such as a protective layer, an intermediate layer, an antistatic layer, an anti-curl layer, a release layer, and a matte layer, if necessary.

In particular, the protective layer (PC) preferably contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant, an ultraviolet absorber, and the like. 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 (such as hydroquinones), an ultraviolet absorber, and a white pigment such as TlO2 to prevent color mixing. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity.

In order to impart each of the above-mentioned color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
It may be silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide. The halogen composition within the particles may be uniform, or may have a multiple structure with different compositions on the surface and inside (Japanese Patent Laid-Open Nos. 57-154232, 58
-108533, 59-48755, 59-5
No. 2237, US Patent No. 4433.048 and European Patent No. 10Q984).

In addition, the thickness of the particles is 0.5 μm or less, and the diameter is at least 0.
．． Tabular grains with a diameter of 6 μm and an average aspect ratio of 5 or more (U.S. Pat. No. 4,414,310, U.S. Pat. No. 4,435,499, OLS No. 3,241.646 A1, etc.)
, or monodispersed emulsions with nearly uniform particle size distribution (JP-A-57-178235, JP-A No. 58-100846,
No. 58-14829, International Publication No. 83102338A1
No. 64412A3 and European Patent No. 83377A
1 etc.) may also be used in the present invention. Two or more types of silver halides having different crystal habit, halogen composition, grain size, grain size distribution, etc. may be used in combination. The gradation can also be adjusted by mixing two or more types of monodispersed emulsions with different grain sizes.

In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, silver chloroiodide, silver iodobromide, silver chloride iodide, silver iodobromide, silver iodobromide, etc. Preference is given to using silver oxide.

Such a silver salt can be obtained by adding a silver nitrate solution to a potassium bromide solution to form silver bromide grains, and then adding potassium iodide to obtain silver iodobromide having the above characteristics.

In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present.

Furthermore, for the purpose of improving high illumination failure and low illumination failure, water-soluble iridium salts such as iridium (m, IV) chloride and ammonium hexachloroiridate, or water-soluble rhodium salts such as rhodium chloride can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. Known sulfur sensitization methods, orphan 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-58-126526, JP-A-58-215644).
.

In the present invention, an organic metal salt that is relatively stable to light can be used together with the photosensitive silver halide as an oxidizing agent. 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. When an organic metal salt is used in combination in this way, the temperature of the heat-developable photosensitive material is 80°C or higher, preferably 100°C.
It is thought that when heated to a temperature of 1000 C or higher, the organometallic oxidizing agent also participates in redox using the silver halide latent image as a catalyst.

Examples of organic compounds that can be used to form the organic silver salt oxidizing agent include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-hydrogen, and imino group-containing compounds. Can be mentioned.

The silver halide used in the present invention may be spectrally sensitized by methane, color, or the like. The dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar quanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., I/trenine/nucleus, benzinP-renine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
5- to 6-membered heteroartic ring nuclei such as 4-dione nucleus, thiazolidine-2+-9one nucleus, rhodanine nucleus, and thiobarbic acid nucleus can be applied.

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

In the present invention, when photosensitive silver halide is reduced to silver under high temperature conditions, a compound that generates or releases a mobile dye in response to or inversely to this reaction, i.e. Contains a dye-donating substance.

This type of compound can be represented by the following general formula [L].

(Dye-X) n-Y (L engineering) Dye
represents a dye group or a dye precursor group; -Dye and (Dye-X)n
-Y represents a group having the property of causing a difference in diffusivity, n represents 1 or 2, and when n is 2, the two Dye-Xs may be the same or different.

As a specific example of the dye-donating substance represented by the general formula (LI), for example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Pat. No. 3,134,764.

Same No. 3362819, Same No. 359'7;200,
It is described in the same No. 3.544545, the same No. 3,482.972, etc. Also, by intramolecular nucleophilic substitution reaction)
A substance that releases a diffusible dye was disclosed in Japanese Patent Application Laid-open No. 51-6361.
No. 8, etc., a substance that releases a diffusible dye through an intramolecular rewinding reaction of the inoxacilone ring was disclosed in JP-A No. 49-11.
No. 1,628, etc. In all of these methods, the diffusible dye is released or diffused in areas where no development has occurred, and the dye is neither released nor diffused in areas where development has occurred.

Furthermore, with these methods, it is very difficult to obtain images with a high signal-to-noise ratio due to rounding in which development and dye release or diffusion occur in parallel. Therefore, in order to improve this drawback, the dye-releasing compound is made into an oxidized form that does not have dye-releasing ability, and is made to coexist with a reducing agent or its precursor, and after development, it is reduced by the reducing agent that remains unoxidized. A system for releasing a diffusible dye has also been devised, and specific examples of dye-donating substances used therein are disclosed in JP-A No. 53-11α827, JP-A No. 54-13 (1927), JP-A No. 56-164342, It is described in No. 53-35533.

On the other hand, as a substance that releases a diffusible dye in the nine regions where development occurs, there is a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developing agent. Patent No. L33 (No. 1524, Japanese Patent Publication No. 48-39165, U.S. Patent Nos. 344 & 940, etc.) also disclose diffusible dyes due to the reaction between a coupler having a diffusion-resistant group as a leaving group and an oxidized form of a developer. Substances that produce the following are described in U.S. Pat. No. 227.550 and others.

In addition, in systems using these color developers, image contamination due to oxidized dispersions of the developer becomes a serious problem.
In order to improve this problem, dye-releasing compounds that do not require a developer and have reducing properties themselves have also been devised. A method using these dye-providing compounds is described in European Patent No. 7fi492, and the effects of the present invention are most effective in this method. Representative examples are shown below along with literature. Definitions in the general formula are described in each literature.

H U.S. Patent No. 1923312 etc. U.S. Patent No. 4053312 etc. U.S. Patent No. 4055.428 etc. JP-A-51-104343 N -N -R JP-A-51-104343 Ballast JP-A-51-104343 NHSO3-D7 → Research Disclosure Magazine No. 17465 U.S. Patent No. 372-062 U.S. Patent No. 3723113 Balast US Pat. Nos. 344 & 939 Any of the various dye-providing materials described above can be used in the present invention.

Specific examples of imaging materials used in the present invention are described in the patent publications listed above.

In the present invention, the dye-donating substance is US Pat. No. 2,322
．． It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, 7-tanolic acid alkyl esters (dibutyl 7-talate, dioctyl 7-thaletate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (octyl benzoate),
Alkylamides (e.g. diethyl lauryl amide P), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (
high-boiling organic solvents such as tributyl trimesate) or organic solvents with a boiling point of about 30°C to 160°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, After dissolving in β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in hydrophilic colloid 9. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

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 addition, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, and these surfactants include those listed as surfactants elsewhere in this specification. You can use it.

The amount of the high boiling point organic solvent used in the present invention is determined by the amount of the dye-donating substance used. ! i' is 10II or less, preferably 51 or less.

In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Reducing substances include those generally known as reducing agents, as well as the aforementioned dye-donating substances having reducing properties. 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 the reducing agent used in the present invention include inorganic reducing agents such as sodium sulfite and sodium hydrogen sulfite, potassium sulfinic acids, hydroxylamines, hydrazines, hydrazides, borane amine complexes, hydroquinones, aminophenols, Catechols, p-7 22-diamines, 3-pyrazolidino 7s, hydroxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc., as well as those written by T. H. James,
Theth90r70f the photograp
hic process” 4H1, Ed, 291-3
The reducing agents described in Sections 34 and 34 can also be used. Also, JP-A No. 51-13 & 736, No. 57-4Q245, U.S.
Reducing agent precursors described in Japanese Patent No. 433α617 and the like can also be used.

Combinations of various developers 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 0.1 to 10 mol.

An image formation accelerator can be used in the dye-fixing material and photosensitive material of the present invention. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and photosensitive material layers. Functions such as promoting the transfer of dye from the dye fixing layer to the dye fixing layer, and physicochemical functions include interaction with bases or base precursors, nucleophilic compounds, oils, hot solvents, surfactants, silver or silver ions. It is classified as a compound with However, these groups of substances generally have multiple functions) and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators are classified by function and specific examples of each are shown. However, this classification is for convenience, and in reality, one compound has multiple functions. There are many.

(a) Bases Examples of preferred bases include, as inorganic bases, alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates. ; ammonium hydroxide; hydroxide of quaternary alkylammonium; hydroxide of other metals, etc.; examples of organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); )
; Aromatic amines (N-alkyl substituted aromatic amines,
N-human 30xylalkyl-substituted aromatic amines and bis(p-(dialkylamine)phenylcomethanes)
, heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, especially pKa
is preferably 8 or more.

Examples of base precursors include salts of organic acids and bases that decompose by decarboxylation by heating, compounds that release amines by decomposing by reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, and Beckmaff rearrangement. , those which cause some kind of reaction upon heating and release a base are preferably used. A preferred base precursor is British Patent No. 998,949.
Salt of trichloroacetic acid described in US Patent No. 406+
Salt of α-sulfonylacetic acid described in No. 1420, patent application 1972
Salts of propiolic acids described in US Pat. No. 8-55.700, 2-carboxycarboxamide derivatives described in US Pat. hydroxamic carbamates described in Japanese Patent Application No. 58-43860 using Rossen rearrangement, and Japanese Patent Application No. 58-3 which produces dinitrile by heating.
Examples include albiyaci carbamates described in No. L614. Others include British Patent No. 998,945, U.S. Patent No. 32211846, and Japanese Unexamined Patent Publication No. 50-22625.
Also useful are the base precursors described in British Patent No. 2.07C4480 and others.

(e) Nucleophilic compounds water and water-releasing compounds, amines, amidines, guanidines, hydroxylamines, hydrazines, hydrazides 9, oximes, hydroxamic acids, sulfonamides 0, active methylene compounds, alcohols , thiols, and salts or precursors of the above compounds can also be used.

(d) Oil A high boiling point organic solvent (so-called plasticizer) used as a solvent during emulsification and dispersion of hydrophobic compounds can be used.

(el hot solvent) Solid at ambient temperature, it melts near the development temperature and acts as a solvent, including ureas, urethanes, amides, pyrudines, sulfonamides, sulfones, 9 sulfoxides, esters, and ketones. 4 in compounds of the class, ether class
Those that are solid at 0° C. or lower can be used.

(f) Surfactants Pyridinium salts, ammonium salts, phosphonium salts described in JP-A-59-74547, JP-A-59-57
Examples include polyalkylene oxides described in No. 231.

(g) Compound imides that interact with silver or silver ions, nitrogen-containing peterocycles described in Japanese Patent Application No. 58-51657, thiols described in Japanese Patent Application No. 57-222247,
Examples include thioureas and thioethers.

The image formation accelerator may be incorporated into either the photosensitive material or the dye-fixing material, or may be incorporated into both. Further, the layers to be incorporated may be incorporated in the emulsion layer, the intermediate layer, the protective layer, the dye fixing layer, and any layer adjacent thereto. The same applies to forms in which the photosensitive layer and the dye fixing layer are provided on the same support.

Image formation accelerators can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained by using several types in combination.

In particular, when a base or base precursor is used in combination with other promoters, a remarkable promoting effect is exhibited.

In the present invention, various development stoppers can be used in the light-sensitive material and dye-fixing material in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal 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 formic acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, nitrogen-containing heterocyclic compounds, and mercapto compounds. For acid precursors, for example, patent application 1982
-216928 and Japanese Patent Application No. 59-48305, compounds that release sialic acid through Rossen rearrangement described in Japanese Patent Application No. 59-85834, etc., and are replaced with polybases by heating. Examples of electrophilic compounds that cause the reaction include the compounds described in Japanese Patent Application No. 85836/1983.

The above-mentioned development stoppers are particularly effective when a base precursor is used, which is preferable.

In that case, the value of the base precursor/acid precursor ratio (molar ratio) is preferably 1/20 to 20/1, and 115 to 20/1.
5/1 is more preferred.

Further, in the present invention, a compound that activates development and simultaneously stabilizes the image can be used in the dye fixing material or the light-sensitive material. Among them, isothiuroniums represented by 2-hydroxyethyl isothycuronium trichloroacetate described in U.S. Pat. acetate)
Bis(isothiuronium) such as, West German Patent Publication No. 21
Thiol compounds described in No. 62714, U.S. Pat. No. 40
2-amino-2-thiazolium described in No. 12.260
Trichloroacetate, thiazolium compounds such as 2-7minor 5-bromoethyl-2-thiazolium trichloroacetate, bis(2-amino-2-thiazolium)methylenebis(sulfonylacetate) described in U.S. Pat. No. 406α420, 2-amino- Compounds having 2-carboxamide as an acidic moiety such as 2-thiazolium phenylsulfonylacetate are preferably used.

Additionally (azole thioethers and blocked azolinthionic compounds described in Rugie Patent No. 768,071,
4-aryl-1 described in U.S. Patent No. 389a859
-carbamyl-2-tetrazoline-5-thione compound,
Other U.S. Patent No. 3839041, U.S. Patent No. 384478
Compounds described in No. 8, No. 3877;940 are also preferably used.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are L2.4-triazole, LH-tetrazole, thiouracil and L3.4-
Compounds such as thiadiazole. Examples of preferred toning include 5-amino-], a4-thiadiazole-2
-thiol, 3-mercapto-1,2,4-triazole, bis(dimetelcarnozyl):) sulfide, 6
-methylthiouracil, 1-phenyl-2-tetraazoline-5-thione, and the like. Particularly effective toning agents are compounds capable of forming black images.

The binders used in the present invention can be contained alone or in combination.

A hydrophilic binder can be used for this binder. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as proteins such as gelatin, gelatin derivatives, cellulose derivatives, starch,
Natural substances such as polysaccharides such as gum arabic, and water-soluble yts such as polyvinyl pyrroline and acrylamide polymers.
= +) Contains synthetic polymeric substances such as vinyl compounds. Other synthetic polymeric substances include dispersed vinyl compounds in the form of latexes, which increase the dimensional stability of photographic materials, among others.

In the present invention, the photographic light-sensitive material and the dye-fixing material may contain an inorganic or organic hardener in the photographic emulsion layer and other layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, kultaldehyde, etc.),
N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (23-
dihydroxydioxane, etc.), active vinyl compounds (L
3,5-Triacryloyl-hexahydro-8-)IJ
Azine% L3-vinylsulfonyl-2-prononol,
L2-bis(hinylsulfonylacetamido)ethane, etc.), active halogen compounds (24-dichloro-6-hydroxy-5-lyazine, etc.), mucohalogen acids, (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone. Or they can be used in combination.

The supports used in the light-sensitive materials and dye-fixing materials in the present invention are those that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, but also cellulose acetate film, cellulose ester film, vinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and their like. Related films or resin materials are included. Paper supports laminated with polymers such as polyethylene can also be used. Polyesters described in US Pat. No. 634,089 and US Pat. No. 3,725,070 are preferably used.

The dye fixing material used in the present invention has at least one layer containing a mordant), and when the dye fixing layer is located on the surface, a protective layer can be further provided if necessary.

Furthermore, a water absorption layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid or to control the dye transfer aid if necessary. These layers may be adjacent to the dye fixing layer or may be coated via an intermediate layer.

The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, if necessary.

In addition to the above-mentioned layers, the dye fixing element used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl layer, if necessary.

One or more of the above layers may include a base and/or base precursor to promote dye migration, a hydrophilic thermal solvent, an antifade agent to prevent color mixing of the dyes, a UV absorber, a dimensional stability Dispersed vinyl compound for increasing
A fluorescent brightener or the like may also be included.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, gelatin, gelatin conductors, polyvinyl alcohol, proteins such as cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, water-soluble polyvinyl compounds such as dextrin, pullulan, polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Synthetic polymeric substances such as are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

〔Example〕

Example 1 The method for making a benzotriazole silver emulsion will be described.

Gelatin 28I! and benzotriazole 13.2.9 are dissolved in water 300-. This solution is kept at 40°C and stirred. A solution prepared by dissolving 1711f silver nitrate and 100 dK in water was added to this solution over a period of 2 minutes.

The pH of the benzotriazole silver emulsion is adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to 6.30 to obtain an incitriazole silver emulsion with a yield of 400.9.

! We will explain how to make silver halide emulsions for the 5th layer and the 1st layer.

A well-stirred aqueous gelatin solution (containing 20.9 g of gelatin and 3 I of sodium chloride in 1,000 d of water, kept at 75°C), an aqueous solution containing 600 g of IJ and potassium bromide, and silver nitrate. Aqueous solution (water 600
- 59 moles of silver nitrate α dissolved in) at the same time 40
Added at equal flow rates over a period of minutes. In this way, a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.40 μm (
50 mol of bromine (S) was prepared.

After washing with water and desalting, sodium thiosulfate ram 51fq and 4-human 90x-6-methyl-La3't7-tetrazye/
Chemical sensitization was carried out at 60° C. by adding 20 liters of Den.

The yield of emulsion was 600 g.

Next, we will explain how to make silver halide holes for the third layer.

A well-stirred aqueous gelatin solution (containing 20 J of gelatin and 31 ml of sodium chloride in 1000 d of water, kept at 75°C) was mixed with an aqueous solution containing sodium chloride and potassium bromide (600 ml) and an aqueous silver nitrate solution (600 d of water). 0.59 mol of silver nitrate dissolved in the solution) was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

After washing with water and desalting, sodium thiosulfate 511II and 4-human 90x-6-methyl-1,3aa, 7-tetrazaindene 20WI were added to perform chemical sensitization at 60°C. The yield of emulsion was 60ON.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

Yellow dye-providing substance (A) is 511, surfactant is 2-ethyl-hexyl succinate sodium sulfonate, 0.5.9. Weigh 10I of triisononyl phosphate, add 30d of ethyl acetate, and dissolve by heating to about 60°C to form a homogeneous solution. After stirring and mixing this solution and 100 fI of a 10% solution of lime-treated gelatin,
Disperse with a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a yellow dye-providing substance dispersion.

A dispersion of a magenta dye-providing substance was prepared in the same manner as described above, except that the magenta dye-providing substance (B) was used and tricresyl 7 phosphate 7,5 II was used as a high boiling point solvent.

A cyan dye-providing substance (C) was prepared in the same manner as the yellow dye dispersion.

Using these materials, a color photosensitive material having a multilayer structure as shown in the following table was prepared.

Dye-donating substance (A) (B) 1gk133-('') (C) (D-2) (D-3) t Next, we will discuss how to make a gelatin dispersion of the anti-fading agent. Agent (eL) 511 t Gelatin 1
% aqueous solution 100# and milled by glass beads 100.9 with an average particle size of about 0.6 soa.
Pulverized for minutes. Glass peas were separated by t-filtration to obtain gelatin dispersion (α) 1. A gelatin dispersion (A) was obtained using the following anti-fading agent (h) in exactly the same manner.

Note that as another method for obtaining a dispersion, a method using oil emulsion dispersion can also be used.

Anti-fading agent (α) Anti-fading agent <b> Next, the method of preparing the dye fixing material (G) will be described.

First, the following gelatin hardener H-1 (0.75N), H
-2 (0.25g) and add 160d of distilled water, 1
100 I of 0% acid-treated gelatin was added and mixed uniformly.

This mixed solution was uniformly applied onto a paper support laminated with polyethylene in which titanium oxide was dispersed to a wet film thickness of 60 μm, and then dried.

Next, mordant P-1 (10II) and 200 d of distilled water were added, followed by 10 tIb lime-treated gelatin 10019 and mixed uniformly. Apply this mixture onto the above coating.
It was applied uniformly to form a wet film of 5 μm. This sample was dried and used as a dye fixing material (G) having the following mordant P-1t-.

Gelatin hardener H-1 CH2-CH8O2CH2■NH (CH2) 2 volumes ω12
Ta24-CH2 gelatin hardener H-2 CH2-IIc&302CH2ωNH(CH2)3NH
COCH2So2CH Core 2 Mordant P-1 Next, the method of making the dye fixing materials (H) and (I) will be described.

First, the gelatin hardener H-1 (α7511'),
Add H-2 (0, 25, 9) and 160 d of distilled water,
100.9% of gelatin treated with thionic acid was added and mixed uniformly.

This mixed solution was uniformly applied onto a paper support laminated with polyethylene in which titanium oxide was dispersed to a wet film thickness of 60 μm, and then dried.

Next, the above mordant P-1 (10,9), the above anti-fade gelatin dispersion (a) 100 g and 100 g of distilled water were added, and further 10 g of lime-treated gelatin 1001
In addition to 1, mix the mixture uniformly and apply 8 on the above coating.
It was applied uniformly to form a 5 μm wet film. This sample was dried and used as a dye fixing material (H).

Moreover, it was used as a dye fixing material (I) in exactly the same manner except that a gelatin dispersion (bit) of an anti-fading agent was used.

A tungsten light bulb is used in the multilayered color photosensitive material described above, and a G1R1 R three-color separation filter (G is 500 to 600 nm, R is 600 nm, and the density is continuously changed) is used.
~700 nm bunt 9p x fi, kl-1IR is 7
The sample was exposed to light at 500 lux for 1 second through a filter that transmits at least 0.00 nm.

Thereafter, it was heated uniformly for 30 seconds on a heat block heated to 140°C.

Next, apply 1rI on the membrane side of the dye fixing material. After supplying 920-g of water, the heat-treated photosensitive coatings were stacked on a fixing material so that the film surfaces were in contact with each other. After heating for 6 seconds on a heat block at 80°C, the dye-fixing material is peeled off from the light-sensitive material, and yellow, magenta, and cyan colors corresponding to the G, R, and R color separation filters are deposited on the fixing material, respectively. The image was obtained. The dye density of each color was measured using a Macbeth reflection densitometer (RD519).

Next, on the film surface of the dye fixing material having these negative images,
A transparent film having an ultraviolet absorbing layer was superimposed, and xenon light (100,000 lux) was irradiated onto the color image for 3 days using an Atlas CO 65 weatherometer. The color image density before and after xenon light irradiation was measured to evaluate the fastness of the color image to light.

Table 1 shows the dye residual rate at a reflection density of 1.0.

Table 1 Example 2 The same operations and treatments as in Example 1 were carried out except that the mordant in the dye-fixing material of Example 1 was replaced with mordant P-2 having the following structure. ) and (L) were used as dye fixing materials.

The results are shown in Table 2.

From Tables 2 and L2, it is clear that adding an anti-fading agent (cL) or <b> to a dye fixing material containing a mordant greatly improves the light fastness of color images. Ta.

□RiQtsu□

Claims (1)

[Scope of Claims] A dye fixing layer that fixes a mobile dye imagewise distributed on a support, and the dye fixing layer or a layer adjacent thereto has the following general formulas (I) to (IV). A dye-fixing material characterized by containing at least one compound selected from the compounds represented by: General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. Representation,
A, together with ▲There are mathematical formulas, chemical formulas, tables, etc.▼, represents a nonmetallic atom necessary to complete a 5- or 6-membered ring. R
^2, R^3, R^4 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkoxy group, an alkenyl group, an alkenoxy group, an acylamino group, a halogen atom, It represents an alkylthio group, a diacylamino group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, an acyl group, or a sulfonamide group, and these may be the same or different. Further, the compound represented by the general formula (I) includes a 5- or 6-membered ring bisspiro compound containing A. ] General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 is the same as defined in general formula (I)] R^5 is an alkyl group, alkoxy group, alkoxycarbonyl group, arylthio group, arylsulfinyl, arylsulfonyl, aralkyl group, halogen atom, aryl group, acyl group, R^6 is a hydrogen atom,
Alkyl group, alkoxy group (However, R^1O- and R^6
are not the same substituent), aralkyloxy group (however, R^1O- and R^6 are not the same substituent), alkylthio group, aralkylthio group, acylamino group, acyl group , represents an alkylamino group, an arylamino group, or a heterocyclic amino group. R^7 is a hydrogen atom,
Represents a halogen atom, an alkyl group, an arylthio group, an alkylthio group, an arylsulfonyl group, an arylsulfinyl group, an aralkyl group, an aryl group, an aryldithio group, or an aryloxy group. General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc.
The alkenyl group R^9 represents a straight chain, molecular chain alkyl group, or alkenyl group, and R^8 and R^9 may be the same or different from each other. Also, R^1 is R^ of general formula (I)
It has the same meaning as 1. In addition, the above substituents R^8, R^
9 may have an -NHCO- bond within the substituent. General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1^0 is an alkyl group, alkenyl group, aryl group, aralkyl group, heterocyclic group, or R^1^8
CO, R^1^9SO_2 or R^2^0NHCO
represents a group represented by Here R^1^8, R^1^
9 and R^2^0 are each an alkyl group, an alkenyl group,
Represents an aryl group or a heterocyclic group. R^1^1 and R^1^2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, or an alkenoxy group, and R^1^3, R^1^4, R^1^ 5, R
^1^6 and R^1^7 represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. ]