JPH0554944B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Field of Application) The present invention relates to a dye fixing material for heat-developable photography in which silver halide is developed by heating in a substantially moisture-free state. In particular, the present invention relates to a material for forming a movable dye into an image by heat development and for fixing the dye. (Prior art) Photography using silver halide has been the most widely used method since it has excellent photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. I've been exposed to it. 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 developer to a dry processing using heating, etc. It has been. Heat-developable photosensitive materials are well known in the art, and for more information on heat-developable photosensitive materials and their processes, see, for example, 553 of Fundamentals of Photographic Engineering (published by Corona Publishing, 1979).
Pages ~ 555 pages, video information published in April 1978, 40 pages,
Nebletts Handbook of Photography and
Reprography 7th Ed. (Van Nostrand Reinhold
Company), pages 32-34, US Pat. No. 3,152,904,
No. 3301678, No. 3392020, No. 3457075, British Patent No. 1131108, No. 1167777, and Research Disclosure Magazine, June 1978 issue, pages 9-15 (RD-17029). For information on how to obtain a color image,
Many methods have been proposed. Regarding the method of forming a color image by combining an oxidized form of a developer with a coupler, U.S. Pat.
- Aminophenol-based reducing agent has been awarded a Belgian patent
Issue 802519 and Research Disclosure Magazine
September 1975, pages 31 and 32, proposes a sulfonamidophenolic reducing agent, and US Pat. No. 4,021,240 proposes a combination of a sulfonamidophenolic reducing agent and a 4-equivalent coupler. However, this method has the disadvantage that a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a cloudy color image. To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer. It has the disadvantage that it is not easy to transfer. In addition, a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure Magazine, May 1978 issue 54.
Described on page 58 RD-16966. With this method, it is difficult to suppress the release of dye in areas not exposed to light, and a clear image cannot be obtained, so it is not a common method. Furthermore, regarding the method of forming positive color images using the photosensitive silver dye bleaching method, see, for example, Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-14433), December 1976 issue, pages 14-15 of the same magazine. Page (RD-15227), U.S. Pat. No. 4,235,957, and others, useful dyes and bleaching methods are described. However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the bleaching of the dye, and the resulting color images may coexist during long-term storage. It had the disadvantage of being gradually reductively bleached by free silver and the like. Further, regarding the method of forming color images using leuco dyes, for example, US Pat. No. 3,985,565,
No. 4022617. However, this method has the disadvantage that it is difficult to stably incorporate 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 for development, and the resulting images have the drawbacks of high fog 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. (JP-A-58-58543, JP-A-58-
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. However, there is a problem in that the transferred color image formed in the dye fixing layer has low light fastness. The purpose of the present invention is to provide a transferred color image with high density,
The object of the present invention is to provide a photographic element for heat-developable photography that improves the light fastness of transferred color images. It is about providing. (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 has vinyl monomer units having a tertiary imidazole group. The dye fixing layer or a layer adjacent thereto contains a mordant containing the following general formula () to
This is achieved by a dye-fixing material characterized by containing at least one compound selected from the compounds represented by (). Here, R ¹ is a hydrogen atom, preferably having 1 carbon atom
~22 alkyl groups (e.g., methyl, ethyl, propyl, n-octyl, dodecyl, hexadecyl, etc.), acyl groups (e.g., acetyl, benzoyl,
pentanoyl, (24-di-tert-amylphenokyl)acetyl, etc.), sulfonyl groups (e.g., methanesulfonyl, butanesulfonyl, benzenesulfonyl, toluenesulfonyl, bexadecanesulfonyl, etc.), carbamoyl (e.g., N-methylcarbamoyl, N, N-diethylcarbamoyl, N-dodecylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g. N
-methylsulfamoyl, N,N-dimethylsulfamoyl, N-tetradecylsulfamoyl,
N-phenylsulfamoyl, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl,
phenoxycarbonyl, etc.), trialkylsilyl group (e.g., trimethylsilyl, dimethylbutylsilica, etc.), and A represents

[Formula] represents a nonmetallic atom necessary to complete a 5- or 6-membered ring, and this ring may be substituted,
Preferred substituents include 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, etc.), and aryloxy groups. (e.g., phenoxy), aralkyl groups (e.g., benzyl, phenethyl, etc.), aralkoxy groups (e.g., benzyloxy, phenethyloxy, etc.), alkenyl groups (e.g., allyl), N-substituted amino groups (e.g., alkylamino,
dialkylamino, N-alkyl-N-arylamino, piperazino, etc.), heterocyclic groups (e.g. benzothiazolyl, benzoxazoyl, etc.), and even if substituted by a residue forming a condensed ring. good. Preferred substituents for the alkyl and aryl groups mentioned above include halogen atoms, hydroxy groups, carboxy groups, alkoxycarbonyl groups, acyloxy groups, sulfo groups, sulfonyloxy groups, amide groups (e.g. acetamide, ethanesulfonamide, benzamide, etc.),
It may be substituted with an alkoxy group, an aryloxy group, etc. R ² , R ³ , and R ⁴ each represent a hydrogen atom, an alkyl group (e.g., 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., (e.g., phenoxy), aralkyl groups (e.g., benzyl, phenethyl, etc.), aralkoxy groups (e.g., benzyloxy, phenethyloxy, etc.), alkenyl groups (e.g., allyl), alkenoxy groups (e.g., allyloxy, etc.), acylamino groups (e.g., acetylamino), , benzamide, (2,4-di-tert-acylphenoxy)acetylamino, etc.), halogen atoms (e.g., chloro atom, bromine atom, etc.), alkylthio groups (e.g., ethylthio, dodecylthio, octadecylthio, etc.), diacylamino groups (e.g., succinimide, hydantoinyl, etc.), arylthio groups (e.g., phenylthio, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), acyloxy groups (e.g., acetyloxy, benzoyloxy, etc.), acyl groups (e.g., acetyloxy, benzoyloxy, etc.), (for example, methylcarbonyl) or a sulfonamide group, which may be the same or different from each other. Furthermore, for the compound represented by the general formula (), A
Included are 5- or 6-membered ring bisspiro compounds containing. Among them, the bisspiro compound useful in the present invention is represented by the following general formula ('). R ¹ , R ² , R ³ , R ⁴ , R ¹ ′ in general formula (′),
R ² ′, R ³ ′, and R ⁴ ′ are R ¹ , R ² , and
It has the same meaning as R ³ and R ⁴ . R ² , R ³ , R ⁴ and A in the general formula () preferably have a total of 8 or more carbon atoms, and those represented by the general formula (') have low diffusivity, making it difficult to identify dye-fixing materials. It is suitable for being selectively present in the hydrophilicity of. Also, for general purposes, preferably in the general formula () in which the total number of carbon atoms contained in the molecule is up to about 40,
5-hydroxycoumarans and 6-hydroxychromans in which one of R ² and R ³ is a hydrogen atom, and 6,6'- represented by the general formula (')
Dihydroxybis-2,2'-spirochromans are particularly useful. More preferably, the general formula (),
Furthermore, R ² , R ³ , R ⁴ , R ² ′, R ³ ′, and R ⁴ ′ in (′) are an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or an alkylthio group. In the formula, R ¹ is the same as defined in the general formula (), and R ⁵ is preferably a substituted or branched alkyl group having 1 to 22 carbon atoms (e.g. methyl, t-
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., phenylsulfinyl, etc.), arylsulfonyl (e.g., phenylsulfonyl, etc.), aralkyl groups (e.g., benzyl, phenethyl, etc.), halogen atoms (e.g., chlorine atom, bromine atom, etc.) atom), an aryl group (e.g., phenyl, α-, or β-naphthyl, etc.), an acyl group (e.g., acetyl, butanoyl, benzoyl, etc.), and R ⁶ is preferably a hydrogen atom or a group having 1 to 22 carbon atoms. Alkyl groups (e.g. methyl,
ethyl, t-butyl, t-octyl, n-dodecyl, n-hexadecyl, etc.), alkoxy groups having 1 to 22 carbon atoms (e.g. methoxy, n-butyloxy, n-octyloxy, n-tetradecyloxy, 2-ethylhexyl) Oxygen, etc., however, R ¹
O- and R ⁶ are not the same substituent), aralkyloxy groups having 7 to 22 carbon atoms (e.g., benzyloxy, β-phenethyloxy, etc., however,
R ¹ O- and R ⁶ are not the same substituent),
Alkylthio groups having 1 to 22 carbon atoms (e.g., methylthio group, octylthio group, dodecylthio group, hexadecylthio group, etc.), aralkylthio groups (e.g.,
benzylthio group, β-phenoxythio group, etc.),
Acylamino group having 2 to 22 carbon atoms (e.g. acetylamino group, benzamide group, etc.), 2 to 22 carbon atoms
22 acyl groups (e.g., acetyl group, butanoyl group, benzoyl group, etc.), alkylamino groups having 1 to 22 carbon atoms (e.g., methylamino group, ethylamino group, N,N-dimethylamino group, N-methyl- N-dodecylamino group, etc.), C6-22 arylamino group (e.g., phenylamino group,
N-phenyl-N-methylamino group, β-naphthylamino group, etc.), heteroacid amino group (e.g.

【formula】

【formula】

[Formula], etc.). R ⁷ is preferably a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), a carbon number of 1 to 22
an alkyl group (e.g. methyl group, ethyl group, t-
Butyl group, t-octyl group, t-amyl group, t-
hexyl group, n-hexadecyl group, etc.), arylthio group having 6 to 22 carbon atoms (e.g. phenylthio group, etc.), alkylthio group having 1 to 22 carbon atoms (e.g. methylthio group, octylthio group, dodecylthio group, octadecylthio group, etc.), Arylsulfonyl groups having 6 to 22 carbon atoms (e.g. phenylsulfonyl group), arylsulfinyl groups having 6 to 22 carbon atoms (e.g. phenylsulfinyl group), aralkyl groups having 7 to 32 carbon atoms (e.g. benzyl basis,
α- or β-phenethyl group, etc.), carbon number 6 or more
32 aryl groups (e.g. phenyl, α- or β
-naphthyl, etc.) 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 ⁵ , R ⁶ , and R ⁷ above are further R 5 , R ⁶ , and R 7 .
R ⁶ and R ⁷ may be substituted with any substituent or hydroxyl group. In the formula, R ⁸ is preferably a hydrogen atom, 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, an i-propyl group, t-pentyl group, t-hexyl group, n-octadecyl group, 3-methyl-3-
pentyl group, 3-ethyl-3-pentyl group, etc.),
Alkenyl groups having 3 to 22 carbon atoms (e.g. allyl group,
1-t-butyl-1-allyl group, etc.), R ⁹ is preferably a linear or branched alkyl group having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, t-butyl group, t-octyl group, etc.). group, i-propyl group, t-pentyl group, t-hexyl group, n-octadecyl group,
3-methyl-3-pentyl group, 3-ethyl-3-
pentyl group, etc.), or an alkenyl group having 3 to 22 carbon atoms (eg, allyl group, 1-t-butyl-1-allyl group, etc.), and R ⁸ and R ⁹ may be the same or different. Moreover, R ¹ represents the same meaning as R ¹ in the general formula (). In addition, the above substituents R ⁸ and R ⁹ are -
It may have an NHCO- bond. where R ¹⁰ is an alkyl group (e.g. methyl, ethyl, propyl, n-octyl, tert-octyl, benzyl, hexadecyl), an alkenyl group (e.g. allyl, octenyl, oleyl), an aryl group (e.g. phenyl, naphthyl) ) aralkyl group (e.g. benzyl etc.), heterocyclic group (e.g. tetrahydropyranyl, pyrimidyl) or
Represents a group represented by R ¹⁸ CO, R ¹⁹ SO ₂ or R ²⁰ NHCO. Here, R ¹⁸ , R ¹⁹ and R ²⁰ are each an alkyl group (e.g. methyl, ethyl, n-
propyl, n-butyl, n-octyl, tert-octyl, benzyl), alkenyl groups (e.g. allyloctenyl, oleyl), aryl groups (e.g. phenylmethoxyphenyl, naphthyl) or heterobases (e.g. pyridyl, pyrimidyl)
represents. R ¹¹ and R ¹² are each a hydrogen atom, a halogen atom (e.g., oxygen, chlorine, bromine), an alkyl group (e.g., methyl, ethyl, n-butyl, benzyl), an alkenyl group (e.g., allyl, hexenyl, octenyl), Alkoxy groups (e.g.
methoxy, ethoxy, benzyloxy), or alkenoxy groups (e.g. 2-propenyloxy,
hexenyloxy), R ¹³ , R ¹⁴ , R ¹⁵ ,
R ¹⁶ and R ¹⁷ are hydrogen atoms, alkyl groups (e.g. methyl, ethyl, n-butyl, benzyl), alkenyl groups (e.g. 2-propenyl, hexenyl,
octenyl), or an aryl group (eg, phenyl, methoxyphenyl, chlorophenyl, naphthyl). Specific examples of organic compounds having aromatic rings that help prevent photofading of general formulas (') and (') containing general formulas () to () used in the present invention are shown below, but are not limited thereto. isn't it. -1 -2 -3 -4 -5 -6 -7 -8 -9 −10 −11 −12 '-1 '-2 '-3 '-4 '-5 '-6 '-7 '-8 -1 -2 -3 -4 -5 -6 -7 -8 -9 −10 −11 -1 -2 -3 -4 -5 -6 -7 -8 -9 −10 −11 −12 −13 -1 -2 -3 -4 -5 -6 -7 -8 -9 −10 −11 −12 −13 −14 −15 −16 −17 −18 −19 −20 −21 −22 −23 −24 Among the compounds represented by the general formula (), preferred from the viewpoint of the effects of the present invention are the compounds represented by the general formula ('). Here, B is -S-, -S-S-, -O-, -
CH ₂ −S−CH ₂ −, −SO ₂ −, −SO−, −CH ₂ −O
−CH ₂ −,

【formula】

[Formula] or

[Formula] is shown. R ²¹ , R ²² , R ²³ , and R ²⁴ are each preferably a hydrogen atom or 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, or an allyloxy group. , −COOR ²⁹ , −NHCOR ²⁹ ,
_-NHSO2R29 , _-SO2R29 ^, -O- ^{COR29 ,}

【formula】

[Formula] or (-CH ₂ ) _-o represents A. R ²⁵ represents a hydrogen atom, an alkyl group, or an aryl group, and R ²⁶ and R ²⁷ each represent a hydrogen atom,
It represents an alkyl group, an aryl group, or a substituted 5- or 6-membered ring bonded to each other. R ²⁸ represents a hydrogen atom or a methyl group. R ²⁹ represents an alkyl group or an aryl group, and R ³⁰ and R ³¹ are each a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an aralkyl group, or a 5- or 6-membered group bonded to each other and having any of the above-mentioned substituents. Indicates a member heterocycle. A is an ester group or

[Formula] is shown. m and n represent integers of 1 to 3. '-1 '-2 '-3 '-4 '-5 '-6 '-7 '-8 '-9 ′−10 ′−11 ′−12 ′−13 ′−14 ′−15 ′−16 ′−17 ′−18 ′−19 Also, chroman compounds or coumaran compounds represented by the general formula (), phenolic derivatives represented by the general formula (), or general formula ()
The hydroquinone derivative represented by the formula () or the spiroindane derivative represented by the general formula () may be used alone or in combination of two or more. Furthermore, the general formula (′),
Antifading agents or antioxidants other than those represented by general formulas () to () containing (') may also be used. Furthermore, U.S. Patent No. 2360290, U.S. Patent No. 2418613, U.S. Patent No.
No. 2675314, No. 2701197, No. 2704713, No.
No. 2728639, No. 2732300, No. 2735765, No. 2735765, No. 2732300, No. 2735765, No.
No. 2710801, No. 2816028, British Patent No. 1363921,
Hydroquinone derivatives described in et al., US patent
Gallic acid derivatives described in US Pat. No. 3457079, US Pat. No. 3069262, etc.; p described in US Pat.
-Alkoxyphenols, US Pat. No. 3,432,300;
P-oxyphenol derivatives described in JP-A No. 3573050, JP-A No. 3574627, JP-A No. 3764337, JP-A No. 52-35633, JP-A No. 52-14743, JP-A No. 52-152225, etc. are also dye fixing materials for thermal development photography. It can be used as a photofading inhibitor. The photofading preventive agent represented by the general formulas () to () used in the present invention is usually suitably used in an amount of about 0.01 to 10 moles per mole of the dye-providing substance.
Particularly preferred is about 0.1 mol to about 5 mol. The above-mentioned anti-fading agent is dissolved in an aqueous solution of a hydrophilic colloid such as gelatin, or an emulsified dispersion is prepared by a conventional oil dispersion method or solid dispersion, and the aqueous solution or emulsified dispersion is applied to a dye-fixed form or a layer adjacent to it. It can be added to the coating solution for use. 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). In the present invention, the dye fixing layer contains a mordant (hereinafter also referred to as a polymer mordant) containing a vinyl monomer unit having a tertiary imidazole group.
Specific examples of this mordant include U.S. Pat.
No. 4282305, No. 4115124, No. 3148061, Patent Application
The following may be mentioned, including the mordants described in Nos. 58-226497 and 58-232071.

【formula】 【formula】

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group and a quaternary imidazolium salt include British Patent Nos. 2056101, 2093041, and British Patent Nos.
1594961, U.S. Patent No. 4124386, U.S. Patent No. 4115124,
The following may be mentioned, including mordants described in 4273853, 4450224, and JP-A-48-28225. However, the tertiary amino group of the tertiary imidazole group may exist in the same imidazole group as the quaternary amino group, or may exist in a different monomer unit. Usually, the dye fixing layer is composed of the above-mentioned mordant and a hydrophilic colloid (binder). Gelatin is the most typical hydrophilic colloid, and other materials such as polyvinyl alcohol can also be used in the present invention. Those skilled in the art can easily determine the mordant/gelatin ratio depending on the type and composition of the mordant, the image forming process used, etc., but the mordant/gelatin ratio is 20/80 to 80/20 (weight ratio), and the amount of mordant applied is 0.2~15g/ ^m2 is suitable, preferably
Preferably it is used at 0.5g/ ^m2 to 8g/m2. The molecular weight of the polymer mordant of the present invention is suitably 1,000 to 1,000,000, particularly preferably 10,000 to 200,000. 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. 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 the dye transfer aid, a liquid or a hot solvent that can dissolve the dye to be transferred at least in a heated state 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 it may be directly included in the layer in advance, or it may be adsorbed onto a polymer or crystal. 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, propanol, butanol, benzyl alcohol, etc. Monohydric alcohols, polyhydric alcohols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and glycerol, ethers with alcoholic OH groups such as furyl alcohol, methyl cellosolve, and cellosolve, acetone, acetylacetone, methyl ethyl ketone, hexanone, Ketones such as cyclohexanone, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, n-butyl phosphate,
Examples include nitrogen-containing solvents such as diethylamine, dibutylamine, pyridine, and 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. can be transferred and fixed. By heating in the presence of a hydrophilic hot solvent,
In the image forming method in which the mobile dye is transferred to the dye fixing layer, the transfer of the mobile dye may start simultaneously with the release of the dye, or may occur after the release of the dye is completed. Therefore, heating for transfer may be performed after or simultaneously with heat development. Heating for dye migration improves the storage stability of photosensitive materials,
From the viewpoint of workability, etc., the temperature is between 60℃ and 250℃, so
In the present invention, it is possible to appropriately select a solvent that can function as a hydrophilic thermal solvent within this temperature range. It goes without saying that hydrophilic thermal solvents must be able to quickly assist the movement of dyes upon heating, but if we also consider the heat resistance of photosensitive materials, the requirements for hydrophilic thermal solvents are The melting point is 40
The temperature is preferably from 40° to 200°C, more preferably from 40° to 150°C. The hydrophilic thermal solvent is a compound that is solid at room temperature but becomes liquid when heated, and has an (inorganic/organic) value > 1 and a water solubility of 1 or more at room temperature. is defined as
Inorganicity and organicity are concepts for predicting the properties of compounds, and the details thereof 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, from the viewpoint of molecular size, it is considered preferable that molecules that can move by themselves without inhibiting the movement exist around 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. The hydrophilic thermal solvent is sufficient as long as it can substantially assist the movement of the hydrophilic dye generated by heat development to the dye fixing layer, so it can not only be included in the dye fixing layer, but also in the photosensitive layer, etc. A hydrophilic thermal solvent can be contained in the photosensitive material, in both the dye fixing layer and the photosensitive layer, or in the photosensitive material or in an independent dye fixing material having a dye fixing layer. It is also possible to provide independent layers. From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, it is preferable that the hydrophilic thermal solvent is contained in the dye fixing layer and/or the layer adjacent thereto. 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,
Examples include imides, alcohols, oximes, and other heterocycles. Specific examples of the hydrophilic heat solvent and particularly preferred examples thereof are disclosed in Japanese Patent Application No. 149 of 1982-42092.
Mention may be made of the compounds described on pages 1 to 158. These hydrophilic heat solvents can be used alone or in combination of two or more. The hydrophilic thermal solvent is used in an amount of 10 to 300% by weight, preferably 20 to 200% by weight, particularly preferably 30% by weight of the total coating thickness excluding the hydrophilic thermal solvent in the photosensitive material or dye fixing material. It can be used in a range of 150% by weight. The dye fixing material of the present invention is used in combination with a photosensitive material as described above, and there are two types of combinations: one is a peelable type and the other is a 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 latter case, which does not require peeling, a white reflective layer must be interposed 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 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 yellow, magenta, and cyan, the photosensitive material used in the present invention consists of at least three layers of silver halide, each sensitive to a different spectral region. It is necessary to have an emulsion layer. Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, 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, etc. In addition, here, the infrared light-sensitive emulsion layer is 700 nm.
The above refers to an emulsion layer that is particularly sensitive to light of 740 nm or more. The light-sensitive material used in the present invention may include emulsion layers sensitive to the same spectral region, if necessary.
The emulsion may be divided into two or more layers depending on the sensitivity of the emulsion. Each of the above emulsion layers and/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 each contain one of a dye-donating substance and a dye-donating 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 dye-providing substances having the same hue may be used in combination. 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 can 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 TiO ₂ 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, silver iodide, or silver chlorobromide, silver chloroiodide,
Either silver iodobromide or silver chloroiodobromide may be used. 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 Application Laid-open No. 154232/1983, 108533/1983, 59/1982).
No. 48755, No. 59-52237, US Pat. No. 4,433,048 and European Patent No. 100,984). In addition, tabular grains with a grain thickness of 0.5 μm or less, a diameter of at least 0.6 μm, and an average aspect ratio of 5 or more (U.S. Pat.
4414310, 4435499, OLS No. 3241646A1, etc.), or monodispersed emulsions with a nearly uniform grain size distribution (JP-A-57-178235).
No. 58-100846, No. 58-14829, International Publication
83/02338A1, European Patent No. 64412A3 and
83377A1 etc.) can 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, X
Silver chloroiodide, silver iodobromide, which has a line pattern,
Preference is given to using silver chloroiodobromide. For example, silver bromide grains are prepared by adding a silver nitrate solution to a potassium bromide solution, and by further adding potassium iodide, silver iodobromide having the above characteristics can be obtained. In the process of particle formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, etc. may be present. Further, for the purpose of improving high illuminance failure and low illuminance failure, water-soluble iridium salts such as iridium chloride (2) 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. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-open No. 1986-1999).
126526, 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, the temperature of the heat-developable photosensitive material is 80°C or higher, preferably 100°C.
When heated to a temperature of .degree. C. or higher, the organometallic oxidizing agent is also considered to participate 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 with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments,
Holopolar cyanine dye, heminanine dye,
Included are 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. That is, pyrroline 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 of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric 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., a dye-donating compound, is used. Contains sexual substances. This type of compound can be represented by the following general formula [LI]. (Dye-X) _o -Y [LI] Dye represents a dye group or a dye precursor group,
represents a simple bond or linking group, and Y corresponds to or inversely corresponds to a photosensitive silver salt having a latent image in the form of an image ( _Dye -X). , or a group that releases Dye and has the property of causing a difference in diffusivity between the released Dye and (Dye-X) _o -Y, n represents 1 or 2, and n represents At 2, 2
The two Dye-Xs may be the same or different. Specific examples of the dye-donating substance represented by the general formula [LI] include dye developers in which a hydroquinone developer and a dye component are linked, as disclosed in U.S. Pat. No. 3,134,764, U.S. Pat. , No. 3544545, No. 3482972, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction was published in JP-A-51
JP-A-49-111628 and other publications disclose substances that release diffusible dyes through an intramolecular rewinding reaction of isoxazolone rings. In both of these methods, the diffusible dye is released or diffused in areas where no development has occurred.
No dye is released or diffused where development occurs. Furthermore, in these methods, development and dye release or diffusion occur in parallel, so it is very difficult to obtain an image with a high S/N ratio. 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 method of releasing a diffusible dye has also been devised, and specific examples of dye-donating substances used therein are disclosed in JP-A No. 53-110827, JP-A No. 54-130927, JP-A No. 56-164342, and JP-A No. 53- Described in No. 35533. On the other hand, as a substance that releases a diffusible dye in the area where development occurs, 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 developer is disclosed in British Patent No. 1330524. No. 48-39165, U.S. Pat. No. 3,443,940, etc., substances that generate diffusible dyes through the reaction of a coupler having a diffusion-resistant group as a leaving group and an oxidized form of a developer are disclosed in the United States. It is described in Patent No. 3227550, etc. In addition, in systems using these color developers, image contamination due to oxidized dispersion of the developer is a serious problem.In order to improve this problem, we developed a method that does not require a developer and has its own reducing properties. Dye-releasing compounds have also been devised. A method using these dye-providing compounds is described in European Patent No. 76492, 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. U.S. Patent No. 3928312 etc. U.S. Patent No. 4053312 etc. U.S. Patent No. 4055428 etc. U.S. Patent No. 4,336,322 Japanese Patent Publication No. 59-65839 Japanese Patent Publication No. 59-69839 Japanese Patent Publication No. 53-3819 Japanese Patent Publication No. 51-104343 Japanese Patent Publication No. 51-104343 Japanese Patent Publication No. 51-104343 Research Disclosure Magazine No. 17465 U.S. Patent No. 3725062 U.S. Patent No. 3728113 U.S. Patent No. 3443939 JP-A-58-116537 Any of the various dye-donating substances described above can be used in the present invention. Specific examples of imaging materials for use in the present invention are described in the patent documents cited above. In the present invention, the dye-donating substance is
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 2322027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used. For example, phthanolic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate) ,
High boiling point organic solvents such as benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) , or boiling point of about 30℃
After dissolving in an organic solvent at 160°C, such as a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, or cyclohexanone, it is hydrophilized. Dispersed into sex colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. Furthermore, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid.
As such surfactants, those listed as surfactants elsewhere in this specification can be used. The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g or less per 1 g of the dye-providing substance used. 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 reducing agents used in the present invention include inorganic reducing agents such as sodium sulfite and sodium hydrogen sulfite, benzenesulfinic acids, hydroxylamines, hydrazines, hydrazides, borane amine complexes, hydroquinones, aminophenols, In addition to catechols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc., TH James, “The
theory of the photographic process”4Hi,
Reducing agents described in Ed., pages 291-334 can also be used. Also, JP-A-51-138736, JP-A No. 57-40245,
Reducing agent precursors such as those described in US Pat. No. 4,330,617 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 the reducing agent added is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol, per 1 mol of silver. An image formation accelerator can be used in the dye-fixing material and photosensitive material of the present invention. Image formation promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents;
It has functions such as promoting reactions such as the production of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and promotion of transfer of dyes from the light-sensitive material layer to the dye-fixing layer. Based on their functions, they are classified into bases or base precursors, nucleophilic compounds, oils, heat solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups generally have multiple functions, and usually have several 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 may have multiple functions. many. (a) Base Examples of preferred bases include alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates as inorganic bases. ; ammonium hydroxide; hydroxide of quaternary alkylammonium; hydroxide of other metals, etc.; examples of organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines); ); aromatic amines (N-alkyl-substituted aromatic amines, N-hydroxylalkyl-substituted aromatic amines and bis[p-(dialkylamine)
phenyl]methanes), heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those having a pKa of 8 or more are particularly preferred. (b) Base precursor Base precursors include salts of organic acids and bases that decompose by decarboxylation upon heating, and compounds that decompose and release amines through reactions such as intramolecular nucleophilic substitution reactions, Lothsen rearrangement, and Beckman rearrangement. Those that cause some kind of reaction upon heating and release a base are preferably used. Preferred base precursors include trichloroacetic acid salts described in British Patent No. 998949, α-sulfonylacetic acid salts described in U.S. Patent No. 4060420, propiolacetic acid salts described in Japanese Patent Application No. 58-55700, US Patent No.
2-carboxycarboxamide derivatives described in No. 4088496, salts with thermally decomposable acids using an alkali metal or alkaline earth metal in addition to an organic base as the base component (Patent Application No. 1988-69597), utilizing Lotusene rearrangement Hydroxam carbamates described in Japanese Patent Application No. 1986-43860, which produce nitriles by heating
Examples include aldoxime carbamates described in No. 58-31614. Others, UK Patent No. 998945
No., U.S. Patent No. 3220846, Japanese Patent Application Publication No. 50-22625,
Base precursors such as those described in British Patent No. 2079480 are also useful. (c) Nucleophilic compounds Water and water-releasing compounds, amines, amidines, guanidines, hydroxylamines, hydrazines, hydrazides, oximes, hydroxamic acids, sulfonamides, active methylene compounds, alcohols, thiols It is also possible to use salts or precursors of the above compounds. (d) Oil A high-boiling organic solvent (so-called plasticizer) used as a solvent when emulsifying and dispersing hydrophobic compounds can be used. (e) Thermal solvents Solid at ambient temperature, melts near the development temperature and acts as a solvent, such as ureas, urethanes, amides, pyrudins, sulfonamides,
Compounds such as sulfones, sulfoxides, esters, ketones, and ethers that are solid at 40°C or lower can be used. (f) Surfactant Pyridinium salts described in JP-A-59-74547;
Ammonium salts, phosphonium salts, JP-A-59
Examples include polyalkylene oxides described in No.-57231. (g) Compounds that interact with silver or silver ions Imides, nitrogen-containing heterocycles described in Japanese Patent Application No. 58-51657, thiols, thioureas, and thioethers described in Japanese Patent Application No. 57-222247. can be mentioned. 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. The image formation accelerator can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained when several types are used 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 Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include oxime esters described in Japanese Patent Application No. 58-216928 and Japanese Patent Application No. 59-48305, compounds that release acid by lotusene rearrangement described in Japanese Patent Application No. 59-85834, and the like. Examples of electrophilic compounds that undergo a substitution reaction with a base when heated 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 this case, the base precursor/acid precursor ratio (molar ratio) is preferably 1/20 to 20/1, more preferably 1/5 to 5/1. 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, U.S. Patent No.
Isothiuroniums represented by 2-hydroxyethylisothiuronium trichloroacetate described in No. 3301678, 1,8-(3,6-dioxaoctane)bis(inchuronium trichloroacetate) described in U.S. Patent No. 3669670 Bis(inchuronium) such as, West German Patent Publication No.
Thiol compounds described in 2162714, U.S. Patent No.
Thiazolium compounds such as 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate described in No. 4012260, U.S. Pat.
Bis(2-amino-2-thiazolium)methylenebis(sulfonylacetate) described in No. 4060420,
Compounds having 2-carboxamide as an acidic moiety, such as 2-amino-2-thiazolium phenylsulfonylacetate, are preferably used. Furthermore, azole thioether and blocked azolinthion compounds described in Belgian Patent No. 768071, 4-aryl-1-carbamyl-2-tetrazoline-5-thione compounds described in U.S. Patent No. 3893859, and other U.S. Patent No. 3839041,
Compounds described in No. 3844788 and No. 3877940 are also preferably used. In the present invention, an image toning agent may be contained if necessary. Effective toning agents are 1, 2,
Compounds such as 4-triazole, 1H-tetrazole, thiouracil and 1,3,4-thiadiazole. Examples of preferred toning include 5-
Amino-1,3,4-thiadiazole-2-thiol, 3-mercapto-1,2,4-triazole, bis(dimethylcarbamyl) disulfide,
Examples include 6-methylthiouracil and 1-phenyl-2-tetraazoline-5-thione. 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, and cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric materials include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes. In the present invention, the photographic light-sensitive material and the dye fixing material may contain an inorganic or organic hardening agent in the photographic emulsion layer and other binder layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-
dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-
2-propanol, 1,2-bis(vinylsulfonylacetamido)ethane, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-
triazine, etc.), mucohalogen acids, (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or 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, as well as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and related materials. Contains film or resin materials. Paper supports laminated with polymers such as polyethylene can also be used. Polyesters described in US Pat. No. 3,634,089 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. It may be coated through 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 may 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 transfer, a hydrophilic thermal solvent, an antifade agent to prevent color mixing of the dyes, a UV absorber, a dimensional stability agent, etc. A dispersed vinyl compound, a fluorescent whitening agent, etc. may be included to increase the brightness. The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, cellulose derivatives,
Natural substances such as polysaccharides such as starch and gum arabic, synthetic polymeric substances such as water-soluble polyvinyl compounds such as dextrin, bullulan, polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers are used. Among these, gelatin and polyvinyl alcohol are particularly effective. [Examples] Example 1 A method for making a benzotriazole silver emulsion will be described. 28g gelatin and 13.2g benzotriazole in water
Dissolve in 300ml. This solution is kept at 40°C and stirred. A solution of 17 g of silver nitrate dissolved in 100 ml of water is added to this solution over 2 minutes. Adjust the pH of this benzotriazole silver emulsion,
Allow to settle and remove excess salt. Then the PH
6.30, yielding 400 g of benzotriazole silver emulsion. This article describes how to make silver halide emulsions for the 5th and 1st layers. A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water, 75
600 ml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (0.59 mol of silver nitrate dissolved in 600 ml of water) were simultaneously added at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (50 mol % bromine) with an average grain size of 0.40 μm was prepared. After washing with water and desalting, 5 mg of sodium thiosulfate and 4-
Chemical sensitization was carried out at 60° C. by adding 20 mg of hydroxy-6-methyl-1,3,3a,7-tetrazaindene. The yield of emulsion was 600 g. Next, I will explain how to make silver halide milk for the third layer. A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water, 75
600 ml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (0.59 mol of silver nitrate dissolved in 600 ml of water) were simultaneously added at equal flow rates 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, 5 mg of sodium thiosulfate and 4-
Chemical sensitization was carried out at 60° C. by adding 20 mg of hydroxy-6-methyl-1,3,3a,7-tetrazaindene. The yield of emulsion was 600g. Next, how to make a gelatin dispersion of a dye-donating substance will be described. Weigh out 5 g of yellow dye-donating substance (A), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 10 g of triisononyl phosphate, add 30 ml of ethyl acetate, and add about 60 g of ethyl acetate. Heat and dissolve at ℃ to make a homogeneous solution.
This solution was stirred and mixed with 100 g of a 10% solution of lime-treated gelatin, and then mixed with a homogenizer for 10 minutes.
Disperses at 10000rpm. This dispersion is called a yellow dye-providing substance dispersion. Using magenta dye-donating substance (B) and 7.5g of tricresyl phosphate as a high boiling point solvent
A dispersion of a magenta dye-providing substance was prepared in the same manner as described above, except for using the same method as above. A cyan dye-donating substance (C) was used 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.

【table】

[Table] Dye-donating substances (A) (B) (C) (D-1) (D-2) (D-3) Next, we will discuss how to make a gelatin dispersion as an anti-fading agent. 5 g of the following anti-fade agent (a) was added to 100 g of a 1% gelatin aqueous solution and ground for 10 minutes in a mill with 100 g of glass beads having an average particle size of about 0.6 mm. Gelatin dispersion (a) was obtained by over-separating the glass beads. A gelatin dispersion (b) was obtained using the following anti-fading agent (b) 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 (a) Anti-fade agent (b) Next, how to make the dye fixing material (G) will be described. First, the following gelatin hardener H-1 (0.75g),
Add H-2 (0.25g) and 160ml of distilled water to make 10%
100 g of 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 (10 g) and 200 ml of distilled water were added, followed by 100 g of 10% lime-treated gelatin and mixed uniformly. Apply this mixture onto the above coating.
It was applied uniformly to form a wet film of 85 μm.
This sample was dried and used as a dye fixing material (G) containing the following mordant P-1. Gelatin hardener H-1 CH ₂ =CHSO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂
CH=CH ₂ Gelatin hardener H-2 CH ₂ = CHSO ₂ CH ₂ CONH(CH ₂ ) ₃ NHCOCH ₂ SO ₂
CH=CH ₂ mordant P-1 Next, how to make the dye fixing materials (H) and (I) will be described. First, the gelatin hardener H-1 (0.75 g),
Add H-2 (0.25g) and 160ml of distilled water to make 10%
100 g of 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, the above mordant P-1 (10 g), 100 g of the above anti-fade gelatin dispersion (a) and 100 ml of distilled water were added, and further 100 g of 10% lime-treated gelatin was added, and the mixture was mixed uniformly. on the coating
It was applied uniformly to form a wet film of 85 μm.
This sample was dried and used as a dye fixing material (H). Further, it was used as a dye fixing material (2) in exactly the same manner except that gelatin dispersion (b), which is an anti-fading agent, was used. A tungsten light bulb is used in the color photosensitive material with the above multilayer structure, and G, whose concentration continuously changes,
R, IR three-color separation filter (G is 500-600nm,
R is 600-700nm bandpass filter, IR is
The sample was exposed to light at 500 lux for 1 second through a filter (constructed using a filter that transmits at least 700 nm). Then 30 minutes on a heat block heated to 140℃.
Heat evenly for seconds. Next, 20 ml of water was supplied to the membrane side of the dye-fixing material ^per square meter, and the heat-treated photosensitive coatings were stacked on the fixing material so that the membrane 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 photosensitive material, and yellow, magenta, and cyan color images are formed on the fixing material corresponding to the G, R, and IR three-color separation filters, respectively. was gotten. The dye density of each color was measured using a Macbeth reflection densitometer (RD519). Next, a transparent film with an ultraviolet absorbing layer is placed on the film surface of the dye fixing material having these negative images, and xenon light (100,000 lux) is applied onto the color image using an Atlas C.I65 Weather-Ometer. It was irradiated for 3 days. 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 each reflection density of 1.0.

【table】

[Table] Dye concentration after irradiation with xenon light for 3 days
Dye residual rate:

Claims (1)

[Scope of Claims] 1. A dye fixing layer for fixing a mobile dye imagewise distributed on a support, the dye fixing layer containing a mordant containing a vinyl monomer unit having a tertiary imidazole group, A dye-fixing material characterized in that the dye-fixing layer or a layer adjacent thereto contains at least one compound selected from compounds represented by the following general formulas () to (). General formula () [In the formula, R ¹ represents a hydrogen atom, an alkyl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a trialkylsilyl group, and A completes a 5- or 6-membered ring together with [Formula] Represents the nonmetallic atoms necessary for R ² , R ³ , and 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, and an alkylthio group. ,
It represents 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. Furthermore, the general formula ()
The compounds represented by include A-containing 5- or 6-membered ring bisspiro compounds. ] General formula () [In the formula, R ¹ is the same as defined in the general formula (), and R ⁵ is an alkyl group, an alkoxy group,
It represents an alkoxycarbonyl group, an arylthio group, an arylsulfinyl group, an arylsulfonyl group, an aralkyl group, a halogen atom, an aryl group, or an acyl group, and R ⁶ is a hydrogen atom, an alkyl group, or an alkoxy group (however, R ¹ O- and R ⁶ are not the same substituent), aralkyloxy group (however, R ¹ O
- and R ⁶ are not the same substituent), an alkylthio group, an aralkylthio group, an acylamino group, an acyl group, an alkylamino group, an arylamino group, or a heterocyclic amino group. R ⁷ is a hydrogen atom,
It 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 () [In the formula, R ⁸ represents a hydrogen atom, a linear or branched alkyl group, or an alkenyl group, R ⁹ represents a linear or molecular chain alkyl group, or an alkenyl group, and R ⁸ and R ⁹ may be the same or different. Good too. Moreover, R ¹ represents the same meaning as R ¹ in the general formula (). Further, the above substituents R ⁸ and R ⁹ may have an -NHCO- bond within the substituent. General formula () [In the formula, R ¹⁰ is an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, or
Represents a group represented by R ¹⁸ CO, R ¹⁹ SO ₂ or R ²⁰ NHCO. Here, R ¹⁸ , R ¹⁹ and R ²⁰ each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ¹¹ and R ¹² are each a hydrogen atom,
Represents a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, or an alkenoxy group,
R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. ]