JPH0535851B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide photographic material,
In particular, the present invention relates to a silver halide photographic material that uses epoxies that are poorly soluble in water to improve the storage stability of color images. (Prior art) When a silver halide photosensitive material is exposed to light and then subjected to color development processing, an aromatic primary amine developing agent oxidized by silver halide and a dye-forming coupler react to form a color image. Ru. In this method, a subtractive color reproduction method is often used, and in order to reproduce blue, green, and reddish, yellow, magenta, and cyan color images, which are complementary colors, are formed, respectively. Conventionally, phenols or naphthols are often used as couplers for forming cyan images. However, several problems remain in the storage stability of color images obtained from conventional phenols and naphthols. For example, U.S. Pat.
No. 2367531, No. 2369929, No. 2423730, and No. 3772002 disclose color images obtained from the described 2-acylaminophenol cyan couplers, but these generally have poor heat fastness. , and U.S. Pat. No. 2,772,162 and
The color images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 2895826 generally have a drawback of poor light fastness. Additionally, the color images obtained with the 2-ureidophenolic cyan couplers described in U.S. Pat. No. 3,446,622 and U.S. Pat. It was unsatisfactory in terms of heat (particularly wet heat) fastness. (Problems to be Solved by the Invention) In order to improve the balance of these fastnesses, it was proposed in JP-A-59-100440 to use a mixture of a phenolic cyan coupler and a 2,5-diacylaminophenolic cyan coupler. However, by mixing the two, the heat fastness is not significantly improved to the superior level of the latter, but becomes dependent on the inferior level of the former, and the effect does not satisfy the purpose. I couldn't say it was possible. On the other hand, using an epoxy coupler solvent, 2-
U.S. patents show that dissolving acylaminophenolic cyan couplers improves fastness.
Although it is described in No. 4239851 and No. 4540657, this method cannot be said to have sufficient robustness. The latter also describes that yellowing, or stain, generated by heat and light can be reduced by adding epoxy to the red-sensitive layer, but this paper uses a 2-acylaminophenol cyan coupler. Although there was an improvement in heat resistance, it was still not sufficient. Also, JP-A-54-104339
describes a silver halide photographic light-sensitive material having a hydrophilic colloid layer in which a 2-acylaminophenol cyan coupler is dispersed in the coexistence of an epoxy, but it has high light fastness but poor heat fastness. An object of the present invention is to improve these drawbacks and provide a silver halide photographic material with excellent fastness to light and heat. (Means for Solving the Problems) An object of the present invention is to provide a silver halide photograph containing at least one kind of a cyan dye-forming coupler represented by the general formula [] and a cyan dye-forming coupler represented by the general formula []. This is achieved by incorporating into the photosensitive material an epoxy that is hardly soluble in water and is represented by the general formula []. General formula [] General formula [] General formula [] (In the formula, R ₁ is an alkyl group, and R ₄ has 1 to 1 carbon atoms.
3 represents an alkyl group or phenyl group, R ₅ represents an alkyl group, R ₂ represents an aliphatic group, R ₃ and R ₆ each represent a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group. R ₇ , R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, or a carbamoyl group (provided that R ₇ , R ₈ , R ₉ and R ₁₀ (Not all of them are hydrogen atoms at the same time, and the total number of carbon atoms is 8 to 60), and Z ₁ and Z ₂ represent a hydrogen atom or a group or atom that can be separated upon coupling with a developing agent. ) However, in the present invention, R ₂ and R ₃ in the general formula [], R ₅ and R ₆ in the general formula [], and R ₇ and R ₉ in the general formula [] form a 5- to 7-membered ring, respectively. In the general formula [], R ₁ , R ₂ ,
Either R ₃ or Z ₁ , or one group of R ₄ , R ₅ , R ₆ or Z ₂ in the general formula [] independently or jointly forms a dimer or more. A multimeric coupler may be formed, and these cases are also included. Below, R ₁ in the general formulas [], [], []
~R ₁₀ and Z ₁ and Z ₂ will be explained in detail. In general formula [] and general formula [], R ₁
and R ₅ each preferably have 1 to 36 carbon atoms
represents an alkyl group, and these groups further include an aryl group, a heterocyclic group, an alkoxy group (e.g., methoxy group, 2-methoxyethoxy group, etc.), an aryloxy group (e.g., 2,4-di-tert-amylphenoxy group, etc.). group, 2-chlorophenoxy group, 4-
cyanophenoxy group, etc.), alkenyloxy group (e.g., 2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.),
Ester groups (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide groups (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.) groups), aliphatic or aromatic sulfonyl groups (e.g., methanesulfonyl groups, phenylsulfonyl groups, etc.),
It may be substituted with a group selected from aliphatic or aromatic thio groups (eg, ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, carboxy group, nitro group, sulfo group, halogen group, etc. The alkyl group having 1 to 3 carbon atoms or phenyl group of R ₄ may further include an aryl group, an alkyl group, a heterocyclic group, an alkoxy group (e.g., a methoxy group, a 2-
methoxyethoxy group, etc.), aryloxy group (e.g., 2,4-di-tert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (e.g., 2
-propenyloxy group, etc.), acyl group (e.g.
acetyl group, benzoyl group, etc.), ester group (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g.
dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl group, (e.g., phenylsulfonyl group), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxyl group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. You may do so. As used herein, the term "aliphatic group" refers to a linear, branched, or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups. Representative examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, icosenyl group, iso-
propyl group, tert-butyl group, tert-octyl group,
Examples include tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2-hexadecenyl group, and propargyl group. In the general formula [], R ₂ preferably represents an aliphatic group having 1 to 20 carbon atoms, and may be substituted with a permissible substituent for R ₁ . In general formula [] and general formula [], R ₃
and R ₆ are each a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), preferably an aliphatic group having 1 to 20 carbon atoms, and preferably an aliphatic oxy group having 1 to 20 carbon atoms. , or an acylamino group having 1 to 20 carbon atoms (e.g., acetamido group, benzamide group, tetradecaneamide group, etc.), in which these aliphatic groups, aliphatic oxy groups, and acylamino groups are substituted with permissible substituents for R ₁ May be replaced. In the general formula [], R ₇ , R ₈ , R ₉ and R ₁₀
each represents a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group (e.g., dodecyloxycarbonyl group, allyloxycarbonyl group, etc.), or a carbamoyl group (e.g., tetradecylcarbamoyl group, phenyl-methylcarbamoyl group, etc.). , R ₇ , R ₈ , R ₉ and R ₁₀ are not all hydrogen atoms at the same time, and the total number of carbon atoms is 8 to 60. These groups may have a substituent. Z ₁ in the general formula [] and Z ₂ in the general formula [] represent a hydrogen atom or a coupling-off group, such as a halogen atom (e.g.
fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy groups (e.g., 4
-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetradecanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., amide groups (e.g., dichloroacetylamino group, heptafluoroptyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.),
Alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy groups, benzyloxycarbonyloxy groups, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy groups, etc.), aliphatic or aromatic thio groups (e.g.,
Examples include ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide groups (eg, succinimide group, hydantoinyl group, etc.), and aromatic azo groups (eg, phenylazo group, etc.). These leaving groups may include photographically useful groups. In the general formula [], R ₂ and R ₃ may jointly form a 5- to 7-membered ring. In the general formula [], R ₅ and R ₆ may jointly form a 5- to 7-membered ring. In the general formula [], R ₇ and R ₉ may form a 5- to 7-membered ring. Any of R ₁ , R ₂ , R ₃ or Z ₁ in the general formula [], or R ₄ , R ₅ , R ₆ in the general formula []
Alternatively, any one group of Z ₂ may independently or jointly form a dimer or more multimeric coupler. In the case of dimers, these groups can be used as simple bonds or as divalent linking groups (e.g., alkylene groups, arylene groups, ether groups,
divalent groups such as ester groups, amide groups, and divalent groups combining these groups), and when forming oligomers or polymers, these groups are either in the polymer backbone or in the form of dimers. Preferably, it is attached to the polymer backbone through a divalent group such as. When forming a polymer, even if it is a homopolymer of the coupler derivative, other non-color-forming ethylene-like monomers (e.g., acrylic acid, methacrylic acid, methyl acrylate n-butylacrylamide, β-hydroxy methacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone, etc.). In general formula [], R ₁ and general formula []
R ₅ is a substituted or unsubstituted alkyl group, and as a substituent for the alkyl group, an optionally substituted phenoxy group or a halogen atom is particularly preferable (as a substituent for the phenoxy group, an alkyl group, an alkoxy group, a halogen atom is particularly preferable). Atom, sulfonamide group, and sulfamide group are more preferable.) In the general formula [], R ₄ is preferably a substituted alkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted phenyl group; The group is particularly preferably a halogen atom, and the phenyl group is particularly preferably an unsubstituted phenyl group or a phenyl group substituted with at least one halogen atom or sulfonamide group. In the general formula [], preferred R ₂ is an optionally substituted alkyl group having 1 to 20 carbon atoms.
The substituent for R ₂ is preferably an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imido group, a ureido group, or an alkyl or arylsulfonyl group. In the general formula [], R ₃ is preferably a hydrogen atom, a halogen atom (particularly preferred are a fluorine atom and a chlorine atom), or an acylamino group, and particularly preferably a halogen atom. In the general formula [], R ₆ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group,
Particularly preferred is a hydrogen atom. In the general formula [], it is preferable that R ₂ and R ₃ are an alkyl group and an acylamino group and form a 5- to 6-membered ring. In the general formula [], it is preferable that R ₅ and R ₆ form a 5- to 6-membered nitrogen-containing heterocycle. In the general formulas [] and [], Z ₁ and Z ₂ are preferably chlorine atoms. In the general formula [], at least one of R ₇ , R ₈ , R ₉ , R ₁₀ is preferably hydrogen, and 2
It is further preferred that each is hydrogen. In the general formula [], at least one of R ₇ , R ₈ , R ₉ , and R ₁₀ is preferably an ester group, an amide group, or an alkyl group substituted with an aryl or alkyl ether group. Specific examples of compounds represented by general formula [], general formula [] and general formula [] are shown below,
The present invention is not limited to these. (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (−12) (-13) (-14) (-15) (-16) (-17) (-1) (-2) (-3) (-4) (-5) (-6) (-7) (-8) (-9) (-10) (−11) (−12) (-13) (-14) (-15) (-16) (-17) (-18) (-19) The epoxies represented by the general formula [] are preferably added in the same layer (red-sensitive layer) as the cyan dye-forming couplers (hereinafter abbreviated as cyan couplers) represented by the general formula [] and the general formula []. It can also be added to other adjacent layers (for example, an intermediate layer, a green-sensitive layer, etc.). The amount of the epoxy compound represented by the general formula [] to be added is from 0.1 to 20, preferably from 0.2 to 2, relative to the weight ratio of the cyan coupler represented by the general formula [] and the general formula []. The cyan couplers represented by the general formula [] and the general formula [] can be synthesized by known methods. For example, the cyan coupler represented by the general formula [] is synthesized by the method described in US Pat. No. 2,423,730 and US Pat. No. 3,772,002. The cyan coupler represented by the general formula [] is disclosed in U.S. Patent Nos. 2895826 and 4333999.
No. 4327173, etc. Epoxies represented by the general formula [] can be synthesized by oxidizing a compound having a corresponding double bond with a peracid. An example is U.S. Patent No.
It is described in No. 4239851 and No. 4540657. The magenta couplers that can be used in the present invention include, but are not limited to, the following couplers. (M-1) (M-2) (M-3) (M-4) (M-5) (M-6) (M-7) (M-8) (M-9) (M-10) (M-11) (M-12) (M-13) (M-14) (M-15) (M-16) (M-17) (M-18) (M-19) (M-20) (M-21) (M-22) (M-23) (M-24) (M-25) (M-26) (M-27) Any silver halide, silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride, may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention to produce color prints. Preferred silver halides for direct viewing materials include silver chloroiodobromide containing 3 mol% or less of silver iodide;
Silver iodochloride, silver iodobromide, or silver chlorobromide.
Preferred for photographic materials is silver iodobromide containing from about 2 mole percent to about 25 mole percent silver iodide. The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. The grain size of silver halide may be fine grains of about 0.1 micron or less, or large grains with a projected area diameter of about 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. good. Silver halide photographic emulsions that can be used in the present invention are:
It can be produced by a known method, for example, Research Disclosure (RD), No. 17643 (December 1978), 22
～Page 23, “1. Emulsion preparation
and types)” and same, No. 18716 (November 1979),
The method described on page 648 can be followed. As the silver halide photographic emulsion used in the present invention, two or more types of separately formed silver halide emulsions may be mixed and used. Two or more types of silver halide emulsions formed separately may be mixed and used. The silver halide emulsion consisting of the regular grains described above can be obtained by controlling pAg and PH during grain formation. For more information, see Photographic Science and Engineering Vol.
Volume, pp. 159-165 (1962); Journal of Photographic Science
Photographic Science), Vol. 12, pp. 242-251 (1964), U.S. Patent No. 3655394 and British Patent No.
Described in No. 1413748. Furthermore, as a monodisperse emulsion, the average particle diameter is approximately
Silver halide grains larger than 0.1 micron, of which at least about 95% by weight are ±40% of the average grain diameter
A typical example is an emulsion like the one in the average particle diameter is about 0.25 to 2 microns, and at least about 95
Emulsions in which at least about 95%, by weight or number, of silver halide grains are within ±20% of the average grain diameter can be used in the present invention. Methods for making such emulsions are described in US Pat. No. 3,574,628, US Pat. No. 3,655,394 and British Patent No. 1,413,748. Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are
Gutoff, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4434226
No. 4414310, No. 4433048, No. 4439520, and British Patent No. 2112157. The use of tabular grains has advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as detailed in U.S. Pat. No. 4,434,226 cited above. ing. The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1027146, US Patent No. 3505068;
It is disclosed in No. 4444877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. Also, mixtures of particles of various crystal forms may be used. The emulsion of the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are described in Research Disclosure No. 17643 and Research Disclosure No. 18716, and the relevant sections are summarized in the table below. Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

[Table] Various color couplers can be used in the present invention, and specific examples thereof are described in the patents listed in Research Disclosure (RD) No. 17643, -C to G. There is. As dye-forming couplers, couplers that give the three primary colors (i.e., yellow, agenta, and cyan) in subtractive color development are important. Specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers include the aforementioned RD17643,
In addition to the couplers described in the patents listed in Sections -C and D, the following can be preferably used in the present invention: A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. Specific examples thereof are described in US Pat. No. 2,407,210, US Pat. No. 2,875,057, and US Pat. No. 3,265,506. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
Oxygen atom separation type yellow couplers described in No. 3933501 and No. 4022620, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4401752, U.S. Pat.
No. 4326024, RD18053 (April 1979), British Patent No.
No. 1425020, West German Published Application No. 2219917, same no.
Typical examples thereof include nitrogen atom separation type yellow couplers described in Japanese Patent Nos. 2261361, 2329587, and 2433812. α-Bivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are the aforementioned
The patent couplers described in RD17643, Sections ~F are useful. The color photographic material according to the present invention is as described above.
RD, No. 17643, pages 28-29 and the same, No. 18716.
651 can be developed by the usual methods described in the left column to right column. The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment. In the washing process, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this step, 2 to 9 countercurrent baths are required.
Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, various buffers (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia) to adjust the membrane pH (e.g., PH 3 to 8). Typical examples include carboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid,
using various additives such as phosphonocarboxylic acids, etc.), bactericidal agents (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole, halogenated phenols, etc.), surfactants, optical brighteners, and hardening agents. Alternatively, two or more of the same or different target compounds may be used in combination. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane PH regulator after treatment. The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. The present invention also provides research and
It can also be applied to black-and-white light-sensitive materials using a mixture of three-color couplers as described in Disclosure 17123 (July 1978). (Effects of the Invention) The present invention combines the cyan coupler represented by the general formula [] with a cyan dye-forming coupler represented by the general formula [], and further uses an epoxy compound represented by the general formula [] in this. Something,
This eliminates the disadvantages of conventional combinations of 2-acylaminophenolic cyan couplers and 2,5-diacylaminophenolic cyan couplers, and provides silver halide photographic materials with excellent fastness to light and heat. Such excellent effects of the present invention can only be achieved by using the above two types of cyan couplers together. There is no difference even if it is added. (Examples) Next, the present invention will be described in more detail based on Examples. Example 1 Samples were prepared by coating a coating solution with the composition shown in the table on a polyethylene (PET) support, and then coating gelatin (1500 mg/m ² ) as a protective layer (Samples A-1 to A-18). ). The above coating liquid was prepared as follows. First, 5.0 g of cyan coupler (-1) and 6.3 g of cyan coupler (-3) shown in the table were mixed into an epoxy compound (-9).
11.3g, heated and dissolved in 20ml of ethyl acetate, 10g of gelatin and sodium dodecylbenzenesulfonate
It was added to 100 g of an aqueous solution containing 1.0 g and emulsified and dispersed.
The entire amount of this emulsion is converted into a photographic emulsion containing 25 g of silver chlorobromide.
A coating solution was prepared by adding 235 g of the solution. 2,4-dichloro-6-hydroxy-S-triazine-sodium salt was used as a hardening agent and coated on the support, and gelatin (1000 mg/m ² ) was further applied as a protective layer.
was coated and dried to obtain sample A-1. Other samples were prepared in a similar manner. These samples were exposed to red light through a continuous wedge and then developed using the following processing steps. Processing steps Temperature Time Developing solution 33°C 3 minutes 30 seconds Bleach-fixing solution 33°C 1 minute 30 seconds Water washing 28-35°C 3 minutes The formulation of the processing solution used is as follows. Developer Benzyl alcohol 15ml Diethylene glycol 8ml Ethylenediaminetetraacetic acid disodium salt 5g Sodium sulfite 2g Hydroxyamine sulfate 3g 4-Amino-N-ethyl-N-(β-methasulfonamidoethyl)-m-toluidine 2/3
Sulfate monohydrate 5g Sulfate monohydrate 5g Add water to adjust pH to 10.20 Bleach-fix solution Ethylenediaminetetraacetic acid disodium salt 2g Ethylenediaminetetraacetic acid ferric salt 40g Sodium sulfite 5g Ammonium thiosulfate 70g Add 1000 ml of water to adjust the pH to 6.80. After the development process, each sample was stored at 100°C for 2 weeks and exposed to light for 8 days in a xenon fading tester (100,000 lux) to perform a discoloration test. Macbeth RD− for each sample after the test at the point where the concentration before the test was 1.0.
Concentration was measured using a Model 514 densitometer. The results are shown in the table.

【table】

[Table] From the results in the table, samples A-1, A-7, and A-11 made of the combinations of the present invention all have extremely high fastness to light and heat compared to comparative samples made of other combinations. It can be seen that the effect of improving the fastness is excellent. That is, the color image obtained from the coupler of the general formula [] has excellent light fastness but poor heat fastness. On the other hand, color images obtained from couplers of the general formula [] have excellent heat fastness but poor light fastness. The hue of the color image obtained with the coupler of the general formula [] has a high absorption of green light, which deteriorates the color reproducibility of color photographic materials.In order to improve these drawbacks, the coupler of the general formula [] If couplers of the general formula [] are mixed and used, the characteristic of the coupler of the general formula [], which inherently has good heat fastness, will not be fully utilized, and the heat fastness of the mixed system will not be as good as expected (for example, A-2 and A-4,
Comparison with A-6). The effect of adding an epoxy compound is that in the combination of the present invention (for example, 52% improvement in comparison of samples A-1 and A-2), coupler of general formula [] alone (for example, in samples A-3 and A-4) 22% improvement in comparison) and is significantly larger than the coupler of general formula [] alone. Example 2 A color photographic material was prepared by coating the first layer (lowest layer) to the seventh layer (top layer) on double-sided polyethylene laminated paper as described in Tables 1 and 2. (Samples BF) The coating liquid for the first layer was prepared as follows. That is, the yellow coupler shown in the table
100 g was dissolved in a mixed solution of 100 ml of dibutyl phthalate (DBP) and 200 ml of ethyl acetate, and this solution was emulsified and dispersed in 800 g of a 10% aqueous gelatin solution containing 80 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate. Next, the entire amount of this emulsified dispersion was mixed with 1450 g (containing 66.7 g of Ag) of a blue-sensitive silver chlorobromide emulsion (Br80%) to prepare a coating solution. Coating solutions for other layers were prepared in the same manner. As a hardening agent for each layer, 2,4-dichloro-6-hydroxy-S-triazine sodium salt was used. The following spectral sensitizers were used for each emulsion. Blue-sensitive emulsion layer: 3,3'-di-(γ-sulfopropyl)-selenacyanine sodium salt (2x per mole of silver halide)
10 ^-4 mol) Green-sensitive emulsion layer; 3,3'-di-(γ-sulfopropyl)-5,5'-diphenyl-9-
Ethyloxacarbocyanine sodium salt (2.5 x 10 ^-4 mol per mol of silver halide) Red-sensitive emulsion layer; 3,3'-di-(γ-sulfopropyl)-9-methyl-thiadicarpocyanine sodium salt ( (2.5×10 ^-4 mol per mol of silver halide) The following dyes were used as anti-irradiation dyes in each emulsion layer. Green sensitive emulsion layer red sensitive emulsion layer In the table, TNP represents trinonyl phosphate, DBP represents dibutyl phthalate, and TCP represents tricresyl phosphate, and the chemical structures of the compounds (*a) to (*g) are as follows. (*a) Magenta coupler (*b) Anti-fading agent (*c) Anti-fading agent (*d) Yellow coupler (*e) Anti-fading agent *f Ultraviolet absorber (1:5:3 mixture) *g Ultraviolet absorber (1:3:3 mixture)

【table】

【table】

[Table] These samples were exposed to red light through a continuous wedge, and then developed in the same manner as in Example 1. After processing, each sample was stored at 100℃ for 2 weeks.
A discoloration test was conducted. After the test, the concentration of each sample was measured using a Macbeth RD-514 densitometer at a location where the concentration before the test was 1.0. The results are shown in the table.

[Table] From the results in Table 1, the samples of the present invention have a remarkable effect of improving the fastness against heat, and samples D and E
It can be seen that even if epoxy compounds are added to other layers, there is a significant effect. In addition, samples B to E were subjected to a xenon irradiation test (100,000 lux) in the same manner as in Example 1, and showed excellent fastness to light. Example 3 The sample of Example 1 except that (-18) or (-19) was used as the epoxy compound in the coating solution and a mixed system of coupler (-1) or (-2) and (-3) was used. Sample A- in the same manner as A-1.
19, A-22 were prepared as shown in the table. Also,
Samples A-20, A-21, A-23, outside the scope of the present invention
A-24 was prepared as shown in the table below. These samples were exposed to red light through a continuous wedge and then developed in the same manner as in Example 1. Then, as in Example 1, these samples were
℃, stored for 2 weeks and irradiated with light for 8 days in a xenon fading tester (100,000 lux), and the concentration before the test was 1.0.
The concentration was measured at the following locations. The results are shown in the table.

[Table] From the results in the table, it can be seen that the samples containing the epoxy compound (-18) or (-19) and the coupler mixture exhibit excellent heat fastness and light fastness of color images.

Claims (1)

[Scope of Claims] 1. At least one cyan dye-forming coupler represented by the following general formula [] and at least one cyan dye-forming coupler represented by the general formula [],
1. A silver halide photographic light-sensitive material characterized by containing an epoxy compound, which is represented by the following general formula [ ], and which is sparingly soluble in water. General formula [] General formula [] General formula [] (In the formula, R ₁ is an alkyl group, and R ₄ has 1 to 1 carbon atoms.
3 represents an alkyl group or phenyl group, R ₅ represents an alkyl group, R ₂ represents an aliphatic group, R ₃ and R ₆ each represent a hydrogen atom, a halogen element, an aliphatic group, an aliphatic oxy group, or an acylamino group. R ₇ , R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, or a carbamoyl group (however, all of R ₇ , R ₈ , R ₉ and R ₁₀ are never hydrogen atoms at the same time, and the total number of carbon atoms is 8 to 60), and Z ₁ and Z ₂ represent a hydrogen atom or a group or atom that can leave when coupled with a developing agent (leaving group). , R ₂ and R ₃ in the general formula [], R ₅ and R ₆ in the general formula [], R ₇ and R ₉ in the general formula []
may each form a 5- to 7-membered ring, and in the general formula [], R ₁ , R ₂ , R ₃ or Z ₁ , and in the general formula [], R ₄ , R ₅ ,
Any one group of R ₆ or Z ₂ may independently or jointly form a dimer or more multimeric coupler. )