JPS62129853A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having good durability against light and heat by incorporating a cyan coloring matter forming coupler shown by a specific formula and an epoxy compd. which is shown by a specific formula and is hard to be soluble in water to the titled material. CONSTITUTION:The titled material comprises a combination of the cyan coupler shown by formula I and the cyan coloring matter forming coupler shown by formula II and the epoxy compd. shown by formula III. In formulas I and II, Z1 and Z2 are each hydrogen atom or a group capable of cleaving by the coupling reaction. The amount of the epoxy compd. to be added shown by formula III is 0.1-20, preferably 0.2-2 on the weight ratio basis of the cyan couplers shown by formulas I and II. Thus, by jointly using 2 kinds of the cyan couplers, the titled material having an excellent durability against heat and light is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to silver halide photographic materials, and in particular to silver halide materials that have improved storage stability of one-color images by using epoxies that are poorly soluble in water. It relates to photographic materials.

(Prior art) After a silver halide photosensitive material is exposed to light, it is subjected to a color development treatment, whereby an aromatic-grade amine developing agent oxidized by silver halide reacts with a dye-forming coupler, etc.
A color image is formed.

In this method, a subtractive color reproduction method is often used, and in order to reproduce blue, green, and reddish, images of yellow, magenta, and cyan, 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. Patent No. 2.367.531, U.S. Pat.
No. 9,929, No. 2,423,730 and No. 3
．． No. 772.002 discloses color images obtained from the described 2-acylaminophenolic cyan couplers, but these generally have poor heat fastness, and US Pat. No. 2,895,82
The color images obtained from the 2,5-diacylaminophenol cyan coupler described in No. 6 generally have a drawback of poor light fastness. Also, U.S. Patent No. 3,446,62
The color images obtained from the 2-ureidophenol cyan couplers described in No. 2 and No. 4,333,999 are as follows:
In general, l-hydroxy-2-natutamido cyanogen coverrs have poor light fastness, and are generally susceptible to light and heat (especially moist heat).
It was unsatisfactory in both terms of robustness.

(Problem to be solved by the invention) In order to improve the balance of these robustness,
-100440 with phenolic cyan coupler and 2.5-
Is it proposed to use a mixture of diacylaminophenolic cyan couplers? By mixing the two, the heat fastness is not significantly improved to the level of the latter, which is superior, but is inferior to the level of the former. The effect could not be said to satisfy the purpose.

U.S. Pat. No. 4,239,851 shows that dissolving an acylaminophenolic cyanide coupler improves fastness.
However, this method cannot be said to have sufficient robustness. The latter also states that by adding an epoxy to the red-sensitive layer, it is possible to reduce stain, which is produced by heat and light. Although there is some improvement in robustness, it was still satisfactory.

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 containing at least one kind of a cyan dye-forming coupler represented by the general formula CI) and a cyan dye-forming coupler represented by the general formula (II). In photographic light-sensitive materials, there are epoxies that are poorly soluble in water, represented by the general formula [III]; (n) OH General formula (m) (wherein R,, R4 and R5 are each an aliphatic group,
represents an aromatic group, a heterocyclic group, an aromatic amino group, or a heterocyclic amino group, R2 represents an aliphatic group, R and R6 each represent a hydrogen atom, a halogen atom, an aliphatic), (, an aliphatic oxyno, (or represents an acylamino group, R7,
R8, R9 and R10 each represent a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, or a carbamoyl group, provided that R7, R8゜R and R10 are all hydrogen atoms at the same time. (the total number of carbon atoms is 8 to 60), Z and Z2 represent hydrogen b; R3, R5 and R6 in general formula (II)
In the general formula [III], R and R or R7 and R9 may each form a 5- to 7-membered ring, and in the general formula CI), any one of R, R2, R3 or z, or the general In formula (IF), any one group of R4, R5, R6 or Z2 may independently or jointly form a dimer or more multimeric coupler. ), R in general formula [I], (II), (m) below
-Rlo and 2. ．． 22 will be explained in detail.

In general formula [I] and general formula (II), R1, R4
and R5 are each preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms (e.g. phenyl group, naphthyl group, etc.), a heterocyclic group (e.g. 3
-pyridyl group, 2-furyl group, etc.) or an aromatic or heterocyclic amino group (e.g., anilino group, naphthylamino group, 2-benzothiazolylamino group, 2-pyridylamino group, etc.), and these groups Roughly, an alkyl group, 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, 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, phenoxy group, etc.) Carbonyl group, acetoxy group, benzoyloxy group, butoxycarbonyl group 1 (,
toluenesulfonyloxino, (etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.) ), imide groups (e.g., succinimito group, hydantoinyl group, etc.), ureido groups (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl groups (e.g., methanesulfonyl group, phenylsulfonyl group, etc.)
, an aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom, etc. .

The term "aliphatic group" as used herein 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 thereof Examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, icosenyl M, is.

Examples include -propyl group, tert-butyl group, tert-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl, +1(,2-hexadecenyl group, propargyl group).

In general formula [I], R2 preferably has 1 to 20 carbon atoms
represents an aliphatic group, which may be substituted with a permissible substituent for R1.

In the general formula [I] and the general formula (I[), R3 and R6 are each a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), preferably an aliphatic group having 1 to 20 carbon atoms, Preferably, an aliphatic oxy group having 1 to 20 carbon atoms or an acylamino group having 1v prime number 1 to 20 (for example, an acetamide group, a penzamide group, a tetradecaneamide group, etc.); may be substituted by substituting 2 allowed for R1.

In the general formula ([1), R7, Ra, R9 and R
IQ is hydrogen x 'r-1, aliphatic group, aliphatic oxycarbonyl group, dodecyloxycarbonyl group, allyloxycarbonyl group, etc.), aromatic oxycarbonyl group (e.g., phenoxycarbonyl group, etc.), or carbamoyl group, respectively. (e.g., tetradecylcarbamoyl group, phenyl-methylcarbamoyl group, etc.),
R7, R8°R and R10 are never all hydrogen atoms at the same time, and the sum of the 15 prime numbers is 8-60. These groups may have substituents.

Zl in general formula [I], Z in general formula (II)
2 represents a hydrogen atom or a coupling-off group, examples of which include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g., ethoxy group, dodecyloxy group, methoxyethylcarbamoyl group). methoxy group, carboxypro and ruoxy group, methylsulfonyl ethoxy group, etc.), aryloxy group (e.g.

4-chlorophenoxy group, 4-methoxyphenoxy group,
4-carboxyphenoxy group, etc.), acyloxy group (
(e.g., acetoxy group, tetrazocallyloxy group, benzoyloxy group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (e.g., dichloroacetylamino group, heptafluorobutyryl group, etc.) amino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), Examples include aliphatic or aromatic thio groups (eg, ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide groups (eg, succinimide group, hydantoinyl group, etc.), aromatic azo groups (eg, phenylazo group, etc.).

These leaving groups may include photographically useful groups.

In general formula [I], R2 and R5 are jointly 5 to 7
It may form a member ring.

In general formula (n), R5 and R6 jointly represent 5 to 7
(May form 1g5.

In general formula (m), R7 and R8 or R7 and R9
Alternatively, it may form a 5- to 7-membered ring.

= Any of R1, R2, R3 or Zl in general formula [I], or R4゜R5, R6 in general formula (II)
Alternatively, any one group of z2 may independently or jointly form a dimer or more multimeric coupler. In the case of a dimer, their ni, (e.g. divalent groups in combination) and when forming oligomers or polymers, those groups are either in the polymer backbone or are attached to the polymer backbone through divalent groups such as those described for dimers. When forming a polymer, even if it is a homopolymer of a coupler derivative, other non-chromogenic ethylene-like monomers (for example, acrylic acid, methacrylic acid, methyl acrylate n-butylacrylamide, β-hydroxy methacrylate,
vinyl acetate acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone, etc.),
A copolymer may be formed with one or more of them.

Preferred R1 in general formula [I] and general formula (II
), R5 is preferably a substituted or unsubstituted alkyl group or aryl group, and the substituent for the alkyl group is particularly preferably a phenoxy group, which may be substituted, or a halogen atom (the substituent for the phenoxy group is an alkyl group). The aryl group is particularly preferably a phenyl group substituted with at least one halogen atom, alkyl group, sulfonamide group or acylamino group.

In the general formula [■], R4 is preferably an n-substituted alkyl group or a substituted or unsubstituted aryl group, and as the 21st substituent of the alkyl group, a halogen atom is particularly preferable, arylno, (represents a phenyl group or a halogen atom, a sulfone Particularly preferred is a phenyl group substituted with at least lff1m by an amide group.

In the general formula (1), R2 is preferably an optionally substituted alkyl group having 20 to 20 carbon atoms.

The substituent for R2 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 [I], R3 is preferably a hydrogen atom, a halogen atom (particularly preferably a fluorine atom or a chlorine atom), or an acylamino group, and particularly preferably a halogen atom.

In the general formula (If), R5 is a hydrogen atom, i & prime number 1~
20 alkyl groups and alkenyl groups are preferred, and hydrogen atoms are particularly preferred.

In general formula [I], R2 and R3 are preferably an alkyl group and an acylamino group, forming a 5- to 6-membered ring.

In general formula (II), it is preferable that R5 and R6 form a 5- to 6-membered nitrogen-containing heterocycle.

In general formulas [I] and (II), it is preferable to have a chlorine atom.

In general formula [III], R7'R8'R9' R
It is preferable that at least one of the 10 is hydrogen, and it is more preferable that at least 2 of the 10 are hydrogen.

In general formula (m), at least one of R7'R8' R9 and R10 is preferably an ester group, an amide group, or an alkyl group substituted with an aryl or alkyl ether group.

General formula (1), general formula (n) and general formula (m) are shown below.
Specific examples of compounds represented by are shown below.

The present invention is not limited to these.

・2゛, - m-/- (I-1) C flood P ShiU (+-7) - ShiU ([-10) (II-11) OR (II-12) Shiki (II-13) (If-14) (1 to 15) (II-16) (II-17) TJ (, +l-7-18) (II-19) (II-1) (I-2) (Ill-3) ( Ill-4) (I[-5) 2H5 2H5 (III-7) (II-8) (, Il[-9) (Ill-11) (I[[-12) (III-13) (In-14 ) (lIh15) (III-16) (III-18) C2115C2H5 Epoxies represented by the general formula [III] are represented by the general formula (
1) and the cyan dye-forming coupler represented by the general formula [■] (hereinafter abbreviated as cyan coupler), it is preferable to add it in the same layer (red sensitive layer), but it is preferable to add it in the same layer (red sensitive layer), but it is preferable to add it in the same layer (red sensitive layer) as the cyan dye forming coupler (hereinafter abbreviated as cyan coupler) represented by the general formula [■]. It can also be added to the sensitive layer, etc.).

The amount of the epoxy compound represented by the general formula (m) to be added is O81 to 20, preferably 0.2 to 2, based on the weight ratio of the cyan coupler represented by the general formula [I] and the general formula (II). used.

Cyan couplers represented by general formula [I] and general formula (II) can be synthesized by known methods. For example, general formula [I
] The cyan coupler represented by
, No. 730, No. 3,772.002, etc. Cyan couplers represented by the general formula (IT) are disclosed in U.S. Pat. Nos. 2,895,826 and 4,
No. 333,999, No. 4,327,173 and the like.

Epoxies represented by general formula (m) can be synthesized by oxidizing a compound having a corresponding double bond with a peracid. Examples are described in U.S. Pat. No. 4,239,851 and U.S. Pat. No. 4,540,657.

The following couplers can be mentioned as magenta couplers that can be used in the present invention, but the invention is not limited thereto.

C+U (M-6) r.

HO building 502 building 0- and H gate + (CH2) 3"ゝ(λ4-
174 -17) () CH2CH2 (M-21) (M-22) (M-23) (M-24) (M-2S) (M-26) (M27) shin3 uti3 Photographs used in the present invention In the photographic IL agent layer of the photosensitive material,
No matter which silver halide, silver halide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride, is used, the preferred silver halide for direct viewing materials such as color prints is 3 mol% or less of iodide. Silver chloroiodobromide containing silver.

Silver iodochloride, silver iodobromide, or silver chlorobromide.

lJ! Preferred for the shadow material 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 the silver halide may be fine grains of about 10 microns 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.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Diskrono+-(
RD), No. 17643 (December 1978), 22
-p. 23, “■, Emulsion production (E+mulsionpre
parity and types)” and the same,
No. 18716 (November 1979), p. 648 can be followed.

In the silver halide photographic emulsion used in the present invention, two or more types of silver halide holes formed separately 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 pA[l and l)H during grain formation. For more details, please refer to 7 Otographic Science and Engineering (PI+otographic).
ic 5science and engineering
g) Volume 6, pages 159-165 (1962); Journal of Photographic Science
al ofPhotographic 5science
) + vol. 12, p. 242-251 (1964), U.S. Patent No. 3.655.394 and British Patent No. 1.413
．． It is described in No. 748.

A typical monodisperse emulsion is an emulsion in which silver halide grains have an average grain diameter of greater than about 0.1 micron, and at least about 95% by weight of the silver halide grains are within ±40% of the average grain diameter. The average grain diameter is between about 0.25 and 2 microns, and at least about 95% by weight or at least about 95% by number of silver halide grains have an average grain diameter of ±20 microns.
% can be used in the present invention. A method for producing such an emulsion is described in US patent fi 3,574.6.
No. 28, No. 3,655.394 and British Patent No. 1
, No. 413,748.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are 1117M, 7
PhotoFlraphicSci
ence and Engineering)+ffi
Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,226, No. 4,414,310, No. 4,433.048, No. 4,439,520 and British Patent No. 2゜yI4 can be easily produced by the method described in No. 112,157. When tabular grains are used, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited U.S. Pat. No. 4,434.226, etc. is described in detail.

These emulsion grains, which may have a uniform crystal structure, may have different halogen compositions inside and outside, or may have a layered structure, are disclosed in British Patent No. 1.027,1
No. 46, U.S. Patent No. 3.505.068, No. 4,44
No. 4,877 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 oxide or lead oxide may be bonded.

In addition, the emulsion of the present invention, which uses a mixture of grains of various crystalline forms, is usually used which has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in Research Disclosure +-No. 17.
643 and No. 18716, and the relevant parts 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.

Additive type @ RDI Flow 43 RD18 Flu 1
61 Chemical sensitizers Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
649￥L Right column 4 Brightening agent 24 pages 5 Anti-fog agent 24-25 pages 64949 Right column Stabilizer 6 Light absorber, 7 25-26 pages 649 Right column - Ilter dye 650 Left column Ultraviolet absorber 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10 Bayingu page 26 Same as above 11 plasticizer, lubricant page 27 650 right column 12 coating aid, Tables 26-2
Page 7 Same as above Surface activator 13 Static prevention Page 27 Same as above Stop agent Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) No. 17643, ■-C to G, the important couplers are couplers that provide the three primary colors (i.e., yellow, agenta, and cyan) in subtractive color development. Specific examples of diffusion-resistant 4-equivalent or 2-equivalent couplers are R
In addition to the couplers described in the patents D17643, ■-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. A specific example is U.S. Pat.
No. 407.210, US Pat. No. 2.875.057, and US Pat. No. 194, No. 3,447.928
No. 3.933.501 and No. 4,022,
620, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,4 OL752, No. 4,326,024
No., RD18053 (April 1979), British Patent No. 1
, No. 425,020, West German Application No. 2,219.91
No. 7, No. 2,261,361, No. 2.329,5
Typical examples include the nitrogen atom separation type yellow couplers described in No. 87 and No. 2,433,812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while couplers that release photographically useful residues upon a-pen coupling are also preferred in the present invention. Can be used.

The DIR coupler that releases the development inhibitor is the aforementioned RD17.
The patent couplers described in No. 643, Sections 1-F are useful.

The color photographic material according to the present invention includes the above-mentioned RD, N
o, 17643, 28-29a and same, No. 187
The color photographic material of the present invention described in the left column to right column of 651 of 16 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 types of tanks are generally flushed with water to save water. A representative example of the stabilization treatment is a multi-stage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing process.In the case of 0 steps, 2 to 9
A tank countercurrent column is 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, 7 ammonia water) to adjust the membrane pH (e.g., pH 3-8). Typical examples include (using a combination of carboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. In addition, water softeners (non-fi + hexanic acids, amide/polycarboxylic acids, organic phosphoric acids,
aminopolyphosphonic acid, phosphonocarboxylic acid), fungicides (benzointhi-7zolinone, irithi-7zolinone, 4-
Various additives such as thi7zoline benzimigsol, halogenated phenol, etc.), surfactants, optical brighteners, hardeners, etc. may be used, and two or more compounds for the same or different purposes may be used in combination. You may.

Further, it is preferable to add various heptadmonium salts such as ammonium chloride, ammonium 9/I#, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium periosulfate, etc. as a membrane pH 111g agent 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 box film, and color reversal vapor. The present invention also relates to Research Disclosure 17123 (1978
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in J.

(Effects of the Invention) The present invention combines a cyan coupler represented by the general formula CI) with a cyan dye-forming coupler represented by the general formula (II), and further includes an epoxy compound represented by the general formula [III]. This makes it possible to combine the conventional 2-acylaminophenol cyan coupler with the 2-acylaminophenol
, 5-diacylaminophenol cyan couplers can be overcome, and a silver halide photographic material having excellent fastness to light and heat can be obtained. Such excellent effects of the present invention can be achieved by using the above two types of cyan couplers together, and this is because the above epoxies are added to the layer adjacent to the cyan coupler-containing layer (red sensitive layer). Even if you add it to it, nothing will change.

(Example) After coating a coating solution having the composition shown in Table 1 on a polyethylene (PET) support, gelatin (1500
m v /rn') tzhia shita u HG 4'
(Samples A-1 to A-22).

The above coating liquid was prepared as follows. First, 5.0 g of cyan coupler (I-1) and (II-3) 6 shown in Table I
．． 3 g of epoxy compound (m-9) and 20 m of ethyl acetate were heated and dissolved, and the mixture was added to 100 g of an aqueous solution containing 10 g of gelatin and sodium dodecylbenzenesulfonate, and was emulsified and dispersed. The entire amount of this emulsion was added to 235 g of a photographic emulsion containing 25 g of silver chlorobromide to prepare a coating solution. As a hardening agent, 2,4-dichloro-6-hydroxy-S-)riazine-sodium salt was used to coat the support, and as a protective layer, gelatin (LOOO
Sample A-1 was prepared by coating and drying the sample A-1.Other samples were prepared in the same manner.

These samples were exposed to red light through a continuous wedge and then developed using the following processing steps.

Processing process Temperature Time Developer 33
℃ 3 minutes 30 seconds bleach-fix solution 33℃ 1 minute 30 seconds washing with water 2
The formulation of the treatment solution used at 8-35°C for 3 minutes is as follows.

Symbol Benzyl alcohol 15m Diethylene glycol 8ml ) Luizine 2/3 sulfate hydrate 5g Add water and adjust to 1000ml pH 1O, 20 Ethylenediaminetetraacetic acid disodium salt 2g ethylenediaminetetraacetic acid ferric salt 40g Sodium sulfite
5g ammonium thiosulfate
Add 70g water and 1000m
After 31-section development at pH 6.80, each sample was stored at 100° C. for 2 weeks and exposed to light for 8 days in a Canon fading tester (100,000 lux) to perform a discoloration test. After the test, each sample was added to the pre-test concentration 1.
．． The concentration was measured at the point 0 using a Macbeth RD-514 type densitometer.

From the results in Table H, sample A-1 according to the combination of the present invention,
It can be seen that both A-7 and A-11 have extremely high fastness to heat, and are superior in improving the fastness to light and heat compared to comparative samples of other combinations.

In other words, color images obtained from couplers of general formula [I] have good light fastness or poor heat fastness, while color images obtained from couplers of general formula [■] have poor heat fastness. However, it has poor light fastness. The hue of the color image obtained from the coupler of general formula (II) has a high absorption of green light, which deteriorates the color reproducibility of color photographic materials. If a coupler and a coupler of general formula (n) are mixed and used, the characteristic of the coupler of general formula (n), which inherently has good heat fastness, will not be fully utilized, and the heat fastness of the mixed system will be less than expected. do not(
For example, comparison of sample A-2 with A-4 and A-6).

The effect of adding an epoxy compound is 1. In the combination of the present invention (for example, 52% improvement when comparing samples A-1 and A-2), the coupler of general formula [I] alone (for example, sample A-3,
(22% improvement in comparison with A-4) and is significantly larger than the coupler of general formula (n) 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 M and II.

(Samples B to F) The coating liquid for the first layer was prepared as follows. That is, 100 g of the yellow coupler shown in Table 1 was mixed with 100 ml of dibutyl phthalate (DBP) and 20 ml of ethyl acetate.
Dissolve in a 0mM mixture and add this solution to a 10% solution containing 80ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate.
First, the entire amount of this emulsified dispersion was emulsified and dispersed in 800 g of gelatin aqueous solution.
A coating solution was prepared by mixing 450 g (containing 66.7 g of Ag). Coating solutions for other layers were prepared in the same manner. 2,4-dichloro-6-hydroxys-triazine sodium salt was used as a hardening agent for each layer.

The following spectral sensitizers were used for each emulsion.

Blue-sensitive emulsion layer: 3.3°-G (γ-sulfopropyl)
- Selenacyanine sodium salt (2 x 10-4 mol per mol of silver halide) Green-sensitive emulsion layer: 3.3°-G (γ-sulfopropyl)
-5,5'-diphenyl-9-ethyloxacarbocyanine sodium salt (2.5XIO-' moles per mole of silver halide) Red-sensitive emulsion layer, 3,3'-di(γ-sulfopropyl)
-9-Methyl-thiadicarbocyanine sodium salt (2.5xlO-' 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 SOs
The chemical structures of the compounds of ) to (book 4) are as follows.

(a) Magenta coupler V ($b) Anti-fading agent h (lIC) Anti-fading agent (-d) Yellow coupler (umbrella e) Anti-fading agent *f Ultraviolet absorber (1:5:3 *g Ultraviolet absorption f of agent (1:3:3 mixture) These samples were exposed to red light through a continuous wedge and then developed in the same manner as in Example 1.

After the development process, each sample was stored at 100''C for 2 weeks and a discoloration/fading test was performed.After the test, each sample was treated at a pre-test concentration of 1.
The concentration was measured at the point 0 using a Macbeth RD-514 type densitometer. The results are shown in Table-■.

From the results in Table-■ Table-■, it can be seen that the sample of the present invention has a remarkable effect of improving the fastness against heat, and it is also found that adding an epoxy compound to other layers has a remarkable effect compared to sample F. .

In addition, Samples D 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.

Patent Applicant Fuji Photo Film Co., Ltd. Agent Patent Attorney Ii 1) Toshi 3 Proceeding Officer nIE Chiyo (Voluntary) April 17, 1985 Commissioner of the Patent Office Michibu Uga 1, Indication of Case Patent Application 1985 No. 270062 2, Name of the invention Silver halide photographic light-sensitive material 3, Relationship with the person making the amendment Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520)
Fuji Photo Film Co., Ltd. Representative: Sho Ohnishi 4, Agent Address: 7th floor, Midoriya 2nd Building, 3-7-3 Shintachibana, Minato-ku, Tokyo Telephone: (03) 591-7387 Name: (7643) Patent Attorney Satoshi Ii 1) 35. Date of amendment order Motu 6. AO7 of IJI increased by amendment, "Detailed explanation of the invention" column 8 of the specification subject to amendment, Contents of amendment (1) Page 17 of the specification, No. 4 - In line 5, "So, do they have chlorine atoms?" are corrected to "So, do Zl and Z2 have chlorine atoms?"

(2) Specification No. 19 page r (I-5) Structural formula of J will be corrected.

Claims (1)

[Scope of Claims] At least one cyan dye-forming coupler represented by the following general formula [I] and at least one cyan dye-forming coupler represented by the general formula [II], and a water-resistant compound represented by the general formula [III]. A halogenated photographic material characterized by containing a molten epoxy. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 , R_4 and R_5 each represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R_2 represents an aliphatic group, and 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_1_0 each represent a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, or a carbamoyl group (provided that R_7, R_8, R_9 and R_1_0 are all hydrogen atoms at the same time). Z_1 and Z_2 represent a hydrogen atom or a group or atom (leaving group) that can be separated upon coupling with a developing agent, and the general formula [I] R_2 and R_3 in general formula [II], R_5 and R_6 in general formula [III], R_7 and R_8 or R_7 and R_
9 may each form a 5- to 7-membered ring, and in the general formula [I], R_1, R_2, R_3 or Z_
1, or R_4, R_ in general formula [II]
Any one group of 5, R_6 or Z_2 may independently or jointly form a dimer or more multimeric coupler. )