JPS5952825B2 - Color photographic material containing dye image fading inhibitor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic material, and in particular to a color photographic material that prevents color fading in the dye image areas and unexposed areas of a dye image obtained by processing a silver halide color photographic material. It concerns photographic materials.

In silver halide color photographic materials, exposed silver halide grains are developed using an aromatic primary amine compound, and a dye image is formed by the reaction between the oxidation product of the amine and the coupler, resulting in a color image. It is known to obtain.

This method typically uses cyan, magenta, and yellow.
Phenol or naphthol couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, intazolones or cyanoacetyl couplers and acylacetamide or benzoylmethane couplers are used to form dye images of, respectively.

It is desired that the dye image obtained in this manner does not change color or fade even when exposed to light for a long time or stored under high salt and high humidity conditions. However, the fastness to ultraviolet rays or visible light is still not satisfactory, and it is well known that the color easily changes and fades when irradiated with these actinic rays. In order to eliminate these defects, various couplers with less fading properties than conventional ones are selected and used, ultraviolet absorbers are used to protect dye images from ultraviolet rays, and anti-fading agents are used to prevent fading due to light. A method using For example, various methods have been proposed for adding and blending ultraviolet absorbers to color photographic materials to improve the light resistance of dye images. However, in order to provide satisfactory lightfastness to a dye image using a UV absorber, a relatively large amount of UV absorber is required, and in this case, the dye image may be significantly contaminated due to the appearance of the UV absorber itself. There were many things I ended up doing. Furthermore, even when an ultraviolet absorber is used, it has no effect on preventing dye images from fading due to visible light, and there are limits to the improvement of light resistance by ultraviolet absorbers. Further, anti-fading agents η) having a phenolic hydroxyl group or a group that can be hydrolyzed to produce a phenolic hydroxyl group, bisphenols, US Pat. No. 262 specifies pyrogallol, carlic acid and its esters, U.S. Pat. No. 2,360,290 and JP 51-273
No. 33 describes α-tocopherols and their acyl derivatives, U.S. Pat. No. 3,432.300, U.S. Pat.
No. 74,627 describes 6-hydroxychromans,
U.S. Patent No. 3,573,050 describes the use of 5-hydroxycoumaran derivatives, and Japanese Patent Publication No. 49-20977 describes the use of 6,6'-dihydroxy-2,2'-bisspirochromans. Proposed. However, although these compounds are effective in improving the light fastness of dyes, their effect is not sufficient, and the anti-fading effect rapidly decreases or disappears after a certain point during long-term storage of color photographic materials. areas where unreacted coupler remains, that is, unexposed areas, may cause so-called yellowing (hereinafter referred to as Y-stain) due to ultraviolet rays, or may have low solubility in the solvent used when adding it to color photographic materials. ,
Due to their low diffusion resistance, they may diffuse into high pH processing solutions, and some compounds are relatively effective in preventing fading of dye images obtained from magenta couplers.
The reality is that dye images obtained from yellow and cyan couplers do not have a fading prevention effect and may fade, or even accelerate fading, and are still unsatisfactory.

The purpose of the present invention is to have an excellent anti-fading effect, excellent solubility in high boiling point solvents, excellent dispersion stability, excellent diffusion resistance, and no adverse effect on other photographic additives. Another object of the present invention is to provide a color photographic material containing an anti-fading agent that does not inhibit color development of couplers.

As a result of studies, the present inventors have found that at least one of the cyan dye image forming layer, the yellow single dye image forming layer, and their adjacent layers contains at least a compound represented by the following general formula [1] (hereinafter referred to as the compound of the present invention). It has been found that the above object can be achieved by using a color photographic material containing one type of color photographic material.

General Formula [1] In General Formula [1], R is a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group. Rl, R2, R3 are hydrogen atoms, halogen atoms, substituted and unsubstituted alkyl groups, alkylthio groups, alkoxy groups, aryl groups, aryloxy groups, arylthio groups, acyl groups, acylamino groups, diacylamino groups, acyloxy groups, A sulfonamide group, alkylamino group, cycloalkyl group or alkoxycarbonyl group, Z represents an atomic group necessary to form a chroman or coumaran ring, and R and R are further cyclized with each other to form a chroman or coumaran ring. These chroman and coumaran rings may form a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, an N-substituted amino group, a heterocyclic group or a fused ring. may be substituted with a residue.

Among the compounds represented by the general formula [1], compounds useful in the present invention include compounds represented by the general formulas [], [], and [].

Dan 9 E. R, Rl in the general formulas [], [] and [],
R2 and R3 have the same meaning as R in the general formula [1], w has the same meaning as R in the general formula [1], and R'1 has the same meaning as R1 in the general formula [1] ( R and w and R'1 and R may be the same or different.

) R4, R5, R6, R7, R8 and R are hydrogen atoms, halogen atoms, alkyl groups, alkyloxy groups, alkylthio groups, alkenyl groups, alkenyloxy groups, aryl groups, aryloxy groups, N-substituted amino groups, or It represents a heterocyclic group, and R8 and R9 may be cyclized with each other to form a carbocycle, and the carbocycle may be substituted with an alkyl group. The above general formula], I[l
and at the top, R and R' are each substituted or unsubstituted alkyl group or cycloalkyl group, R,,R2$
3 and R3 are hydrogen atoms, alkyl groups or cycloalkyl groups, R4, R5, R6, R7, R8 and R are hydrogen atoms, halogen atoms, alkyl groups or cycloalkyl groups, and R and R are cyclized with each other. Particularly useful are compounds having a chroman ring and the necessary atomic groups for R8 and R to cyclize together to form a carbocyclic ring.

Furthermore, among the compounds represented by the general formula [1], compounds represented by the general formula [1] are also included as compounds useful in the present invention. In the general formula concave, Rl, R2 and R3 are the general formula [
1], and Y4'1, R'2 and R'3 have the same meanings as R1, R2 and R3.

R4, R5, R6, R7, R8 and R have the same meanings as in the base and the top of the general formula (3), and R'
4, R'5, R'6, R'7 and R5, are R4, R5
, R6, R7, R8 and R. X is an alkylene group to which the carbon chains of the alkylene group may be bonded via -0-, -S-, -NH- or -SO2-;
It represents a phenylene group, a cycloalkylene group, or a divalent heterocyclic group. In the general formula concave, R1 and R'
1 is an alkyl group, R2, R'2, R3 and R'3 are hydrogen atoms, R4, W4, R8, R'8. , R, and W,
is an alkyl group, R5, R'5, R6, R'6, R78 and R'7 are hydrogen atoms, and X is an alkylene group or an alkylene group in which the carbon chains of the alkylene group are bonded via one SO2-. Compounds are particularly useful.

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

Exemplary Compounds The compounds of the present invention can be found in the aforementioned U.S. Pat. No. 3,432.300, U.S. Pat.
6-hydroxychroman, 5-hydroxycoumaran and 6,6'- obtained by the method described in Publication No. 0977 etc.
By reacting dihydroxy-2,2'-bisspirochromans with halides, sulfuric esters, or vinyl compounds in the presence of an alkali, which is a general alkylation method, or by reacting the dihydroxy-2,2'-bisspirochromans with a halide, a sulfuric acid ester, or a vinyl compound in the presence of an alkali, or according to German Patent No. 1,938,672. Specification, Journal of the American Chemical
Society (JournalOftheAmerica)
anchemicalSOciety) Volume 66, No. 15
Pages 23-5, Journal of the Chemical Society.
It can be synthesized by bonding a phenol having an ether bond at the p-position by the method described in P.Ociety, pp. 1850-2 (1958) and p. A synthesis example is shown below for reference.

Synthesis Example 1 (Synthesis of Exemplified Compound 1 (2)) 2.2, 4,
Dissolve 7-tetramethyl-6-chromanol 2061 and n-octyl bromide 1939 in 21 acetone,
Anhydrous potassium carbonate 69f! Add and heat under reflux for 15 hours while stirring on a hot water bath.

After the reaction, the inorganic substances produced are filtered off, the solvent is distilled off, and the residue is distilled under reduced pressure to obtain viscous liquid 2809 with a boiling point of 152-3/0.1 mmHg. Elemental analysis results (C2lH34O
2) Unit: % calculated value C: 79.25H: 10.
69 Experimental value C: 79.03H: 10.82 Synthesis example
2 (Synthesis of Exemplified Compound 1 (5)) p-benzyloxyphenol 2f! , Phytol 3g benzene 25mi!
25 TIt of formic acid was added thereto, and the mixture was heated under reflux for 20 hours.

The benzene layer was separated, washed with an aqueous alkali solution and then with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was distilled under reduced pressure, and the fraction with a boiling point of 130-1400/0.00111Hg was further purified by column chromatography to obtain a viscous liquid 3.
．． Obtain 2fI. Elemental analysis value (C,,H,OO,)
Unit: % Calculated value C: 82.85H: 10.46 Experimental value C: 82.63H: 10.54 Synthesis example 3 (Synthesis of exemplified compound 1 (31)) 6,6 dihydroxy-7,
7'-Jime Senruichi 4, 4, 4'. 4-tetramethylbis-2,2-spirochroman 1849 and n-octyl bromide 1939 are dissolved in ethanol 11, potassium hydroxide 569 is added, and the mixture is heated under reflux on an oil bath for 3 hours.

After the reaction, the precipitated inorganic salt was filtered off, the solvent was distilled off, and the residue was recrystallized from methanol to give colorless crystals 47 with a melting point of 93-4°C.
3f! get. Elemental analysis results (C3, H6OO4) Unit: % Calculated value C: 79.05H: 10.14 Experimental value C: 78.92H: 10.31 The compound of the present invention is preferably added to the silver halide emulsion layer. may be added to other layers, such as adjacent layers to the silver halide emulsion layer.

The compounds of the invention are oil soluble and generally described in U.S. Pat.
, 322,027, 2,801,170, 2,801,171, 2,272,191 and 2,304,940. It is preferable to dissolve and disperse the silver halide emulsion in a high boiling point solvent together with a low boiling point solvent if necessary.At this time, couplers, hydroquinone derivatives, ultraviolet absorbers or known There is no problem in using anti-fading agents etc.

At this time, there is no problem even if two or more of the compounds of the present invention are used as a mixture. Further, to explain in detail the method of adding the compounds of the present invention, one or more of the compounds are added to an organic acid amide simultaneously with a coupler, a hydroquinone derivative, an ultraviolet absorber, a known anti-fading agent, etc., as required. kind,
Carbamates, esters, ketones, urea derivatives, etc., especially di-n-butyl phthalate, tricresyl phosphate, di-isooctyl acelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N,N
- In a high boiling point solvent such as di-ethyl-caprylamide, n-pentadecyl phenyl ether or fluorine paraffin, ethyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane tetrahydrofuran, etc. as necessary. Anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or It is mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing a nonionic surfactant such as zorbitan sesquioleate and zorbitan monolaurate, and emulsified and dispersed using a high-speed rotating mixer, colloid mill, or ultrasonic dispersion device. , can be added to silver halide emulsions for use. If the coupler used at this time is diffusive, the coupler may be added to a color developing solution to emulsify and disperse only the compound of the present invention, and then added to a silver halide emulsion for use.

Further, the compound of the present invention has a sufficient effect even if it is incorporated into a color photographic material obtained after developing the silver halide color photographic material.

The amount of the compound of the present invention to be added is not particularly limited since the compound is substantially colorless and does not cause any adverse effects such as layer color staining by itself, but it is present in about 159 per mole of the dye formed by color development processing. Mainly for economical reasons, in silver halide color photographic materials containing couplers it is preferably 5 to 300% by weight, especially 10 to 100% by weight, based on the commonly used couplers. is preferred, and in silver halide color photographic materials containing no coupler, 10% per mole of silver halide.
~100f! , especially 15-60f! is preferred.

Examples of UV absorbers used with the compounds of the present invention include U.S. Pat. No. 2,739,888;
No. 04,896, No. 3,253,921, No. 3,
No. 533,794, No. 3,692,525, No. 3
, 705,805, 3,738,837, 3,754,919, 3,052.636, 3,707,375 and British Patent No. 1,321,
It is advantageous to use the hand azolidone, benzotriazole, acrylonitrile, and benzophenone compounds described in No. 355, etc. to prevent fading due to short-wavelength actinic rays.
It is advantageous to use 6, 327, and 328 (manufactured by Chiba Gaiki Co., Ltd.) alone or in combination.

Typical dye image-forming couplers that can be used in the silver halide color photographic material of the present invention include compounds described in the following patents.

Among these, yellow one-dye image-forming couplers include benzoylacetanilide type, hivaloylacetanilide type, or two-equivalent type yellow in which the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction (a so-called split-off group). monodye image-forming couplers, such as those described in U.S. Pat. No. 2,875
, No. 057, No. 3,265,506, No. 3,66
No. 4,841, No. 3,408,194, No. 3,4
No. 47,928, No. 3,277,155, No. 3,
Specification No. 415,652, Japanese Patent Publication No. 49-13,576, Japanese Patent Application Publication No. 48-29,432, Japanese Patent Application Publication No. 48-66,8
No. 34, JP-A-49-10,736, JP-A-49-1
22,335, JP-A-50-28,834, and JP-A-50-132,926.

The cyan dye image-forming couplers include phenolic, naphthol, or two-equivalent cyan dye image-forming couplers having a split-off group, and these are described, for example, in U.S. Pat. Nos. 2,423,730 and 2,474,29.
No. 3, No. 2,801,171, No. 2,895,8
No. 26, No. 3,476,563, No. 3,737,
No. 326, No. 3,758,308, No. 3,839
, 044 specification, JP-A-47-37,425, JP-A-50-10.135, JP-A-50-25,228, JP-A-50-112.038, JP-A-50. -117
, No. 422 and Japanese Unexamined Patent Publication No. 130,441/1983. Specific representative examples of dye image-forming couplers used in the present invention are shown below. (Y-1) α-(4-carboxyphenoxy)-α-pivalyl-2
-Chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-2) α-benzoyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)buthylamide]acetanilide.

(Y-3) α-benzoyl-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide.

(Y-4) α-(4-carboxyphenoxy)-α-pivalyl-2
-Chloro-5-[α-(3-pentadecylphenoxy)
butylamide] acetanilide.

(Y-5)α-(1-benzyl-2,4-dioxo-3
-imidazolidinyl)-α-pivalyl-2-chloro-5
-[γ-(2,4-di-t-amylphenoxy)butylamide]acetanilide.

(Y-6) α-[4-(1-Benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-pivalyl-2-chloro-5-[γ-(2 .4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-7) α-acetoxy-α-{3-[α-(2.4-di-t-
amylphenoxy)butyramide]benzoyl}-2-
Methoxyacetanilide.

(Y-8) α-{3-[α-(2,4-di-t-amylphenoxy)butylamide]benzoyl}-2-methoxyacetanilide.

(Y-9) α-[4-(4-benzyloxyphenylsulfonyl)
phenoxy]-α-pivalyl-2-chloro-5-[γ-
(2,4-di-t-amylphenoxy)butyramide]
Acetanilide.

(Y-10) α-pivalyl-α-(4,5-dichloro-3(2H)-
pyridazol-2-yl)-2-chloro-5-[(hexadecyloxycarbonyl)methoxycarbonylacetanilide.

(Y-11) α-pivalyl-α-[4-(p-chlorophenyl)-5
-oxo-ΔLtetrazolin-1-yl]-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide.

(Y-12)α-(2,4-dioxo-5,5-dimethyloxazolidin-3-yl)-α-pivalyl-2-chloro-5-[α-(2,4-di-t- amylphenoxy)butyramide]acetanilide.

(Y-13) α-pivalyl-α-[4-(1-methyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)
]-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(Y-14) α-pivalyl-α-[4-(p-engineer phenyl)-5
-oxo-Δ2-tetrazoli-1-yl]-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide.

(C-1) 1-Hydroxy-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide.

(C-2) 2,4-dichloro-3-methyl-6-(2.
4-di-t-amylphenoxyacetamido)phenol.

(C-3) 2,4-dichloro-3-methyl-6-[α-(2,4-
di-t-amylphenoxy)butyramide]phenol.

Z4 (C-4) 1-Hydroxy-4-(3-nitrophenylsulfonamide)-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide.

(C-5) 1-Hydroxy-4-[(β-methoxyl)carbamoyl]methoxy-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide.

(C-6) 1-Hydroxy-4-(isopropylcarbamoyl)methoxy-N-dodecyl-2-naphthamide (C-7) 2-perfluorobutylamide-5-[α-(2.4-
di-t-amylphenoxy)hexaneamide]phenol.

(C-8) 1-Hydroxy-4-(4-nitrophenylcarbamoyl)oxy-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide O(C-9 ) 2-(α,α,β,β-tetrafluoropropionamide)-5-[α-(2,4-di-t-amylphenoxy)butyramide]phenol.

(C-10) 1-Hydroxy-N-dodecyl-2-naphthamide.

(C-11) 1-Hydroxy-(4-nitro)phenoxy-N-[δ
-(2,4-di-t-amylphenoxy)butyl]-2
- Naphthamide.

(C-12) 1-Hydroxy-4-(1-phenyl-5-tetrazolyloxy)-N-[δ-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide.

(C-13) 2-(α,α,β,β-tetrafluoropropionamide)-4-β-chloroethoxy-5-[α-(2.4-
di-t-amylphenoxy)butyramide]phenol.

(C-14) 2-chloro-3-methyl-4-ethylcarbamylmethoxy-6-[α-(2,4-di-t-amylphenoxy)butyramide]phenol.

When the coupler used in the silver halide color photographic light-sensitive material according to the present invention is present in the silver halide color photographic light-sensitive material, it is generally 5 to 50 mol based on the silver halide. , preferably 10 to 30 mol? It is not used in the developer, and when present in the developer, it is generally 0.5 to 3.0 y.
/11, preferably 1.0 to 2.09/l. In this case, each of the yellow, magenta, and cyan couplers may be used alone or in combination of two or more types, and when two or more types are used in combination, the amounts mentioned above are sufficient. . Furthermore, silver halide emulsions contain hydroquinone derivatives, which are antioxidants that have been known for a long time, such as U.S. Pat. Nos. 3,236,893 and 3,062,8.
No. 84, No. 2.816,028, No. 2,735,
No. 765, No. 2.732,300, No. 2.728
, No. 659, No. 2.722.556, No. 2.71
No. 0,801, No. 2.704,713, No. 2.7
No. 01,197, No. 2.675,314, No. 2.
No. 418,613, No. 2,403,721, No. 2
．． 384,658, 2.360,290, 2.336,327, British Patent No. 557,750,
No. 557,802, German Published Patent No. 2.149,
Specification No. 789, Japanese Patent Publication No. 44-54,116, Japanese Unexamined Patent Publication No. 46-2.128, Journal of the Organ Chemistry Vol. 72, pp. 772-774 (J
OwnOftheOrganicChemist
ry) etc. may be used in combination.

Among these hydroquinone derivatives, those in which the substituent on the aromatic nucleus is a substituted or unsubstituted alkyl group are particularly preferred, and particularly preferred compounds include 2,5-dioctyl-hydroquinone, 2,5-di-Tert- There are amyl-hydroquinone and 2,5-di-Tert-butyl-hydroquinone. The silver halide emulsion used in the silver halide color photographic light-sensitive material according to the present invention generally has silver halide grains dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide, silver iodide, etc. Silver,
These are silver chlorobromide, silver chloride bromide, silver chloroiodobromide, and mixtures thereof.These silver halides can be produced by various methods such as the ammonia method, the neutral method, the so-called compounding method, and the simultaneous mixing method. It will be done.

In addition, gelatin, phthalated gelatin, and derivative gelatin such as malonated gelatin are commonly used as hydrophilic colloids for dispersing silver halide. Alternatively, albumin, agar, gum arabic, alginic acid, casein, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, imidized polyacrylamide, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used. Furthermore, these silver halide emulsions can be optically sensitized using various sensitizing dyes in order to impart photosensitivity in a desired photosensitive wavelength range. Preferred sensitizing dyes include, for example, U.S. Pat.
No. 9,201, No. 2,072.908, No. 2,7
No. 39,149, No. 294,763, No. 2,21
No. 3,995, No. 2.493,748, No. 2,5
19,001, West German Patent No. 929,080, and British Patent No. 505,979, cyanine dyes, merocyanine dyes, or composite cyanine dyes can be used alone or in combination of two or more, Furthermore, if necessary, chemical sensitizers such as thioether compounds, quaternary ammonium salt compounds or polyalkylene oxide compounds, triazoles, imidazoles, azaindenes, benzothiasoriums, zinc compounds, cadmium compounds, mercabutanes, etc. Stabilizers such as: chromium salts,
Zirconium salt, mucochloric acid, Special Publication No. 34-7, 1
No. 33, Japanese Patent Publication No. 46-1,872, U.S. Patent No. 6
No. 82,641, No. 3,736,320, No. 3,
362,827, British Patent No. 3,325,287, British Patent No. 686,440, and British Patent No. 1,332,647. Hardeners such as amide and ethyleneimine; dihydroxyalkane plasticizers such as glycerin and 1,5-pentanediol;
Various photographic additives such as fluorescent brighteners, antistatic agents, and coating aids can be used alone or in combination of two or more, and the resulting silver halide emulsion can be used in accordance with the present invention as described above. Contains a dispersion of a compound represented by the general formula according to the above formula, and if necessary, via a subbing layer, intermediate layer, protective layer, etc. A silver halide color photographic light-sensitive material is obtained by coating it on a support such as a synthetic resin film, baryta paper, polyethylene-coated paper, or a glass plate.

The silver halide color photographic light-sensitive material of the present invention can be applied to an internal type silver halide color photographic light-sensitive material containing a coupler or an external type silver halide color photographic light-sensitive material containing a coupler in a developer. This is advantageous for internal silver halide color photographic materials, and after exposure,
It is advantageous to carry out the color development by a color development method.

Furthermore, the coupler and the color developing agent are protected so that they do not come into contact with each other when unexposed and are present in the same layer, and can be used in silver halide color photographic materials where they can come into contact with each other after exposure, or silver halide colors containing couplers. It can also be used in silver halide color photographic materials in which a color developing agent is contained in a layer that does not contain the coupler in a photographic light-sensitive material, and when an alkaline processing solution is permeated, the color developing agent is moved and can come into contact with the coupler. Furthermore, in a silver halide color photographic light-sensitive material for diffusion transfer, the compound of the present invention can be added to the light-sensitive element and/or the image-receiving element of the light-sensitive material, and in particular, it can be present in the image-receiving element. is advantageous. The reversal process involves development in a black and white negative developer, followed by white exposure or treatment in a bath containing a caprior such as a boron compound, and color development in an alkaline developer containing a color developing agent. At this time, there is no problem in including a capri agent in an alkaline developer containing a color developing agent. A silver image is produced by bleaching with a color developing solution and a bleaching solution containing ferricyanide or a ferric salt of aminopolycarboxylic acid as an oxidizing agent, and then with a fixing solution containing a silver salt solvent such as thiosulfate. and removes residual silver halide, leaving a dye image. Instead of using a bleach solution and a fixing solution, a one-bath bleach fixing solution containing an oxidizing agent such as a ferric salt of an aminopolycarboxylic acid and a silver salt solvent such as thiosulfate may be used for bleaching and fixing. can. Also, in combination with color development, bleaching, fixing, or bleach fixing,
Various treatments such as preduralization, neutralization, water washing, termination, and stabilization can also be performed. In particular, processing steps in which the silver halide color photographic light-sensitive material of the present invention is advantageously developed include, for example, color development, washing with water if necessary, bleaching and fixing, washing with water, stabilizing if necessary, and drying. This treatment step is carried out at a high temperature of, for example, 30° C. or higher and within a very short time. Typical treatment steps and typical compositions of each treatment liquid used are shown below. Color developer composition: Benzyl alcohol 5.0mJ Sodium hexametaphosphate 2.5f! Anhydrous sodium sulfite 1.9f! sodium bromide
1.4f! potassium bromide
0.5f! Borax (Na2B4O7・10H20)
39.1f! N-Ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline sulfate 5.09 Add water to make 11, add sodium hydroxide to PHlO. Adjust to 3O.

Bleach constant phase liquid composition: Ethylenediaminetetraacetate iron ammonium 61.0y ethylenediaminetetraacetate diammonium
5.0f! Ammonium thiosulfate 124
．． 5f1 Sodium metabisulfite 13,3V
Anhydrous sodium sulfite 2.79 Add water to make 11, and adjust the pH to 6.5 using aqueous ammonia.

Stabilizing liquid composition: Glacial acetic acid 20mj! Add 800 TILI of water, add sodium acetate and adjust the pH.
After adjusting to 3.5 to 4.0, water is further added to bring the value to 11.

Particularly useful color developing agents used for color development of the silver halide color photographic light-sensitive material of the present invention include primary phenylene diamines, aminophenols, and derivatives thereof. This can be cited as an example.

N,N-dimethyl-p-phenylenediamine, N,N-
Diethyl-p-phenylenediamine, N-carbamidomethyl-N-methyl-p-phenylenediamine, N-carbamidomethyl-N-tetrahydrofurfuryl-2-methyl-p-phenylenediamine, N-ethyl-N- Carboxymeryl-2-methyl-p-phenylenediamine, N
-Carbamide salt-N-ethyl-2-methoxyl-p-phenylenediamine, N-ethyl-N-tetrahydrofurfuryl-2-methyl-p-aminophenol, 3-acetylamino-4-aminodimethylaniline , N-ethyl-N-β-methanesulfonamidoethyl-4-aminoaniline, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N-methyl-N - Salts of β-sulfoethyl-p-phenylenediamine with inorganic acids such as hydrochloric acid and sulfuric acid, or with organic acids such as p-toluenesulfonic acid. A silver halide color photographic light-sensitive material using the compound of the present invention may be processed using a color developing solution containing both a primary aromatic amine color developing agent and an oxidizing agent that subjects the metallic silver image to a redox reaction. It is valid.

When these color developing solutions are used, the color developing agent is oxidized by an oxidizing agent and then coupled with a photographic color coupler to form a dye image.

Such a color developing solution is disclosed, for example, in Japanese Patent Application Laid-Open No. 4819729, and the preferred oxidizing agent for this purpose is a cobalt complex salt having a coordination number of 6. Color photographic processing using such a color developer is particularly effective for so-called silver-saving color photographic materials, which have a smaller amount of silver than ordinary silver halide color photographic materials. Particularly useful cobalt complex salts contain ligands selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetraamine, amines, nitrates, nitrites, azides, chlorides, thiocyanates, isothiocyanates, water and carbonates. and (1) at least 2 ethylenediamine ligands, or (2) at least 5 amine ligands, or (3) at least 11b151 triethylenetetraamine ligands.

A particularly preferred cobalt complex salt is, for example, a complex salt represented by the following formula. [CO(En)2(N3)2]X;
[CO(En)2C1(NCS)]X; [CO(En)
2(NH3)N3]X:[CO(En)El2]X;
CO(En)2(SCN)2]X; [CO(En)2(
NCS)2]X; and [CO(NH3)6]XO In the above formula, En represents ethylenediamine, and , thiocyanate, isothiocyanate and hydroxide.

The most preferred complex salts are hexamine salts of cobalt, such as chlorides, bromides, sulfites, sulfates, perchlorates,
Nitrite and acetate. The cobalt complex salt used in the color developer is generally about 0 for color developer 11.
．． 19-509, more preferably about 1f.
A concentration range of 1 to about 159 is used. Further, the silver halide color photographic light-sensitive material using the compound of the present invention is developed in a color developer containing a primary aromatic amino color developing agent, and then preferably exposed to light during the color development step. is received in the layer and an intensifying bath (Anlplifyi
A color photographic processing method comprising the presence of a color developing agent transferred into an ngbath) and brought into contact with an intensifying solution containing an oxidizing agent as described above, such as a cobalt complex having a coordination number of 6. It is also useful to use

Further, as another oxidizing agent which is preferable for this purpose, for example, a peroxyhydrogen solution as disclosed in Japanese Patent Application No. 49-80,321 is also useful. It is preferable that the intensifying solution contains a silver halide development inhibitor in addition to the oxidizing agent to process the silver halide color photographic light-sensitive material. Then,
The reinforcing process can be carried out under indoor lighting.
By following this method, it is possible to observe the formation of pigments,
It can then be stopped after reaching the desired dye concentration. Preferred development inhibitors are water-soluble bromide compounds such as potassium bromide, and heterocyclic compounds such as tetrazole, azaintene and triazole groups that do not contain mercapto or ionic iodide groups.
The concentration of cobalt complex salt contained in the intensifier is generally about 0.
2f1~about 20f! /11 most preferably about 19 to about 1
5 V/l and the concentration of the hydrogen peroxide solution is generally about 0.
01-10%, most preferably 0.5-5%.

When a water-soluble bromide is used as a development inhibitor, the material generally contains about 1y to about 40f in the intensifier.
On the other hand, development inhibitors consisting of compounds having a complex structure are usually included in an amount of about 0.019 to about 3! !
used at a concentration of /l. Reinforcing baths generally have a pH of 6 to
14, preferably at pH 8-12. In addition to the above-mentioned development inhibitor, the intensifying solution may further contain a development accelerator, a stabilizer, a water softener, a thickening agent, an agent for preventing uneven processing, etc., if necessary.

Furthermore, the compound of the present invention is sufficiently effective in preventing fading of diazo photosensitive materials. The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 The yellow coupler shown in Table 1-1 and the compound of the present invention were dissolved in the solvent shown in the same table, and 2,5-di-t-octylhydroquinone 150T19 was further added to dissolve the solution. Sodium benzenesulfonate 3
．． The resulting dispersion was added to 1000 CC of a 5% gelatin aqueous solution containing 0 g, and then dispersed with a homogenizer. 5% of amide
After adding 10 WIJ of methanol solution, the mixture was coated on polyethylene coated paper and dried to obtain a silver halide photographic light-sensitive material.

After performing optical wedge exposure on these samples, they were processed according to the processing method shown in the text, and then exposed for 50 hours using a xenon fade meter to determine the post-exposure concentration (D before exposure). Percentage (DA) of concentration (DO=1.0).

×100) using a Sakura color densitometer PD-16 model (manufactured by Konishiroku Photo Industry Co., Ltd.), the dye fading rate was measured with blue light, and the unexposed area Y-stain increase rate was measured with blue light. It is shown in Table 1-2. However, in the comparative samples in Table 1-2, couplers and anti-fading agents were used in combination as shown in Table 1-3.

A known anti-fading agent is O-1 using a compound having the following structure.
As is clear from the results in Table 2, the known compounds do not have an effect of preventing yellow dye images from fading, and even have the effect of promoting fading, whereas the compounds of the present invention have no effect on yellow dye images. It can be seen that it has an excellent anti-fading effect even when exposed to light, and also effectively prevents Y-stain in unexposed areas.

Example 2 Cyan coupler (C-1) at 46f! ;2,5-di-t
- Okuteru Hydroquinone 200 Instant and Anti-Fade Agent (
Types and amounts in Table 2) 409 dipsilphthalate, 120f acetic acid! Dissolve this solution in a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate.
After adding it to CC, it was dispersed with a homogenizer, and the resulting dispersion was added to 1000 cc of a red-sensitive silver chlorobromide (silver chloride 20 mol%) emulsion, and 2.4-dichloro-6-hydroxy was added as a hardening agent. After adding 20 d of a 4% aqueous solution of sodium -S-triazine, the mixture was coated on polyethylene coated paper and dried to obtain a silver halide photographic material.

Next, add cyan coupler (C-1) 46y to (C-3) 45
A sample exactly the same as before was prepared except that y was replaced, and it was treated in the same manner as in Example 1.
After 50 hours of exposure, the pigment concentration was measured in accordance with Example 1 except that red light was used, and the results shown in Table 2 were obtained. As is clear from the results in Table 2, known anti-fading methods were used. It can be seen that the compound of the present invention exhibits a good fading prevention effect on cyan images as well, compared to the inhibitor.

Example 3 A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on a polyethylene coated paper from the support side.

(Sample 1) First layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 10 mol% of silver chloride, the emulsion containing 4009 gelatin per mol of silver halide, A yellow coupler (Y-6), which was sensitized using 2.5 x 10-4 mol of a sensitizing dye having the following structure per mol and dissolved and dispersed in dibutyl phthalate, was added at 2X per mol of silver halide.
It contains 10-1 mol of silver, and is coated to give a silver content of 400 to 400/g.

2nd layer: A gelatin layer coated to a dry film thickness of 1 μm (3rd layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 40 mol of silver chloride; contains 500 f! of gelatin per mole of silver halide, and can also be sensitized using 2.5.times.10@-4 moles of a sensitizing dye having the following structure per mole of silver halide.

The magenta coupler, 4,4'-bensyritenehis[1-(2,3,
4,5,6-pentachlorophenyl)-3-{2◆chloro-5-[δ-(2,4-di-t-amylphenoxy)
It contains 2×10 −1 moles of anilinohirazolone] per mole of silver halide, and is coated in a silver amount of 500 η/g.

Layer 4: A gelatin layer with a thickness of 1 μm containing 30 m 9 /day of t-octylhydroquinone dissolved and dispersed in dibutyl phthalate.

5th layer: 20 moles of silver chloride? A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 5009 gelatin per mole of silver halide, and a sensitizing dye having the following structure per mole of silver halide: 2.5 x 10-4 moles Cyan coupler (C-3), which was sensitized using
It contains 1 mole of silver and is coated at a silver content of 500 mg/i.

6th layer: Protective layer (gelatin layer applied to a dry film thickness of 1μ).

The silver halide emulsions used in each photosensitive layer (1st, 3rd, and 5th layers) were prepared by the method described in Japanese Patent Publication No. 46-J Kamo V2, and sodium thiosulfate pentahydrate was used in each case. The film was chemically sensitized and contained 4-hydroxy-16-methyl-1,3,3a,7-tetrazaintene as a stabilizer, bis(vinylsulfonylmethyl) ether as a hardening agent, and saponin as a coating aid. .

Next, the compound of the present invention (30%
) was added to each coupler in an amount of 30 wt%, and the sample 2 was obtained by adding and dispersing.

Next, in the fourth layer of sample 2, 2.(2'-
A gelatin hand liquid prepared by dissolving hydroxy-3',5'-di-t-butylphenyl)penzotriazole in tricresyl phosphate and dispersing it was applied so that the ultraviolet absorber ratio was 0.79/I. Let this be sample 3.

Next, in place of the compound of the present invention used in Sample 2, the same amount of the known compound (Kawa) and (11) were used as Samples 4 and 5, and in Sample 3, the known compound (Kawa) and (11) were used in place of the compound of the present invention. Samples 6 and 7 used the same amounts of () and (self), respectively.

The samples prepared above were exposed to blue light, green light, and red light in a light wedge, and treated according to Example-1. After being exposed for 100 hours using a xenon fademeter, the respective dye concentrations were determined. The results obtained are shown in Table 3.

As is clear from the results in Table 3, compared to the known anti-fading agents that have poor inhibitory effects on dye images other than magenta dye images or tend to promote fading, the compounds of the present invention It can be seen that it is an extremely excellent anti-fading agent that has good anti-fading effects on yellow and cyan dye images.

Claims (1)

[Scope of Claims] 1. At least one of the cyan dye image-forming layer, yellow dye image-forming layer and layers adjacent thereto on the support contains at least one compound represented by the following general formula [I]. color photographic materials. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Hydrogen atoms, halogen atoms, substituted and unsubstituted alkyl groups, alkylthio groups, alkoxy groups, aryl groups, aryloxy groups, arylthio groups, acyl groups, acylamino groups, diacylamino groups, acyloxy groups, sulfonamide groups, alkylamino group, cycloalkyl group or alkoxycarbonyl group, Z represents an atomic group necessary to form a chroman or claman ring, and further R and R_1 may be cyclized with each other to form a chroman or coumaran ring, and these Chroman and coumaran rings are substituted with halogen atoms, alkyl groups, alkylthio groups, alkoxy groups, alkenyl groups, alkenyloxy groups, aryl groups, aryloxy groups, N-substituted amino groups, heterocyclic groups or residues forming fused rings. may be done. ]