JPS6127736B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photographic material, and more particularly to a color photographic material with excellent preservability of dye images obtained by processing a silver halide color photographic light-sensitive material. In a silver halide color photographic light-sensitive material, 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. It is known to obtain images. This method typically uses cyan, magenta,
a phenolic or naphthol coupler, respectively, to form a yellow dye image; 5-
Pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indazolone or cyanoacetyl couplers; and acylacetamide or dibenzoylmethane couplers are used. It is desired that the dye image obtained in this way does not change color or fade even when exposed to light for a long time or stored under high temperature and high humidity. However, the dyes produced in this manner are not yet satisfactory in their fastness mainly to ultraviolet rays or visible rays, and are known to easily change color and fade when irradiated with these actinic rays. For example, magenta dye is below 350nm and
425-550nm, yellow dye below 340nm and
400-500nm, cyan dye below 340nm and 500nm
It is known that the color fades when exposed to light with a wavelength of ~600 nm. In order to eliminate such drawbacks, methods have been proposed that use various couplers that have less fading properties or use anti-fading agents that prevent fading due to light. Examples of such anti-fading agents include bisphenols in Japanese Patent Publication Nos. 48-31256 and 48-31625, pyrogallol, gallic acid and its esters in US Pat. No. 3,069,262, and US Pat. No. 2,360,290. No. and US Pat. No. 4,015,990 describes α-tocopherols and their acyl derivatives, US Pat. No. 3,432,300 and US Pat.
3573050 describes 5-hydroxycoumaran derivatives, and Japanese Patent Publication No. 49-20977 describes 6,6'-
It has been proposed to use dihydroxy-2,2'bispirochromans and the like. However, although these compounds do have an effect on the light resistance of dyes, their effect is not sufficient;
During long-term storage of color photographic materials, the anti-fading effect may suddenly decrease or disappear at a certain point, and areas where unreacted coupler remains, that is, unexposed areas, may turn yellow due to ultraviolet light (hereinafter referred to as Y-stain). In addition, some compounds have a relatively good anti-fading effect on dye images obtained from magenta couplers, but have no anti-fading effect on dye images obtained from yellow and cyan couplers. The reality is that it is still unsatisfactory, as it can cause damage or even promote fading. Therefore, it has been proposed to use these known dye fading inhibitors in combination or in combination with an ultraviolet absorber. However, although it is true that the combination of dye fading inhibitors increases the effect compared to using them alone, the degree of the effect is not satisfactory, and the combination with an ultraviolet absorber simply increases the effect of preventing dye fading against ultraviolet rays. All I could do was be done. The purpose of the present invention is to provide excellent anti-fading effect and Y-
It has stain prevention effect, excellent solubility in high boiling point solvents, excellent dispersion stability, excellent diffusion resistance,
The object of the present invention is to provide a color photographic material that does not adversely affect other photographic additives and does not inhibit color development of couplers. The color photographic material of the present invention contains a compound represented by the following general formula [] and at least one ultraviolet absorber. In the formula, R is R ₆ CO-, an alkyl group or alkenyl group each optionally having a substituent, R ₁ is an alkyl group or an alkoxy group each optionally having a substituent, R ₂ and R ₃ are hydrogen Atom or〓〓〓〓〓
represents an alkyl group which may have a substituent, R' represents a hydrogen atom or a group selected from the above R,
R ₆ represents an alkyl group, an alkenyl group, or an aryl group, each of which may have a substituent. In the general formula [], the following general formula [-2]
Compounds represented by are also included. In general formula [-2], R, R ₁ , R ₂ and R ₃ have the same meanings as in the above general formula [],
X represents an alkylene group, alkenylene group or phenylene group which may have a substituent. These alkylene groups preferably have 1 to 18 carbon atoms. Typical specific examples of the compound represented by the general formula [] are shown below. 〓〓〓〓〓
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The compound represented by the general formula [ ] according to the present invention is described in US Pat. No. 3,764,337 and Japanese Patent Publication No. 49
It can be obtained by alkylating or acylating 6,6'-dihydroxy-bis-2,2-spirochroman compounds obtained by the method described in Publication No. 20977, and furthermore, the patent application Although it can also be synthesized by the methods described in Sho 51-91917 and Sho 51-94667, typical synthesis examples are described below. Synthesis Example 1 (Synthesis of Exemplary Compound (4)) 6,6'-dihydroxy-7,7'-dimethyl-
184 g of 4,4,4',4'-tetramethyl-bis-2,2' spirocuman and 96 g of n-octyl bromide
Dissolved in dioxane 1 and then added potassium hydroxide
Add an aqueous solution of 28 g and 100 ml of water, and heat under reflux on an oil bath for 3 hours. After filtering off the precipitated salt, the solvent is distilled off, and the residual candy-like substance is dissolved in n-hexane, and then washed with an alkaline aqueous solution, whereby the dihydroxy-spirochroman as a raw material is transferred to the alkaline aqueous solution. After washing with water, the solvent is distilled off, and methanol is added to the residue for washing.
6,6'-di-n-octyl-7,7'-dimethyl-4,4,4',4'-tetramethyl-bis- formed as a by-product
Since 2,2'-spirochroman exemplified compound (29) precipitates, this is filtered off and methanol is distilled off to obtain a viscous liquid. The yield was 140 g, and the product was further purified by column chromatography to obtain a viscous liquid. Nuclear magnetic resonance spectrum (NMR), infrared absorption spectrum (IR), and elemental analysis confirmed that the product was the desired product. Elemental analysis value (C ₃₁ H ₄₄ O ₄ ) Unit: % Calculated value C: 77.46 H: 9.23 Experimental value C: 77.34 H: 9.41 Synthesis example 2 (synthesis of exemplified compound (29)) 6,6'-dihydroxy-7 ,7'dimethyl-4,
4,4,4-Tetramethylpis-2,2-spirochroman 1849 and 193 g of n-octyl bromide were dissolved in 1 ethanol, 56 g of potassium hydroxide was added, and the mixture was heated under reflux on an oil bath for 3 hours. After the reaction, the precipitated inorganic salt was separated, the solvent was distilled off, and the residue was
Colorless crystals with a melting point of 93-4℃ recrystallized from alcohol
Obtained 473g. Elemental analysis value (C ₃₉ H ₆₀ O ₄ ) Unit: % Calculated value C: 79.05 H: 10.14 Experimental value C: 78.92 H: 10.31 Synthesis example 3 (synthesis of exemplified compounds (9) and (19)) 6,6'-dihydroxy-7,7'-dimethyl-
4,4,4',4'-tetra-methyl-bis-2,
Dissolve 36.8 g of 2'-spirochroman in 90 ml of 10% aqueous sodium hydroxide solution, cool with water, and add 36 g of caprylic acid chloride dropwise while stirring. After dropping, react at room temperature for 1 hour, add 150 ml of water after reaction,
Extract with ether. The ether layer was washed with dilute aqueous sodium hydroxide solution to remove unreacted 6,6'-dihydroxy-7,7'-dimethyl-4,4,4',4'-tetramethyl-bis-2,2'-spirochroman. remove. Thereafter, the ether layer was washed with water, dried over anhydrous sodium sulfate, and the ether was distilled off to obtain a candy-like substance, which contained exemplified compounds (9) and (19) in a ratio of about 1:3. ing. In practice, there is no problem in using it as it is, but it can be further purified by the method shown below. Both were separated and purified by column chromatography, and exemplary compound (19) was further purified by distillation to obtain 37.3 g of a candy-like substance with a concentration of 230-400/0.02 mmHg.
I got it. It was confirmed to be the desired product by NMR IR elemental analysis. Elemental analysis value (C ₃₉ H ₅₆ O ₆ ) Unit: % Calculated value C: 75.44 H: 9.09 Experimental value C: 75.36 H: 9.25 On the other hand, exemplified compound (9) is a viscous liquid that cannot be distilled and is further subjected to column chromatography. Crystal 11.4g by E
I got it. It was confirmed to be the desired product by NMR IR elemental analysis. Elemental analysis value (C ₃₁ H ₄₂ O ₅ ) Unit: % Calculated value C: 75.27 H: 8.56 Experimental value C: 75.33 H: 8.74 Synthesis example 4 (synthesis of compound example (18)) 6,6'-dihydroxy-7 ,7'-dimethyl-
4,4,4',4'-tetramethyl-bis-2,2'-
Dissolve 365g of spirochroman in 600ml of pyridine,
While stirring, 390 g of benzenesulfonic acid chloride is added dropwise at 30-35°C. After dropping, react at 50-55°C for 2 hours. After reaction, add 780 ml of concentrated hydrochloric acid, 1 ml of water
When poured into a mixture of , methanol and 2, crystals precipitate. The crystals were washed with methanol and recrystallized with a mixture of 1:1 methanol and acetone (1:1) to obtain 434 g of white prismatic crystals. mp198~200℃
It was confirmed to be the desired product by NMR, IR, and elemental analysis. Elemental analysis value (C ₃₅ H ₃₆ O ₈ S ₂ ) Unit: % Calculated value C: 64.75 H: 5.55 S: 9.88 Experimental value C: 65.01 H: 5.53 S: 10.12 In the present invention, together with the compound represented by the general formula [] Any UV absorber can be used, but thiazolidone-based, benztriazole-based, acrylonitrile-based and benzophenone-based UV absorbers are preferred, and these UV absorbers are described, for example, in U.S. Pat. No. 2685512, No. 2739888, No. 2784087,
Same No. 2748021, Same No. 3004896, Same No. 3052636
No. 3215530, No. 3253921, No. 3253921, No. 3215530, No. 3253921, No.
No. 3533794, No. 3692525, No. 3705805, No. 3707375, No. 3738837, No. 3754919,
It is described in British Patent No. 1321355. In the present invention, the following general formula [-1], [-
In particular, the ultraviolet absorber represented by the general formula [-
1] is preferred. Here, R ₁₀ is a hydrogen atom or an acyl group which may have a substituent, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ ,
R ₁₆ , R ₁₇ and R ₁₈ are hydrogen atoms, halogen atoms,
Alternatively, it represents an alkyl group which may have a substituent. ] 〓〓〓〓〓
[In the formula, R ₂₀ is a hydrogen atom, or -OR′ ₂₀ ,
R′ ₂₀ is a hydrogen atom or a flexible alkyl group having 1 to 5 carbon atoms having a substituent, R ₂₁ is a hydrogen atom,
1 to 18 carbon atoms, each of which may have a substituent
Among the alkyl groups of and compounds represented by general formula [-1], compounds useful in the present invention include:
The following general formula [-1-a] or [-1-b]
This includes compounds represented by In general formulas [-1-a] and [-1-b], R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ ,
R ₁₇ and R ₁₈ have the same meaning as in general formula [-1], R' ₁₀ is R ₁₀ , R' ₁₁ is R ₁₁ , R' ₁₂ is
R ₁₂ , R′ ₁₃ is R ₁₃ and R′ ₁₄ is R ₁₄ , R′ ₁₅ is R ₁₅ , R′ ₁₆ is
R ₁₆ ^and R' ₁₇ have the same meanings as R ₁₇ and R' ₁₈ have the same meanings as R ₁₈ , and X' and Y each represent alkylene which may have a substituent. Typical specific examples of ultraviolet absorbers used in the present invention are shown below. 〓〓〓〓〓
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In addition to the patents mentioned above, these UV absorbers are
For example, U.S. Patent Nos. 3215530, 2719086, 3112338, 3168492, 3206431,
Same No. 3042669, Same No. 3794493, Same No. 3936305
No. 3004896, No. 3159646, No. 3159646, No. 3004896, No. 3159646, No.
No. 3253921, No. 3282886, No. 3533794, No. 3692525, No. 3705805, No. 3738837,
It can be easily synthesized according to the methods described in British Patent No. 3754919 and British Patent No. 879144. The compound represented by the general formula [] is known as an anti-fading agent, but although this compound has an effect of preventing dye fading against visible light, it does not have an anti-fading effect against ultraviolet rays. However, the present inventor has found that by combining the compound represented by the general formula [] with an ultraviolet absorber, it not only has the effect of preventing dye fading against both visible light and ultraviolet rays, but also significantly increases the effect of preventing dye fading against visible light. This is a synergistic effect that could not be expected from the combination of known dye fading inhibitors and ultraviolet absorbers. Furthermore, in the present invention, when at least one of the compounds represented by the general formulas [], [] and [] is further combined, an even more excellent dye fading inhibitor is obtained. [In the formula, A is a simple bond, a sulfonyl group, a sulfinyl group, -O-, -S-, -S-S-, -CH ₂
-O-CH ₂ -, -CH ₂ -S-CH ₂ -,

【formula】

[Formula] -O-(CH ₂ ) _n -O- or

[Formula] A ₁ , A ₂ , A ₃ and A ₄ are halogen atoms, carboxy groups, alkyl groups having 1 to 18 carbon atoms, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups , arylthio group,
Alkoxycarbonyl group, aryloxycarbonyl group, acylamino group, acyloxy group, -
SO ₂ A ₉ , -SO ₃ A ₉ , substituted or unsubstituted amino group,

[Formula] or (-CH ₂ )- _o B, A ₅ is a hydrogen atom, an alkyl group, or an aryl group,
A ₆ and A ₇ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aryl groups, or
A ₆ and A ₇ combine with each other to substitute or unsubstitute 5 to 6
A ₈ is a hydrogen atom or a methyl group, A ₉ is an alkyl group or an aryl group, A ₁₀ and A ₁₁ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an aralkyl group. Alternatively, A ₁₀ and A ₁₁ may be bonded to each other to form a substituted or unsubstituted 5- to 6-membered ring, and B is alkoxy〓〓〓〓〓
carbonyl group or

[Formula] and m and n represent integers of 1 to 3. ] [In the formula, A ₁₂ is a secondary or tertiary alkyl group having 3 to 20 carbon atoms, A ₁₃ is a hydrogen atom, substituted,
Unsubstituted alkyl group having 1 to 20 carbon atoms, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, acyl group, acylamino group, alkyl Amino group, arylamino group or dialkylamino group and _A14 represent hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, aryl group, aralkyl group, arylthio group, arylsulfinyl group, arylsulfonyl group . however,
When A ₁₃ is an alkoxy group, aryloxy group or aralkyloxy group, A ₁₄ is never a hydrogen atom. [In the formula, A ₁₅ and A ₁₆ are hydrogen atoms, halogen atoms, hydroxy groups, carboxy groups, aralkyl groups, alkoxy groups having 1 to 5 carbon atoms, aryl groups, arylthio groups, arylsulfinyl groups,
Arylsulfonyl group, aryldithio group or alkyl group having 1 to 4 carbon atoms, A ₁₇ is substituted,
Unsubstituted alkyl group having 1 to 5 carbon atoms, aryl group, aralkyl group, alkoxy group having 1 to 4 carbon atoms, aryloxy group, alkylthio group having 1 to 4 carbon atoms, arylthio group, 1 carbon atom
-5 alkoxycarbonyl group, dialkylamino group, arylamino group or heterocyclic amino group and A ₁₈ and A ₁₉ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] In the above general formulas [], [] and [], the halogen atom is, for example, each atom such as chlorine or bromine, and the alkyl group is, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl, sec-butyl, t-butyl, n-amyl, t-amyl, t-hexyl, n-octyl, t-octyl, decyl, n-dodecyl, t-
Each group such as dodecyl, aryl group such as phenyl group, aralkyl group such as benzyl group, alkoxy group such as methoxy,
Ethoxy and butoxy groups, aryloxy groups such as phenyloxy groups, aralkyloxy groups such as benzyloxy groups, alkylthio groups such as methylthio, ethylthio, butylthio and octylthio groups, and arylthio groups such as phenylthio groups. Examples of substituted amino groups include methylamino, ethylamino, octylamino, and phenylamino groups; examples of secondary or tertiary alkyl groups having 3 to 20 carbon atoms include i-propyl, sec-
Butyl, t-butyl, sec-amyl, t-amyl, t-hexyl, t-octyl, t-dodecyl, t-tetradodecyl, sec-octadecyl,
Examples of the 5- to 6-membered carbon ring formed by bonding each group such as t-octadecyl, t-octadicyl, and t-eicosyl, and A ₆ and A ₇ to each other include cyclopentane, cyclohexane, and cyclohexamonoene rings. Examples of the 5- to 6-membered ring formed by bonding A ₁₀ and A ₁₁ to each other include rings such as pyridine and piperidine. In addition, typical examples of the substituent include those similar to those of the compound represented by the general formula []. Among the compounds represented by the general formulas [], [] and [], those represented by the general formula [] are preferred. In the general formula [], A is a simple bond, a sulfonyl group, a sulfinyl group, -O-, -S-, -
〓〓〓〓〓
S-S-,

[Formula] -O-(CH ₂ ) _n -O- or

[Formula] A ₁ , A ₂ , A ₃ and A ₄ are carboxy groups, carbon thickness number 1 to 18
alkyl group or alkoxy group (A ₁ , A ₂ ,
The total number of carbon atoms in A ₃ and A ₄ is preferably 32 or less. ), A ₆ and A ₇ are hydrogen atoms, number of carbon atoms is 1
~10 alkyl groups or substituted or unsubstituted aryl groups and A ₈ preferably have a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Also, in the general formula [], the general formula [−
Compounds represented by [a] and [-b] are preferred. In general formula [-a] and [-b]
A ₁ , A ₂ , A ₃ , A ₄ and A have the same meanings as in the general formula [], but it is preferred that at least one of A ₁ and A ₂ has a tertiary alkyl group. Next, typical examples of the compounds represented by the above general formulas [], [] and [] will be listed. 〓〓〓〓〓
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Compounds represented by the above general formulas [], [] and [] are described, for example, in US Pat. No. 2,792,428 and US Pat.
It can be easily synthesized according to the method described in No. 2796445, No. 2841619, and Journal of the Chemical Society, page 243 (1954). The compounds represented by the general formulas [ ], [ ], [ ] and [ in the present invention may be contained in any layer constituting the color photographic material, but are preferably contained in the dye image forming layer. It may also be contained in other layers, such as a layer adjacent to the dye image forming layer. The ultraviolet absorber in the present invention may be contained in the dye image forming layer or its adjacent layer together with the compounds represented by the above general formulas [], [], [] and [], The compounds represented by [] and [] may be contained in a separate layer, for example, an adjacent layer. The compounds represented by the general formulas [ ], [ ], [ ] and [ ] and the ultraviolet absorbers (hereinafter referred to as compounds of the present invention) in the present invention are oil-soluble, and are generally disclosed in U.S. Pat.
No. 2801171, No. 2272191 and No.
It is preferable to dissolve it in a high boiling point solvent, optionally in combination with a low boiling point solvent, according to the method described in No. 2304940, disperse it, and add it to a hydrophilic colloid solution such as a silver halide emulsion. At this time, if necessary, a coupler, a hydroquinone derivative, a known anti-fading agent, etc. may be used in combination. Further, to explain in detail the method of adding the compound of the present invention, the compound of the present invention is added to organic acid amides, carbamates, esters, ketones, etc. at the same time as a coupler, a hydroquinone derivative, or a known anti-fading agent, etc., as required. , urea derivatives, etc., especially di-n-butyl phthalate, tricresyl phosphate, di-isooctyl azelate, di-n-
-Butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl, caprylamidobutyl, n-pentadecyl phenyl ether, triphenyl phosphate, di-octyl phthalate, n-nonylphenol, N,N- High boiling point solvents such as diethyl laurylamide, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di-o-chlorophenyl phosphate or fluorinated paraffin, as necessary. Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexanetetrahydrofuran, methyl alcohol, ethyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol monoacetate, acetylacetone, nitromethane ,
Dissolved in low boiling point solvents such as nitroethane, carbon tetrachloride, chloroform (these high boiling point solvents and low boiling point solvents may be used alone or in combination), such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids. Mix with an aqueous solution containing a hydrophilic binder such as gelatin containing an anionic surfactant and/or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate, and use a high-speed rotary mixer, colloid mill or ultrasonic dispersion. It can be emulsified and dispersed in a device or the like and added to a silver halide emulsion for use. The compounds of the present invention are also disclosed in U.S. Patent Nos. 2269158, 2852382,
2772168, 3619195, 2801170 specification, JP 51-59942, 51-59943, 49-
No. 74538, No. 50-17637, No. 51-25132, No. 51
It can also be easily dispersed by a dispersion method using a latex solution such as that described in Japanese Patent No. 110327. The compound of the present invention may be dispersed alone by the above-mentioned dispersion method and added to a silver halide emulsion or a hydrophilic colloid solution. If the coupler used at this time is diffusive, the coupler is added to the color developer,
The compound of the present invention may be emulsified and dispersed and added to a silver halide emulsion or the like 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. Although the amount of the compound of the present invention to be added is not particularly limited, the compound represented by the above general formula Preferably 5-300% by weight〓〓〓〓〓
In particular, it is preferably 10 to 100% by weight, and in silver halide color photographic light-sensitive materials containing no coupler, it is preferably 10 to 100% by weight per mole of silver halide.
g, especially 15 to 60 g is preferred. On the other hand, the amount of the compound represented by the above general formulas [], [] and [] and the ultraviolet absorber to be added, even in a silver halide color photographic light-sensitive material containing a coupler, is as follows:
Also, in silver halide color photographic light-sensitive materials containing no coupler, the amount is preferably 1 to 300% by weight, particularly preferably 2 to 100% by weight, based on the compound represented by the general formula []. Furthermore, there is nothing wrong with using two or more of each of the compounds of the present invention. In this case as well, the same amount as mentioned above is sufficient. Hydroquinone derivatives used in conjunction with the compounds of the present invention include compounds represented by the following general formula []. In the formula, R ₂₀ is an alkyl group (e.g. methyl, t-
Butyl, t-amyl, octyl, t-octyl,
dodecyl, octadecyl, etc.), aryl groups (e.g., phenyl), alkoxy groups (e.g., methoxy, butoxy, dodecyloxy, etc.), aryloxy groups (e.g., phenoxy, etc.), carbamoyl groups (e.g., methylcarbamoyl, dibutylcarbamoyl, octadecylcarbamoyl, nylcarbamoyl, etc.), sulfamoyl groups (e.g. methylsulfamoyl, octadecylsulfamoyl, etc.), acyl groups (e.g. acetyl, octanoyl, lauroyl, etc.), alkoxycarbonyl groups (e.g. methoxycarbonyl, dodecyloxycarbonyl, etc.) or aryloxycarbonyl groups. represents a group (for example, phenyloxycarbonyl, etc.), and the alkyl and aryl in the above groups are halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, carboxy groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and acyl groups. , an acyloxy group, a carbamoyl group, a sulfo group, a sulfamoyl group, a sulfonamido group, an N-alkylamino group, an N-arylamino group, an acylamino group, an imide group, a hydroxy group, etc. Also, one to three of the remaining three hydrogen atoms on the aromatic nucleus of hydroquinone are halogen atoms and
It can be substituted by one to three groups (which may be the same or different) as defined for R ₁₀ . Specific examples of nuclear-substituted hydroquinones used in the present invention include, for example, US Pat. No. 2,336,327;
No. 2360290, No. 2384658, No. 2403721, No. 2360290, No. 2384658, No. 2403721, No.
No. 2418613, No. 2675314, No. 2701197, No.
No. 2704713, No. 2710801, No. 2722556, No.
No. 2728659, No. 2732300, No. 2735765, No. 2735765, No. 2732300, No. 2735765, No.
No. 2816028, No. 3062884, No. 3236893, British Patent No. 557750, Specification of British Patent No. 557802, West German Published Patent No. 2149789, Japanese Patent Publication No. 1973-54116, Japanese Patent Publication No. 1973-2128
Publication, Journal of Organic Chemistry No.
It is described in Volume 22, pages 772-774, etc. Among nuclear-substituted hydroquinone derivatives, those containing 8 or more carbon atoms in total in substituents on the nucleus have low diffusivity and are suitable for selectively existing in a specific hydrophilic layer of a photosensitive material. . Among the hydroquinone derivatives used in the present invention, those in which the substituent on the nucleus is a substituted or unsubstituted alkyl group are particularly useful. Specific examples of hydroquinone derivatives used in the present invention are shown below. (H _q-1 ) 2,5-di-tert-octylhydroquinone (H _q-2 ) 2-t-octyl-5-methylhydroquinone (H _q-3 ) 2,6-di-n-dodecyl-hydroquinone ( H _q-4 ) 2-n-dodecylhydroquinone (H _q-5 ) 2,2'-methylenebis-5,5'-t-butylhydroquinone (H _q-6 ) 2,5-di-n-octyl-hydroquinone (H _q-7 ) 2-dodecylcarbamoylmethylhydroquino〓〓〓〓〓
(H _q-8 ) 2-(β-n-dodecyloxycarbonyl)ethyl-hydroquinone (H _q-9 ) 2-(N,N-dibutylcarbamoyl)hydroquinone (H _q-10 ) 2-n-dodecyl- 5-Chloro-hydroquinone (H _q-11 ) 2-(2-octadecyl)-5-methylhydroquinone (H _q-12 ) 2,5-di-(p-methoxyphenyl)hydroquinone (H _q-13 ) 2 -t-Octylhydroquinone (H _q-14 ) 2-[β-{3-(sulfobenzamide)benzamide}ethylhydroquinone (H _q-15 ) 2,5-dichloro-3,6-diphenylhydroquinone (H _{q- 16} ) 2,6-dimethyl-3-t-octylhydroquinone (H _q-17 ) 2,3-dimethyl-5-t-octylhydroquinone (H _q-18 ) 2-{β-(dodecanoyloxy)ethyl}carbamoyl Hydroquinone (H _q-19 ) 2-dodecyloxycarbonylhydroquinone (H _q-20 ) 2-{β-(4-octanamidophenyl)ethyl}hydroquinone (H _q-21 ) 2-Methyl-5-dodecylhydroquinone These Hydroquinone derivatives may be used alone or in combination of two or more, and the amount added is usually 0.01 to 10 mol per mol of coupler in a silver halide color photographic light-sensitive material containing a coupler, particularly 0.1 to 10 mol. 3 mol is preferable. In addition, in the case of silver halide color photographic light-sensitive materials that do not contain couplers, 0.01
-1.0 mol is preferred, particularly 0.02-0.6 mol. Any coupler can be used as the dye image-forming coupler that can be used in the silver halide color photographic light-sensitive material according to the present invention. Among these, the yellow dye image-forming couplers are of the benzoylacetanilide type, pivaloylacetanilide type, dibenzoylmethane type, or those in which the carbon atom at the coupling position is substituted with a substituent that can be eliminated in the coupling reaction (so-called split-off group). The magenta dye image-forming couplers include 5-pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, indazolone, cyanoacetyl, or 2-equivalent type having a split-off group. The cyan dye image-forming coupler is a two-equivalent cyan dye image-forming coupler having a phenol type, naphthol type or split-off group. 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%, preferably 10 to 30 mol%, based on the silver halide. and when present in the developer, generally 0.5 to 3.0 g/, preferably 1.0 to 2.0
Used in g/. In this case, each of the yellow, magenta, and cyan couplers may be used alone or in combination of two or more kinds, and when two or more kinds are used in combination, the above-mentioned amounts are sufficient. Next, the present invention will be specifically explained using examples. Example 1 A solution of the magenta coupler shown in Table 1-1, the compound of the present invention, and a hydroquinone derivative dissolved in the solvent shown in the same table was added to 500 ml of a 5% gelatin aqueous solution containing 2.5 g of sodium dodecylbenzenesulfonate. , dispersed with a homogenizer, and the resulting dispersion was mixed with 1000 c.c. of green-sensitive silver chlorobromide (containing 85 mol% silver bromide) emulsion solution (halogenated)
10 ml of a 2% methanol solution of N,N',N''-triacryloyl-6H-s-triazine as a hardening agent was added to a polyethylene-coated paper (containing 3.5 × 10 ^-1 moles of silver) and Anatase-type titanium oxide is used as the added white pigment, and on the surface of the support, it has a wavelength of about 25 nm in the ultraviolet region of the spectrum in the range of about 360 to 400 nm.
% or more (coated silver amount: 5 mg/100 cm ² ) to obtain a sample of a silver halide color photographic light-sensitive material. As ultraviolet absorbers, [u-4] 5g, [u-12] 3g, [u-
13] 3 g and [u-14] 5 g were dissolved in 50 c.c. of ethyl acetate (EA) and 16 c.c. of dibutyl phthalate (DBP), followed by 250 c.c. of a 5% aqueous gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate. After adding to the hardener solution, it was dispersed using a homogenizer, and 10 ml of the above hardener solution was added and applied. The sample thus obtained was subjected to optical wedge exposure and then photographically processed according to the processing method shown below, and then subjected to a spectral degradation test (SPW-type manufactured by Suga Test Instruments Co., Ltd.). After 800 hours of exposure, the concentration before exposure (D ₀ =
1.0) using a Sakura color densitometer PD-6 model ( _manufactured by Konishiroku Photo Industry Co., Ltd.). The rate was measured using blue light and the results are shown in Tables 1-2. Processing process (30℃) Processing time Color development...3 minutes 30 seconds Bleach-fixing...1 minute 30 seconds Washing with water...2 minutes Stabilization...1 minute Drying Composition of color developer: [A] Benzyl alcohol 5.0ml Sodium hexametaphosphate _2.5g Anhydrous sodium sulfite _1.9g Sodium bromide 1.4g Potassium bromide 0.5g Boric acid ( _Na2B4O7・_10H2O ) 39.1g N-ethyl-N-β-methanesulfonamidoethyl-4 -aminoaniline sulfate
Add 5.0g water to make 1, and adjust the pH to 10.30 using sodium hydroxide. Bleach-fix composition: Iron ammonium ethylenediaminetetraacetate
61.0g Diammonium ethylenediaminetetraacetate
5.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g Add water to make 1, and use aqueous ammonia.
Adjust to PH6.5. Stabilizing liquid composition: Permanent acetic acid 20 ml Add water 800 ml, add sodium acetate and adjust the pH.
After adjusting to 3.5-4.0, add more water to bring it to 1. Color developer composition: [B] Water 800 ml Sodium hexametaphosphate 0.5 g Anhydrous sodium sulfite 2.0 g 4-Amino-3-methyl-N,N-diethylaniline hydrochloride 2.0 g Sodium carbonate 20.0 g Sodium bromide 1.73 g With water Finish to 1 and adjust the pH using ammonia water.
Adjust to 10.86. The steps when using color developer [B] are: color development at 322°C for 1 minute and 30 seconds, bleach-fixing for 50 seconds, and washing with water for 30 seconds. 〓〓〓〓〓

[Table] 〓〓〓〓〓

【table】

【table】

[Table] 〓〓〓〓〓

【table】

[Table] 〓〓〓〓〓

[Table] As shown in Table 1-2, the compounds used in combination in the present invention have a dye fading prevention effect and Y
- It has a stain prevention effect, and it can be seen that the effect is dramatically improved by the combination of the compounds represented by the general formulas [ ], [ ], [ ] and [ ] and the ultraviolet absorbing agent. Table 1-3 shows the results obtained when sample (6) in Table 1-1 was treated with a developer having the color developer composition [B].

[Table] As shown in Tables 1-3, it can be seen that the color photographic material of the present invention has excellent fading prevention effects and Y-stain prevention effects even when the developing agent is changed. Example 2 A sample was prepared under the same conditions as in Example 1, except that the ultraviolet absorber shown below was used instead of the ultraviolet absorber used in Example 1. This sample was treated and measured according to the method shown in Example 1.

[Table] Regarding the total of 169 types of samples obtained in this way,
Comparative samples were prepared in the same manner as in Example 1, and the dye residual rate and Y-stain increase rate were measured. Although there are some differences between the obtained results among the UV absorbers, they all show the same tendency as the results shown in Example 1, indicating that the effectiveness of the present invention is maintained even when the UV absorber is changed. confirmed. Example 3 A solution of the compound yellow coupler and hydroquinone derivative of the present invention shown in Table 2-1 dissolved in the solvent shown in the same table was added to 500 c.c. of a 5% aqueous gelatin solution containing 3.0 g of sodium dodecylbenzenesulfonate. After addition, disperse with a homogenizer〓〓〓〓〓
The resulting dispersion was converted into a blue-sensitive silver chlorobromide emulsion (95
Silver halide emulsion coating solution 1000c.c. (contains silver halide 4.0×10 ^-1 ml) containing mol% silver bromide)
and 2-hydroxy-4,6 as a hardening agent.
-dichloro-S-triazine sodium salt 4%
After adding 5 ml of aqueous solution and coating on polyethylene coated paper, 12 g of ultraviolet absorber (U-15) EA50 c.c., dibutyl phthalate 10 c.c.
After adding it to 250 c.c. of a 5% aqueous gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate, it was dispersed with a homogenizer, and 5 ml of the above hardening agent solution was added. The amount of UV absorber applied was 7 mg/100.
It was applied to a volume of cm ² . These samples were exposed to light so that the color density after development was 1.0, and then processed using the processing method shown in Example-1 and exposed using the method of Example-1 to determine the dye residual rate using blue light. The results are shown in Table 2-2.

【table】

【table】

[Table] 〓〓〓〓〓

[Table] Samples prepared using a similar method.
As shown in Table 2-2, the compound of the present invention also shows an effect on the light resistance of yellow dye, and this effect can be further improved by using the compounds represented by the general formulas [], [] and [] in combination. This shows that ideal quality can be achieved by using a UV absorber at the same time. Example 4 A solution of the compound of the present invention shown in Table 3-1, a cyan coupler, an ultraviolet absorber, and 0.3 g of 2,5-di-t-octylhydroquinone dissolved in the solvent shown in the same table was mixed with dodecylbenzenesulfone. 500 c.c. of 5% aqueous gelatin solution containing 3.0 g of sodium chloride.
The resulting dispersion was added to a coating solution containing 1000 c.c. (silver halide) containing a red-sensitive silver chlorobromide emulsion (containing 90 mol% silver bromide).
3.5×10 ^-1 mol), 10 ml of a 2% methanol solution of N,N',N''-triacryloyl-6H-S-triazine as a hardening agent was added, and the mixture was coated on polyethylene coated paper and dried. Color photographic materials are obtained.After processing these samples, the color density increases.
1.0, processed using the processing method shown in Example 1, conducted a light fastness test using the method of Example 1, measured the dye residual rate using red light, and reported the results in Section 3-3. It is shown in Table 2. Incidentally, the ultraviolet absorber used in Example 1 was applied to the upper layer of the sample at a concentration of 5 mg/100 cm ² .

[Table] 〓〓〓〓〓

【table】

[Table] As shown in the results in Table 3-2, it can be seen that the samples of the present invention have excellent dye residual rates. Example 5 Polyethylene coated paper (anatase type titanium oxide was used as a white pigment added to the polyethylene layer, and the particle diameter was about 360 to 400 nm on the support surface)
A color photographic material was prepared by sequentially coating each of the following layers from the support side onto a support having an average reflectance of about 25% or more for ultraviolet rays. 1st layer: A blue-sensitive silver halide emulsion containing a yellow coupler (silver chlorobromide emulsion containing 97 mol% silver bromide, containing 470 g of gelatin per mole of silver halide, having the following structure per mole of silver halide) sensitizing dye It was sensitized using 2.5×10 ^-4 mol and coated with a yellow coupler (containing 30 mol % of yellow coupler per mol of silver halide) at a silver amount of 400 mg/m ² . 2nd layer; ultraviolet absorber (U-4) 4g (U-4)
12) 2g (u-13) 2g and (u-14) 4g and 2,5-di-t-butylhydroquinone 5
g in DBP16c.c. and EA 50c.c., containing 2.5g of sodium dodecylbenzenesulfonate.
% gelatin aqueous solution and then dispersed with a homogenizer until the total amount of ultraviolet absorber is 400mg/
It is applied so that it becomes 100cm ² . Third layer: green-sensitive silver halide emulsion containing magenta coupler (silver chlorobromide emulsion containing 90 mol% silver bromide, 500 g of gelatin per mol of silver halide)
A sensitizing dye containing the following structure per mole of silver halide
2.5×10 ^-4 mol and containing 20 mol % coupler per mol of silver) at 3.8 mg/mol of silver.
It is applied so that it becomes ^m2 . In addition, as an anti-irradiation dye. It contains 1.8g per mole of silver. 4th layer: 500% ultraviolet absorber used in the 2nd layer
The gelatin layer contains mg/ ^m2 . 5th layer; red-sensitive silver halide emulsion containing a cyan coupler (silver chlorobromide emulsion containing 90 mol% silver bromide, containing 700 g of gelatin per mol of silver halide, having the following structure per mol of silver halide) sensitizing dye 2.5 x 10 ^-3 mol and containing 30 mol % coupler per mol of silver) at 300 mg/mol of silver.
It is applied so that it becomes ^m2 . In addition, as an anti-irradiation dye. It contains 5g per mole of silver. 6th layer: Gelatin layer coated with 120mg/m ² of gelatin. 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. 46-7772, and chemically treated with sodium thiosulfate pentahydrate. 4- as a sensitizer and stabilizer
Contains hydroxy-6-methyl-1,3,3a-7-tetrazaindene, N,N',N''-triacryloyl-6H-S-triazine as a hardening agent, and saponin as a coating aid. Compounds of the present invention and couplers added to each emulsion layer
- was dispersed, added, and used under the conditions shown in Table 4-1.

[Table] After drying the sample, it was exposed to blue light, green light, and red light respectively (exposed so that the color density after development was 1.0), and then subjected to the same processing method as in Example 1, and as a comparative sample. Comparative sample-1 is a sample prepared by removing the ultraviolet absorber from the second and fourth layers. Comparative sample-2 is a sample prepared by removing the compound represented by the general formula [ ] from the first, third, and fifth layers. Comparative sample-3 is a sample prepared by removing the compound represented by the general formula [] from the first, third, and fifth layers. Comparative sample-4 is a sample prepared by removing the compounds represented by the general formulas [] and [] from the first, third, and fifth layers. Comparative sample-5 is a sample prepared by removing the compound represented by the general formula [ ] [ ] from the first, third, and fifth layers and the compound represented by the general formula [ ] from the second and fourth layers. In addition, in the case of sample 2, only the ultraviolet absorber was removed from the second layer, and the amount of ultraviolet absorber applied in the fourth layer was 300.
mg/ ^m2 , and add 400 mg/m2 of the ultraviolet absorber used in the second layer to the first and fifth layers.
mg/m ² and 200 mg/m ² and coated. 〓〓〓〓〓
Example 6 Exemplified compound (21) 18.5 g (P-60) 10 g (u-
15) 8g (H _q-1 ) 2g of DBP20c.c. and EA40c.c.
After dissolving in 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate (120 c.c.), it was dispersed with a homogenizer, and the resulting dispersion was transformed into a green-sensitive silver chlorobromide emulsion (containing 20 mol% silver chloride). 300c.c.
The mixture was then coated on polyethylene coated paper and dried to obtain a color photographic material. After exposing this color photographic material to light wedge exposure according to the sensitometric method,
Processed at a temperature of ℃. Processing process First development 5 minutes Water washing 4 minutes Exposure Color development 3 minutes Water washing 4 minutes Bleaching 4 minutes Fixing 4 minutes Water washing 10 minutes The first developer, color developer, bleach solution and fixer are as follows. A prescribed treatment solution was used. First developer formulation Anhydrous sodium bisulfite 8.0g Phenidone 0.35g Anhydrous sodium sulfite 37.0g Hydroquinone 5.5g Anhydrous sodium carbonate 28.2g Sodium thiocyanide 1.38g Anhydrous sodium bromide 1.30g Potassium iodide (0.1% aqueous solution) 13.0ml in water 1 finish (adjusted to PH9.9) Color developer formulation Anhydrous sodium sulfite 10.0 g N,N-diethyl-p-phenylenediamine hydrochloride 3.0 g Magenta coupler (M-19) 2.0 g 1 Finish with sodium hydroxide Set the pH to 11.5. (M-19): 1-(2,4,6-trichlorophenyl)-3-(4-nitroanilino)-5-pyrazolone bleaching solution formulation Anhydrous sodium bromide 43.0 g Red blood salt 165.0 g Borax (Na ₂ B ₄ O ₇・10H ₂ O) 1.2 g Finish to 1 with water. Fixer formulation Sodium thiosulfate (pentahydrate) 200 g Anhydrous sodium sulfate 100 g Anhydrous disodium phosphate 15.0 g Finish with water. The dye residual rate and Y-stain increase rate in the unexposed area were determined in the same manner as in Example-1, except that the obtained color photographic material was exposed for 200 hours using a xenon fade meter, and are shown in Table 5-1. We obtained the following results.

[Table] Comparative and reference samples were prepared under the same conditions as shown in Example 1.
From Table 5-1, it can be seen that even so-called external type silver halide color photographic materials containing no coupler have excellent dye fading prevention effects and Y-stain prevention effects. 〓〓〓〓〓

Claims (1)

[Claims] 1. A compound represented by the following general formula [] and the following general formula [-1] in at least one layer on a support.
A color photographic material characterized by containing at least one ultraviolet absorber represented by [-2]. [In the formula, R is R ₆ CO-, an alkyl group or alkenyl group that may each have a substituent, R ₁
each represents an alkyl group or an alkoxy group that may have a substituent, R ₂ and R ₃ represent a hydrogen atom or an alkyl group that may have a substituent, and R' represents a hydrogen atom or a group selected from the above R. ,
R ₆ represents an alkyl group, an alkenyl group, or an aryl group, each of which may have a substituent. [In the formula, R ₁₀ is a hydrogen atom or an acyl group that may have a substituent, R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ ,
R ₁₆ , R ₁₇ and R ₁₈ are hydrogen atoms, halogen atoms,
Alternatively, it represents an alkyl group which may have a substituent. ] [In the formula, R ₂₀ is a hydrogen atom, or -OR′ ₂₀ ,
R′ ₂₀ is a hydrogen atom or a flexible alkyl group having 1 to 5 carbon atoms having a substituent, R ₂₁ is a hydrogen atom,
1 to 18 carbon atoms, each of which may have a substituent
The alkyl groups R ₂₂ , R ₂₃ and R ₂₄ are a hydrogen atom hydroxy group, each a carbon atom which may have a substituent.
Represents an alkyl group or alkoxy group having 1 to 18 children. ]