JPS6124706B2 - - 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 material. 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,
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 has wavelengths below 350nm and
425-550nm, yellow dye below 340nm and
400-500nm, cyan dye below 340nm and
It is known that the color fades when exposed to light with a wavelength of 500 to 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, pyroganol, gallic acid and its esters in US Pat. No. 3,069,262, and US Pat. No. 2,360,290. No. and No. 4015990, α-tocopherols and their acyl derivatives, U.S. Pat. 6. Hydroxycoumaran derivatives and Japanese Patent Publication No. 49-20977
It has been proposed to use 6'-dihydroxy-2,2'-bisspirochromans and the like. However, although these compounds do have an effect on the light fastness of dyes, their effect is not sufficient, and their 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, and some compounds have a comparatively poor fading prevention effect on dye images obtained from magenta couplers. However, the reality is that the dye images obtained from yellow and cyan couplers have no fading prevention effect, or even accelerate fading, and are still unsatisfactory. . Therefore, in the past, these known dye fading inhibitors were used in combination,
Alternatively, it has been proposed to use it 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. As a result of studies, the present inventors have found that the above object can be achieved by using a color photographic material containing a combination of at least one compound represented by the following general formula [] and at least one ultraviolet absorber. (In the formula, R is a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aryl group, or heterocyclic group, R ₁ , R ₂ , R ₃ is a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group, respectively. Alkyl group, alkylthio group, alkoxy group, alkenyl group, alkenyloxy group, alkenylthio group, cycloalkyl group, cycloalkyloxy group, cycloalkylthio group, aryl group, aryloxy group, arylthio group, acyl group, acylamino group, diacyl amino group, acyloxy group,
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 ₁ further cyclize with each other to form a chroman or coumaran ring. These chroman or coumaran rings may contain halogen atoms, alkyl groups, alkoxy groups, alkenyl groups, alkenyloxy groups, aryl groups, aryloxy groups, N-substituted amino groups, heterocyclic groups or fused carbocycles. It may be substituted with the forming residue. ) In the general formula [], examples of the alkyl group include methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, dodecyl, octadecyl, and eicosyl, and these alkyl groups may be linear or branched. It may be. Examples of alkenyl groups include vinyl, allyl, and octenyl; cycloalkyl groups include cyclopentyl, cyclohexyl, cycloheptyl, and norbornyl; and aryl groups include phenyl, α-naphthyl, and β-naphthyl. Examples of the heterocyclic group include imidazolyl, benzimidazolyl, furanyl, benzfuranyl, oxazolyl, benzoxazolyl,
5- to 6-membered heterocyclic groups such as laryl, indazolyl, indolyl, morpholino, piperidino, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidyl, pyrrolyl, quinolyl, tetrazolyl, thiazinyl, thiazolyl, benzthiazolyl, thienyl; examples of alkylthio groups include methylthio , ethylthio, butylthio, octylthio, etc.; examples of alkoxy groups include methoxy, ethoxy, butoxy, octoxy, etc.;
Examples of the aryloxy group include phenoxy,
Each group such as α-naphthoxy and β-naphthoxy; arylthio groups include phenylthio; acyl groups include acetyl, propanoyl, butanoyl, octanoyl, dodecanoyl,
Groups such as benzoyl and naphthoyl, acylamino groups such as acetylamino, propanoylamino, butanoylamino, octanoylamino, benzoylamino and naphthoylamino groups, diacylamino groups such as diacetylamino and acetylbenzoyl Examples of groups such as amino, acyloxy groups include acetyloxy, butanoyloxy, octanoyloxy, and benzoyloxy, and examples of sulfonamide groups include methylsulfonamide, amylsulfonamide, phenylsulfonamide, etc. The alkylamino groups include, for example, methylamino, butylamino, and octylamino groups; the alkoxycarbonyl groups include, for example, methoxycarbonyl, ethoxycarbonyl, and butoxycarbonyl; the halogen atoms include, for example, Fluorine,
Atoms such as chlorine and bromine; examples of alkenyloxy groups include vinyloxy, allyloxy, and octenyloxy; examples of N-substituted amino groups include N-alkylamino, N·N-dialkylamino, N- Examples of the groups such as arylamino, N·N-diarylamino, and N-alkyl-N-arylamino and the condensed carbocycle include 5- to 6-membered substituted and unsubstituted carbocycles. In the general formula [], any substituent may be used, such as a halogen atom, a nitro group, a cyano group, a hydroxy group, a carbonyl group,
Sulfo group, alkyl group, cycloalkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, acyl group, acyloxy group, acylamino group , diacylamino group, sulfonamide group, sulfamoyl group, carbamoyl group, sulfonyl group,
Examples include an alkylamino group, an arylamino group, an oxycarbonyl group, and these substituents may be further substituted. Furthermore, in the general formula [], each group preferably has 1 to 30 carbon atoms. Among the compounds represented by the general formula [], the compounds useful in the present invention include the general formulas [a] and [b]
and [c]. R in general formulas [a] and [b],
R ₁ , R ₂ and R ₃ have the same meanings as in the above general formula []. _R4 , _R5 , _R6 , _R7 , _R8 and _R9
represents a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, an _N -substituted amino group, or a _heterocyclic group; may be cyclized with each other to form a carbocycle, and the carbocycle may be further substituted with an alkyl group. In the general formulas [a] and [b],
R is a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or cycloalkyl group (especially an alkyl group or alkenyl group or cycloalkyl group each having 6 to 30 carbon atoms), R ₁ , R ₂
and R ₃ is a hydrogen atom, an alkyl group (especially an alkyl group having 1 to 12 carbon atoms) or a cycloalkyl group, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are hydrogen atoms,
A compound having a halogen atom, an alkyl group or a cycloalkyl group, and an atomic group necessary for R and R ₁ to cyclize each other to form a chroman ring and R ₈ and R ₉ to cyclize each other to form a carbocycle. Particularly useful. Furthermore, among the compounds represented by the general formula [],
Compounds represented by general formula [c] are also included as compounds useful in the present invention. In the general formula [c], R ₁ , R ₂ and R ₃ have the same meanings as in the general formula [],
R′ ₁ , R′ ₂ and R′ ₃ have the same meaning as R ₁ , R ₂ and R ₃ . R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ have the same meanings as in the above general formulas [a] and [b], and R' ₄ , R' ₅ , R' ₆ , R' ₇ , R′ ₈ and R′ ₉ are R ₄ ,
Has the same meaning as R ₅ , R ₆ , R ₇ , R ₈ and R ₉ . X
The carbon chain of the alkylene group is -O-, -S-, -NH
It represents an alkylene group, phenylene group, cycloalkylene group, or divalent heterocyclic group bonded with or without - or -SO _{2 -} . In the general formula [c], R ₁ and R' ₁ are alkyl groups (especially alkyl groups having 1 to 12 carbon atoms), R ₂ , R' ₂ , R ₃ and R' ₃ are hydrogen atoms, R ₄ ,
R′ ₄ , R ₈ , R′ ₈ , R ₉ and R′ ₉ are alkyl groups, R ₅ ,
R′ ₅ , R ₆ , R′ ₆ , R ₇ and R′ ₇ are hydrogen atoms and X is an alkylene group or an alkylene group to which the carbon chains of the alkylene group are bonded with or without -SO ₂ Particularly useful are compounds that have In the present invention, any UV absorber can be used with the compound represented by the general formula [], but thiazolidone-based, benztriazole-based, acrylonitrile-based, and benzophenone-based UV absorbers are preferred; Absorbents are described, for example, in US Pat. No. 1,023,859;
Same No. 2685512, Same No. 2739888, Same No. 2784087
No. 2748021, No. 3004896, No. 3004896, No. 2748021, No. 3004896, No.
3052636, 3215530, 3253921, 3533794, 3692525, 3705805,
Same No. 3707375, Same No. 3738837, Same No. 3754919
No. 1,321,355. As the ultraviolet absorber used in the present invention, benztriazole compounds are preferred, and compounds represented by the general formula [] are more preferred. (In the formula, R ₁₀ is a hydrogen atom, each substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aryl group, or acyl group; substituted sulfonyl group; each N-substituted carbamoyl group or sulfamoyl group; or each substituted or represents an oxalyl group, oxamoyl group, oxycarbonyl group or oxaacetyl group each having an unsubstituted alkyl group, aryl group, alkoxy group or aryloxy group, R ₁₁ ,
R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are hydrogen atoms, halogen atoms, substituted or unsubstituted alkyl groups, alkenyl groups, aryl groups, alkoxy groups, aryloxy groups, acyloxy basis,
Represents an alkylthio group, an arylthio group, an alkylamino group, an acylamino group, a sulfolamide group, a nitro group, a sulfonic acid group or an ester or salt thereof, a carboxylic acid group or an ester or salt thereof, or a heterocyclic group, and R ₄ and R ₅ is _R15 ,
R ₁₆ , R ₁₇ , and R ₁₈ may be ring-closed with adjacent groups to form a 5- or 6-membered carbon ring. ) In the general formula [], an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a halogen atom, an acyloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonamide group,
Examples of the alkylamino group and substituent include those shown in the general formula [],
Examples of carbamoyl groups include methylcarbamoyl, ethylcarbamoyl, octylcarbamoyl, and phenylcarbamoyl; examples of sulfamoyl groups include methylsulfamoyl,
Examples include groups such as ethylsulfamoyl, octylsulfamoyl, dodecylsulfamoyl, and phenylsulfamoyl. Among the compounds represented by the general formula [], compounds useful in the present invention include compounds represented by the following general formula [-1-a] or [-1-b]. 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 the general formula [], R′ ₁₀ is R ₁₀ , R′ ₁₁ is R ₁₁ , R′ ₁₂ is R ₁₂ , R′ ₁₃
are R ₁₃ and R′ ₁₄ are R ₁₄ , R′ ₁₅ is R ₁₅ , R′ ₁₆ is R ₁₆ , R′ ₁₇ is
R ₁₇ and R' ₁₈ have the same meaning as R ₁₈ , and X' and Y each represent a divalent organic residue, e.g.
X' is substituted or unsubstituted alkylene, alkylene dioxy, alkylene diamine,
Alkylene dicarbonyl or alkylene diamide chain; or alkylene having a substituted or unsubstituted arylene group, a divalent heterocyclic residue, or a heteroatom in the chain;
represents an alkylene dioxy, alkylene diamine, alkylene dicarbonyl, or alkylene diamide chain, where Y is a substituted or unsubstituted alkylene chain; a substituted or unsubstituted arylene group, a divalent heterocyclic residue, or a hetero It represents an alkylene chain having atoms; or a bond having carbonyl, sulfonyl, carbamoyl or sulfamoyl residues at both ends of these chains. In general formulas [-1] and [-1-a], R is preferably a hydrogen atom, an alkyl group, an acyl group, an alkyl group, or an arylsulfonyl group. Further, as preferred ultraviolet absorbers that can be used in the present invention, the following general formulas [-2] and [-
3], [-4], [-5], [-6] and [
-7] can also be mentioned. [In the formula, R ₂₀ is a hydrogen atom or -CR′ ₂₀ , R′ ₂₀ is a hydrogen atom or a substituted or unsubstituted carbon atom number of 1 to
5 alkyl group, R ₂₁ is a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an alkoxy group, an aryl group, an aryloxy group, or

[Formula] R′ ₂₁ is a substituted or unsubstituted lower alkyl group, aryl group or aryloxy group, and R ₂₂ , R ₂₃ and R ₂₄ are hydrogen atoms,
It represents a halogen atom, a nitro group, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, an alkyloxy group, an aryl or an aryloxy group. ] [In the formula, R ₂₅ represents a substituted or unsubstituted alkyl group having 4 to 12 carbon atoms. ] [In the formula, R ₂₆ and R ₂₈ represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ₂₇ represents a hydrogen atom or a hydroxy group, but the number of carbon atoms in the alkyl group of R ₂₆ and R ₂₈ is The total sum is 5 or more. ] [In the formula, R ₂₉ and R ₃₀ represent a hydrogen atom or an alkyl group, and R ₃₁ represents a hydrogen atom or a hydroxy group. ] [In the formula, R ₃₂ and R ₃₃ are hydrogen atoms, substituted or unsubstituted alkyl groups, cycloalkyl groups, or aryl groups, R ₃₄ is -CN,

[Formula] or -SO ₂ - R ₃₅ and R ₃₅ each represent a substituted or unsubstituted alkyl group or aryl group having 1 to 10 carbon atoms, and R ₃₂ and R ₃₃ form a substituted or unsubstituted cyclic compound. You may. ] [In the formula, R' ₃₄ represents a substituted or unsubstituted alkylene group, arylene group, or divalent heterocyclic group, respectively. ] These general formulas [-2], [-3], [-
Each atom and group of the compound represented by [4], [-5], [-6] and [-7] has the general formula [-
Examples include compounds similar to those shown in 1]. In the present invention, compounds represented by the general formula [-1] are most preferred as ultraviolet absorbers. Typical specific examples of the compound represented by the above general formula [] are shown below, but the compounds used in the present invention are not limited thereby. The compounds represented by the general formula [ ] of the present invention are disclosed in U.S. Pat.
It is obtained by the method described in No. 3574627, etc., and is also a general alkylation method for some 6-hydroxychromans and 5-hydroxycoumarans. By reacting halides, sulfates or vinyl compounds in the presence of an alkali, or by
American Chemical Society) Vol. 66 No. 1523-5
Page, Journal of the Chemical Society, No.
1850-2 (1958) and 3350-78 (1959)
It can be synthesized by bonding a phenol having an ether bond at the p-position according to the method described in 2006). Typical examples of the ultraviolet absorbent used in the present invention are shown below, but the ultraviolet absorbent used in the present invention is not limited thereto. 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 a dye fading inhibitor, but although this compound has an effect of preventing dye fading against visible light, it does not have an effect of preventing dye fading against ultraviolet rays. However,
The present inventor has discovered 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 prevention effect can be obtained. [In the formula, A' is a simple bond, a sulfonyl group, a sulfinyl group, -O-, -S-, -S-S-, -CH ₂ -
O- _CH2- , _-CH2 -S- _CH2- ,

【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 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group, or A ₆
and A ₇ may combine with each other to form a substituted or unsubstituted 5- to 6-membered carbon ring, 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 is a hydrogen atom, an alkyl group,
Aryl group, heterocyclic group, aralkyl group or
A ₁₀ and A ₁₁ combine with each other to form substituted or unsubstituted 5~
A 6-membered ring may be formed, and B is an alkoxycarbonyl 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, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, or an aryl group. group, aralkyl group, alkoxy group, aryloxy group, aralkyloxy group,
Alkylthio group, arylthio group, aralkylthio group, acyl group, acylamino group, alkylamino group, arylamino group or dialkylamino group, and _A14 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, It represents an aralkyl group, an arylthio group, an arylsulfinyl group, or an 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 [], examples of the halogen atom include atoms such as base and bromine, and examples of the alkyl group include 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-
Various groups such as dodecyl, aryl groups such as phenyl groups, aralkyl groups such as benzyl groups, alkoxy groups such as methoxy, ethoxy, butoxy, and aryloxy groups such as phenyloxy and aralkyloxy groups. Examples include benzyloxy groups, alkylthio groups such as methylthio, ethylthio, butylthio, octylthio, etc., arylthio groups such as phenylthio, substituted amino groups such as methylamino, ethylamino,
Examples of groups such as octylamino and phenylamino, and secondary or tertiary alkyl groups having 3 to 20 carbon atoms include i-propyl, sec-butyl,
Each group such as t-butyl, sec-amyl, t-amyl, t-hexyl, t-octyl, t-dodecyl, t-tetradecyl, sec-octadecyl, t-octadecyl, t-eicosyl, etc., A ₆ and A ₇ are Examples of 5- to 6-membered carbon rings formed by combining with each other include rings such as cyclopentane, cyclohexane, and cyclohexamonoene rings, and 5- to 6-membered rings formed by combining A ₁₀ and A ₁₁ with each other. Examples include rings such as pyridine and piperidine. In addition, typical substituents include those similar to the compounds 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 just a bond,
Sulfonyl group, 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, number of carbon atoms is 1
~18 alkyl or alkoxy groups (A ₁ ,
The total number of carbon atoms of A ₂ , A ₃ and A ₄ is preferably 32 or less. ), A ₆ and A ₇ preferably have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted aryl group, and A ₈ preferably has 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 compounds represented by the above general formulas [], [] and [] will be listed, but the compounds used in the present invention are not limited to these. 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. ,
They may also be included in other layers, such as layers adjacent to the dye image-forming layer. The ultraviolet absorber in the present invention has the general formulas [], [], [] and []
It may be contained together with the compound represented by the dye image forming layer or a layer adjacent thereto, and it may be contained in a layer other than the compound represented by the general formulas [], [], [] and [], for example, in an adjacent layer. It's okay to be hit. 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 device. It can be used by emulsifying and dispersing it with etc. and adding it to a silver halide emulsion. The compounds of the present invention are also disclosed in U.S. Pat. No. 2,269,158, U.S. Pat.
No. 3619195, Specification No. 2801170, JP-A-51-59942, JP-A-51-59943, JP-A-49-74538
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 Publication 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. The amount of the compound of the present invention added is not particularly limited, but the compound represented by the general formula [] is about 15 g per mole of the dye formed by color development treatment.
The presence of the coupler is sufficient, and mainly for economical reasons, in color photographic materials containing the coupler, it is preferably 5 to 300% by weight, particularly preferably 10 to 100% by weight, based on the commonly used coupler. In color photographic materials containing no silver halide, the amount is preferably 10 to 100 g, particularly 15 to 60 g, per mole of silver halide. On the other hand, the amount of the compound represented by the above general formulas [], [] and [] and the ultraviolet absorber to be added is determined in the silver halide color photographic material containing the coupler and in the silver halide color photographic material not containing the coupler. Also, it 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.), an aryl group (e.g. phenyl, etc.), an alkoxy group (e.g. methoxy, butoxy, dodecyloxy, etc.) ), aryloxy groups (e.g., phenoxy), carbamoyl groups (e.g., methylcarbamoyl, dibutylcarbamoyl, octadecylcarbamoyl, phenylcarbamoyl, 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 (e.g. phenyloxycarbonyl, etc.)
In the above groups, alkyl and aryl are halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, carboxy groups,
Alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, carbamoyl group, sulfo group, sulfamoyl group, sulfonamido group, N-alkylamino group, N-arylamino group, acylamino group, imide group, hydroxy group, etc. 1 to 3 halogen atoms of the remaining 3 hydrogen atoms on the aromatic nucleus of hydroquinone and 1 to 3 of the groups defined for _R10 (same or different). may be replaced by Specific examples of the nuclear-substituted hydroquinones used in the present invention include, for example, US Pat.
No. 2384658, No. 2403721, No. 2418613,
Same No. 2675314, No. 2701197, No. 2704713, Same No.
No. 2710801, No. 2722556, No. 2728659, No.
No. 2732300, No. 2735765, No. 2816028, No. 2732300, No. 2735765, No. 2816028, No.
3062884, 3236893, British Patent No. 557750,
Specification No. 577802, West German Published Patent No. 2149789, Japanese Patent Publication No. 44-54116, Japanese Patent Publication No. 46-2128, Journal of Organic Chemistry Vol. 22, 772
It is described on pages ~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 the hydroquinone derivatives used in the present invention are shown below, but the invention is not limited thereto. (Hq-1) 2,5-di-tert-octylhydroquinone (Hq-2) 2-t-octyl-5-methylhydroquinone (Hq-3) 2,6-di-n-dodecyl-hydroquinone (Hq-4 ) 2-n-dodecylhydroquinone (Hq-5) 2,2'-methylenebis-5,5'-di-butylhydroquinone (Hq-6) 2,5-di-n-octyl-hydroquinone (Hq-7) 2 -Dodecylcarbamoylmethylhydroquinone (Hq-8) 2-(β-n-dodecyloxycarbonyl)ethyl-hydroquinone (Hq-9) 2-(N・N-dibutylcarbamoyl)hydroquinone (Hq-10) 2-n-dodecyl -5-chloro-hydroquinone (Hq-11) 2-(2-octadecyl)-5-methylhydroquinone (Hq-12) 2,5-di-(p-methoxyphenyl)hydroquinone (Hq-13) 2-t -Octylhydroquinone (Hq-14) 2-[β-{3-(3-sulfobenzamide)benzamide}ethylhydroquinone (Hq-15) 2,5-dichloro-3,6-diphenylhydroquinone (Hq-16) 2・6-dimethyl-3-t-octylhydroquinone (Hq-17) 2,3-dimethyl-5-t-octylhydroquinone (Hq-18) 2-{β-(dodecanoyloxy)ethyl}carbamoylhydroquinone (Hq- 19) 2-Dodecyloxycarbonylhydroquinone (Hq-20) 2-{β-(4-octanamidophenyl)ethyl}hydroquinone (Hq-21) 2-Methyl-5-dodecylhydroquinone These hydroquinone derivatives alone, Alternatively, two or more types are used in combination, and the amount added is preferably 0.01 to 10 mol, particularly preferably 0.1 to 3 mol, per mol of coupler in silver halide color photographic materials containing couplers. In the case of a silver halide color photographic material containing no coupler, the amount is preferably 0.01 to 1.0 mol, particularly preferably 0.02 to 0.6 mol, per 1 mol of silver halide. Any coupler can be used as the dye image-forming coupler that can be used in the silver halide color photographic 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 coupler is a 2-equivalent type yellow dye image-forming coupler having a 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indazolone type, cyanoacetyl type or split-off type. 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 material according to the present invention is present in the silver halide color photographic material, it is generally used in an amount of 5 to 50 mol%, preferably 10 to 30 mol%, based on the silver halide. and generally when present in the developer.
It is used in an amount of 0.5 to 3.0 g/, preferably 1.0 to 2.0 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. The silver halide emulsion used in the silver halide color photographic material according to the present invention is generally one in which silver halide grains are dispersed in a hydrophilic colloid.
Silver halides include silver chloride, silver bromide, silver iodide,
These are silver chlorobromide, silver iodobromide, 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 conversion method, and the simultaneous mixing method. It will be done. In addition, gelatin and derivative gelatin such as phthalated gelatin and malonated gelatin are generally used as hydrophilic colloids for dispersing silver halide. 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 wavelength range. Preferred sensitizing dyes include, for example, cyanine dyes, merocyanine dyes, or The complex cyanine dyes can be used alone or in combination, and if necessary, a gold compound, a noble metal salt such as platinum, palladium, iridium, rhodium or mutenium, a sulfur compound, a reducing substance or a thioether compound, a quaternary compound, etc. chemical sensitizers such as ammonium salt compounds or polyalkylene oxide compounds; stabilizers such as triazoles, imidazoles, azaindenes, benzothiazoliums, zinc compounds, cadmium compounds, mercaptans; chromium salts, zirconium salts; , mucochloric acid, aldehyde type, triazine type, polyepoxy compound, active halogen compound, ketone compound, acryloyl type, triethylene phosamide type, ethyleneimine type hardening agent; glycerin,
Dihydroxyalkane plasticizers such as 1,5-pentanediol; fluorescent brighteners; antistatic agents;
Various photographic additives such as coating aids can be added individually or in combination of two or more, and the resulting silver halide emulsion contains a dispersion in which the above-described compound of the present invention is dispersed. Furthermore, if necessary, a synthetic resin film such as cellulose acetate, cellulose nitrate, polycarbonate, polyethylene terephthalate, or polystyrene, baryta, etc. A silver halide color photographic material is obtained by coating on a support such as paper, polyethylene-coated paper, or a glass plate. The silver halide color photographic material according to the present invention can also be applied to an internal type silver halide color photographic material containing a coupler or an external type silver halide color photographic material in which a coupler is contained in a developer. This is advantageous for silver oxide color photographic materials, and it is advantageous to carry out color development by a color development method after exposure. 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 in silver halide color photographs containing couplers. It can also be applied to silver halide color photographic materials in which a color developing agent is contained in a layer that does not contain the coupler in the material, and when an alkaline processing solution is permeated, the color developing agent is moved and can come into contact with the coupler. Further, in a silver halide color photographic material for diffusion transfer, the compound of the present invention can be added to the light-sensitive element and/or image-receiving element of the light-sensitive material, and it is particularly advantageous to have it present in the image-receiving element. . In the reversal method, the image is developed with a black and white negative developer, then exposed to white light or treated with a processing solution containing a fogging agent such as a boron compound, and then color developed with an alkaline developer containing a color developing agent. At this time, there is no problem even if a fogging agent is included in an alkaline developer containing a color developing agent. After color development, it is bleached with a bleaching solution containing ferricyanide or a ferric salt of aminopolycarboxylic acid as an oxidizing agent, and then fixed with a fixing solution containing a silver salt solvent such as thiosulfate to form a silver image. Removes the silver halide, leaving a dye image. Instead of using a bleaching solution and a fixing solution, bleach-fixing can also be carried out using a one-bath bleach-fixing solution containing an oxidizing agent such as a ferric salt of an aminopolycarboxylic acid and a silver salt bathing agent such as thiosulfate. Further, in combination with color development, bleaching, fixing, or bleach-fixing, various treatments such as prehardening, neutralization, water washing, termination, and stabilization may be performed. In particular, processing steps in which the silver halide color photographic material of the present invention is advantageously developed include, for example, color development, washing with water if necessary, bleach-fixing, washing with water, stabilizing if necessary, and drying. For example, the processing process is
It is carried out at high temperatures of 30°C or higher and within an extremely short period of time. Aromatic primary amine compounds which are particularly useful color developing agents used for color developing the silver halide color photographic materials of the present invention include primary phenylene diamines, aminophenols and derivatives thereof; For example, the following can be cited as representative examples. 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-carboxymethyl-
2-Methyl-p-phenylenediamine, N-carbamidomethyl-N-ethyl-2-methyl-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・N-diethyl-3
-Methyl-p-phenylenediamine, N-methyl-N-β-sulfoethyl-p-phenylenediamine, o-aminophenol, p-aminophenol, hydrochloric acid of 5-amino-2-oxy-toluene,
Salts of inorganic acids such as sulfuric acid or organic acids such as p-toluenesulfonic acid. Two or more of the above color developing agents may be used in combination. In addition to the above-mentioned color developing agent, various additives are added to the color developing solution as necessary. Main examples include alkali agents such as alkali metal and ammonium hydroxides, carbonates, and phosphates, acetic acid,
Buffers such as boric acid, PH regulators, development accelerators, antifoggants, stain or sludge inhibitors, interlayer effect accelerators, preservatives, etc. Bleaching agents used in bleaching include ferricyanide such as red blood salt, dichromate, permanganate, hydrogen peroxide, mustard powder, and aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and iminodiacetic acid. Metal complexes include metal complexes of polycarboxylic acids such as malonic acid, tartaric acid, malic acid, and diglycolic acid, ferric chloride, and the like, and these may be used alone or in combination as necessary.
Various additives such as bleaching accelerators can be added to this bleaching solution as needed. The fixing agents used in the fixing process include thiosulfates such as sodium thiosulfate and ammonium thiosulfate;
There are cyanide urea derivatives, and in this fixing process, various additives such as fixing accelerators can be added as necessary. EXAMPLES Next, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereto. Example 1 After adding a solution of the magenta coupler shown in Table 1-1, the compound of the present invention and the hydroquinone derivative dissolved in the solvent shown in the same table to 500 ml of a 5% gelatin aqueous solution containing 2.5 g of sodium dodecylbenzenesulfonate. The resulting dispersion was added to 1000 c.c. of a green-sensitive silver chlorobromide (containing 85 mol% silver bromide) emulsion solution, and N・N′・N″− was added as a hardening agent. Triacryloyl-6H-s
- add 10 ml of 2% methanol solution of triazine;
Polyethylene coated paper (anatase type titanium oxide is used as the white pigment added to the polyethylene layer, and it is approximately 360 to 400 nm on the support surface.
A sample of a silver halide photographic light-sensitive material was obtained by coating (coated silver amount: 5 mg/100 cm ² ) on a support such that the wavelength of the ultraviolet part of the spectrum was about 25% or more in the range of . As ultraviolet absorbers, 5 g of [u-4], 3 g of [u-12], and 3 g of [u-12] were added on top of these samples.
13] 3g and [u-14] 5g EA50c.c.
5% aqueous gelatin solution containing 2.5 g of sodium dodecylbenzenesulfonate after dissolving in DBP16c.c.
After adding to 250 c.c., it was dispersed using a homogenizer, and 10 ml of the above hardener solution was added and applied. The sample thus obtained was exposed to light so that the density after development was 1.0, and then photographically processed according to the processing method shown below. SPW-I type manufactured by the company) was used for 800 hours of exposure, and the concentration before exposure (D ₀ = 1.0) of the concentration after exposure [D]
The percentage [D/D ₀ × 100] of Sakura color densitometer PD-6 type (manufactured by Konishiroku Photo Industry Co., Ltd.)
The residual rate of the dye was measured using green light, and the Y-
The stain increase rate is measured with blue light and the result is
-2 Shown in Table. 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 5.0g Add water to make 1, and adjust the pH to 10.30 using sodium hydroxide. Bleach-fix composition: Ethyleneaminetetraacetate iron ammonium
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 ammonia water to adjust the pH.
Adjust to 6.5. Stabilizing liquid composition: Add 20 ml of glacial acetic acid, 800 ml of water, and add sodium acetate to make the pH 3.5.
After adjusting to ~4.0, add more water to bring it to 1.

【table】

[Table] However, DBC stands for dibutyl phthalate, TCP stands for tricresyl phosphate, and EA stands for ethyl acetate. The coupler used is a compound with the following structure. (M-1) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone (M-2) 1-(2,4,6-trichlorophenyl)-3-
[3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone (M-3) 4,4'-(2-chloro)benzylidenebis[1
-(2,4,6-trichlorophenyl)-3-(2
-Chloro-5-dodecylsuccinimideanilino-5-pyrazolone]

【table】

【table】

[Table] The comparative samples are Comparative Sample-1: A sample in which the ultraviolet absorber was removed from each sample. Comparative sample-2: A sample obtained by removing the compounds represented by the general formulas [], [], and [] from each sample. Comparative sample-3: A sample obtained by removing the compound represented by the general formula [] from each sample. Comparative sample-4: General formula [], [],
This is a sample excluding the compounds shown in [ ] and [ ]. As shown in Table 1-2, it can be seen that the compounds of the present invention used in combination have excellent dye fading prevention effects and Y-stain prevention effects that cannot be obtained when each compound is used alone. . It can be seen that the effect is dramatically improved by further providing a layer containing an ultraviolet absorber on the upper layer. Table 1-3 shows the results when the sample [] in Table 1-1 was treated with the developer shown in color developer composition [B].

[Table] As shown in Table 1-3, it can be seen that even when the developing agent is changed, the samples containing the compound of the present invention have excellent fading prevention effects and Y-stain prevention effects. 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 1 with water PH 10.86 The processing steps when using the color developing solution of composition [B] are as follows. Color development 32.2℃ 1 minute 30 seconds Bleach fixing 50 seconds Washing with water 30 seconds Example 2 Samples were prepared under exactly the same conditions except that the ultraviolet absorber shown below was used in place of the ultraviolet absorber used in Example 1. It was created. The sample was treated according to the method shown in Example 1, and the obtained results were measured in the same manner. Sample No. Ultraviolet absorber Application amount mg/m ² 1 u-77 6 2 u-93 7 3 u-101 7 4 u-102 7 5 u-104 5 6 u-106 5 7 u-108 6 8 u- 110 5 9 u-115 4 10 u-119 4 11 u-124 5 12 u-131 7 13 u-139 7 Sample prepared in this manner A comparative sample was prepared in the same manner as Example 1, and the dye residual rate, Y- The stain increase rate was measured. Although there are some differences between the UV absorbers, the obtained results show the same tendency as the results shown in Example 1, indicating that the present invention is superior even when the UV absorber is changed. confirmed. Example 3 A solution of the compound of the present invention, yellow coupler and hydroquinone derivative shown in Table 2-1 dissolved in the solvent shown in the same table was added to 500 c.c. of 5% aqueous gelatin solution containing 3.0 g of sodium dodecylbenzenesulfonate. The resulting dispersion was added to a coating solution containing 1000 c.c. of blue-sensitive silver chlorobromide emulsion (containing 95 mol% silver bromide).
(containing 4.0×10 ^-1 mol of silver halide) as a hardening agent.
- After adding 5 ml of a 4% aqueous solution of the sodium salt of triazine and applying it on polyethylene-coated paper, exemplified compound (u-101) 10
5 containing 2.5 g of sodium dodecylbenzenesulfonate after dissolving in g, EA50c.c., DBP10c.c.
% aqueous gelatin solution, disperse with a homogenizer, add 5 ml of the above hardener solution,
A sample was prepared by applying (u-101) at a concentration of 7 mg/100 cm ² . These samples were exposed to light to give a color density of 1.0 after development, and then processed according to the processing method shown in Example 1. The dye fading rate was measured using blue light in the same manner as in Example 1. The results are shown in Table 3-2.

【table】

【table】

[Table] The comparative sample was prepared in the same manner as in Example 1. The coupler used had the following structure. (Y-1) α-(1-benzyl-2,4-dioxo-3-
imidazolidinyl)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide (Y-2) α-pivalyl-α-[4-(p-chlorophenyl)- 5-Oxo- ^Δ2 -tetrazolin-1-yl]-2-chloro-5-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide (Y-3) α-pivalyl-α-[4-(1-methyl -2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-2-chloro-5-[γ-(2,4-
Di-t-amylphenoxy)butylamide]acetanilide As shown in Table 3-2, it can be seen that the compounds of the present invention are also excellent in the light resistance of yellow dyes. Example 4 A 5% solution containing 0.3 g of sodium dodecylbenzenesulfonate was prepared by dissolving 0.3 g of the compound of the present invention, cyan coupler, and (Hq-1) shown in Table 4-1 in the solvent shown in the same table. gelatin aqueous solution
500c.c. and then dispersed with a homogenizer, and the resulting dispersion was converted into a red-sensitive silver chlorobromide emulsion (silver
Coating solution (silver halide 3.5
×10 ^-1 mol) added to 1000c.c. To this coating solution, 10 ml of a 2% methanol solution of N・N′・N″-triacryloyl 6-H-S-triazine was added as a hardening agent, and this coating solution was coated on polyethylene coated paper, dried, and halogenated. Samples of silver oxide photographic light-sensitive materials were obtained.These samples were exposed to light such that the color density after development was 1.0.Example 1
Photographic processing was performed according to the same processing method as shown in Example 1, and a light fastness test was performed using the same method as shown in Example 1. The dye fading rate was measured using red light and the results were reported in Section 4-2.
Shown in the table.

[Table] The coupler used had the following structure. (C-1) 2,4-di-chloro-3-methyl-6-[α-
(2,4-di-t-amylphenoxy)butyramide]phenol (C-2) 2-(α,α,β,β-tetrafluoropropionamide)-5-[α-(2,4-di-t- amylphenoxy)butyramide]phenol (C-3) 2-(α・α・β・β-tetrafluoropropionamide)-4-β-chloroethoxy-5-[α
-(2,4-di-t-amylphenoxy)butyramide]phenol (C-4) 1-hydroxy-4-(3-nitrophenethylsulfonamide)-N-[δ-(2,4-di-t −
amylphenoxy)butyl]-2-naphthamide

[Table] The comparative samples are Comparative Sample-1: A sample obtained by removing the compound of the present invention from each sample. Comparative sample-2: This is a sample in which the ultraviolet absorber was removed from each sample. Comparative sample-3: A sample obtained by removing the compound represented by the general formula [] from each sample. Comparative sample-4: This is a sample obtained by removing the compounds represented by the general formulas [], [], and [] from each sample. Comparative sample-5: General formula [], [],
This is a sample excluding the compounds shown in [ ] and [ ]. As shown in the results in Table 4-2, the sample containing the compound represented by the general formula [] and an ultraviolet absorber (Comparative Sample-4) exhibited an excellent dye fading rate compared to other known samples. It can be seen that the samples further containing compounds represented by the general formulas [], [], and [] exhibit an even better dye fading rate than Comparative Sample 04. Example 5 Polyethylene coated paper (anatase type titanium oxide was used as a white pigment added to the polyethylene layer, and the thickness of about 360 to 400 nm on the surface of the support was
A sample of a silver halide color photographic light-sensitive material was prepared by coating each of the following layers sequentially from the support side onto a support whose wavelength in the ultraviolet region of the spectrum was approximately 25% or more in the range of . 1st layer, a blue-sensitive silver halide emulsion (silver chloroiodobromide emulsion containing 1 mol% silver iodide and 89 mol% silver bromide) containing couplers shown in Table 5-1; 470 g of gelatin per mole of silver halide,
Sensitizing dye with the following structure 2.5 x 10 ^-4 mol and 30 mol % of yellow coupler) to give a silver content of 400 mg/m ² . 2nd layer: (u-4)5 as an ultraviolet absorber
g, (u-12)3g, (u-13)3g and (u-
14) After dissolving 5g and 5g of (Hq-1) in DBP16c.c. and EA50c.c., a 5% aqueous gelatin solution containing 2.5g of sodium dodecylbenzenesulfonate
After adding to 250 c.c., disperse with a homogenizer,
The resulting dispersion was applied to a gelatin concentration of 400 mg/100 cm ² . Third layer: A green-sensitive silver halide emulsion containing the magenta coupler shown in Table 5-1 (silver chlorobromide emulsion containing 90 mol% silver bromide, 500 g of gelatin per mol of silver halide, with the following structure) sensitizing dye 2.5×10 ^-4 mol and magenta coupler to 1 silver
The silver content is 380 mg/ ^m2 . In addition, 1.8 g of a compound having the following structure as an irradiation-preventing dye is contained per mole of silver. 4th layer: The dispersion used for the 2nd layer is mixed with gelatin.
This is a gelatin layer coated at a concentration of 500mg/ ^m2 . 5th layer: A red-sensitive silver halide emulsion containing the cyan coupler shown in Table 5-1 (silver chlorobromide emulsion containing 90 mol% silver bromide, 800 g of gelatin per mol of silver halide, with the following structure) sensitizing dye 2.5×10 ^-4 mol and 30 mol% cyan coupler
) is applied to a total amount of 300mg/ ^m2 . Incidentally, 5 g of a compound having the following structure as an irradiation-preventing dye was contained per mole of silver. 6th layer; gelatin protective layer 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 each was made using sodium thiosulfate pentahydrate. Chemically sensitized using 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer and N・N′・N″-triacroyl-6-H as a hardening agent. -S-triazine and saponin as a coating aid.The compounds and couplers of the present invention used in each layer are
As shown in Table 1.

[Table] Among the couplers used, (M-1) and (C
-1) is as described above, and (Y-4),
(M-4) and (C-5) are compounds with the following structures. (Y-4) 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 (M-4) 1-(2,4,6-trichlorophenyl)-3-
(2-chloro-5-octadecylsuccinimideanilino)-5-pyrazolone (C-5) 2-perfluorobutyramide-5-[α-
(2,4-di-t-amylphenoxy)hexaneamidephenol After drying each sample, each sample was exposed to blue light, green light, and red light (exposed so that the color density after development was 1.0). After photo-processing according to the same processing method as 1, 800
The dye fading rate and Y-stain increase rate after exposure were measured according to the method of Example 1, and the results are shown in Table 5-2.

[Table] Example 6 Samples were prepared under exactly the same conditions except that the ultraviolet absorber shown below was used instead of the ultraviolet absorber used in Example 5, and treated in the same manner as shown in Example 5. and conducted measurements. Sample No. Ultraviolet absorber Application amount mg/m ² 1 u-101 7 2 u-106 7 3 u-108 7 4 u-111 5 5 u-115 5 6 u-118 5 7 u-112 6 8 u- 130 6 9 u-138 7 Comparative samples were made in the same manner as in Example 5 for the samples thus prepared, and the dye fading rate and Y-stain increase rate were measured. Although there are some differences between the UV absorbers, the results obtained show the same tendency as shown in Example 5, and even if the UV absorber is changed, the effect of the present invention is not affected in any way. This was confirmed. The comparative sample is Comparative Sample-1; a sample from which the ultraviolet absorber was removed. Comparative sample-2: General formula from the 1st, 3rd, and 5th layers []
This is a sample from which the compound indicated by has been removed. Comparative sample-3: General formula from the 1st, 3rd, and 5th layers []
This is a sample from which the compound indicated by has been removed. Comparative sample-4: General formula from the 1st, 3rd, and 5th layers []
This is a sample from which the compounds shown in and [] have been removed. In the case of sample No. 2, only the ultraviolet absorber in the second layer was removed, and the coating amount of the ultraviolet absorber in the fourth layer was 300 mg/m ² . Example 17 Exemplified compound [I-4] 14.5 g, Exemplified compound [P
-12]8g, (u-103)10g and (Hq-1)
After dissolving 2g in DBP20c.c. and ethyl acetate 40c.c.,
5 containing sodium dodecylbenzenesulfonate
% gelatin aqueous solution, then dispersed with a homogenizer, and the resulting dispersion was added to 300 c.c. of green-sensitive silver chlorobromide emulsion (containing 30 mol% silver chloride), and then polyethylene coated. A sample of silver halide photographic material was obtained by coating on paper and drying. This sample was subjected to optical wedge exposure according to the sensitometric method and then processed at a temperature of 2° C. according to the following sequence. 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 8.0 g Phenidone 0.35 g Anhydrous sodium sulfite 37.0 g Hydroquinone 5.5 g Anhydrous sodium carbonate 28.2 g Sodium thiocyanide 1.38 g Anhydrous sodium bromide 1.30 g Potassium iodide (0.1% aqueous solution) 13.0 ml in water Finished to 1 (PH9.9) Color developer formulation Anhydrous sodium sulfite 10.0 g N.N-diethyl-p-phenylenediamine hydrochloride 3.0 g Magenta coupler (M-5) 2.0 g Finished to 1 with sodium hydroxide, pH 11. Make it 5. Bleach solution formulation Anhydrous sodium bromide 43.0g Red blood salt 165.0g Borax (Na ₂ B ₄ O ₇・10H ₂ O) 1.2g Finish with water to 1. Fixing solution formulation Sodium thiosulfate (pentahydrate) 200 g Anhydrous Sodium sulfate 100 g Anhydrous disodium phosphate 15.0 g Finish with water to 1. Dye fading rate and unexposed color were measured in the same manner as in Example 1, except that the obtained color photographic material was exposed to xenon fademeter for 200 hours. The percentage increase in Y-stain was determined and the results shown in Table 7-1 were obtained. The magenta coupler (M-5) used has the following structure. 1-(2,4,6-trichlorophenyl)-3-
(4-nitroanilino)-5-pyrazolone

[Table] A comparative sample was prepared under the same conditions as shown in Example 1. Table 5-1 shows that the compounds of the present invention have excellent anti-fading and Y-stain preventing effects even in so-called external silver halide color photographic materials that do not contain couplers.

Claims (1)

[Claims] 1. At least one compound represented by the following general formula [] and the following general formula [-1] or [-
2) A color photographic material containing at least one type of ultraviolet absorber shown in item 2]. [In the formula, R is an alkyl group or an alkenyl group that may each have a substituent; R ₁ , R ₂ and R ₃ are a hydrogen atom, a halogen atom, or an alkyl group or a cycloalkyl group that each may have a substituent. The group Z represents an atomic group necessary to form a chroman ring or a coumaran ring, and R and R ₁ may be cyclized with each other to form a chroman ring or a coumaran ring, and these chroman rings and coumaran rings may be substituted with an alkyl group, a cycloalkyl group or a heterocyclic group. ] [In the formula, R ₁₀ is a hydrogen atom, an alkyl group, R ₁₁ , R ₁₂ ,
R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are hydrogen atoms,
Represents a halogen atom, an alkyl group, an alkoxy group, an acyloxy group, or an alkylsulfonic acid group. ] [In the formula, R ₂₀ is a hydrogen atom, or -OR′ ₂₀ , R′ ₂₀
is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ₂₁ is an alkyl group or alkoxy group having 1 to 18 carbon atoms, R ₂₂ , R ₂₃ and R ₂₄ are hydroxy groups,
Each represents an alkyl group or an alkoxy group having 1 to 18 carbon atoms. ]