JPH0438342B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a silver halide color photographic light-sensitive material with improved dye image storage stability, and in particular to a silver halide color photographic material that prevents coloring or discoloration due to light, temperature, and heat in the late color development area and the dye image area. Regarding color photographic materials. [Prior art and its problems] In a silver halide color photographic light-sensitive material (hereinafter abbreviated as color photographic material), exposed silver halide grains are developed using an aromatic primary amine compound. It is known that a color image can be obtained by forming a dye by reacting an oxidation product of an aromatic primary amine compound with a coupler. In this method, to form cyan, magenta and yellow pigments, respectively,
Phenol or naphthol coupler, 5
-pyrazolones, pyrazolinobenzimidazoles,
Pyrazolotriazole, indazolone or cyanoacetyl couplers, and acylacetamide or dibenzoylmethane couplers are used. It is desired that the dye image obtained in this manner does not discolor or fade even when exposed to light for a long period of time or stored under high temperature and high humidity. For this purpose, conventional methods have been proposed, such as selecting couplers with less discoloration and fading properties, using ultraviolet absorbers, and using discoloration and fading inhibitors to prevent discoloration and fading due to light. However, conventional discoloration and fading improvement technologies mainly focus on improving discoloration due to light, humidity, and heat.
In particular, there has been a lack of more effective techniques for coloring uncolored areas. As a result, although sufficient durability of the dye image against light, humidity, and heat is obtained, the coloring, especially in uncolored areas, has not been significantly improved, and this point is becoming a turning point in image storage stability. Improvements in coloring of uncolored areas by conventional light are as follows:
This is primarily done by adding significant amounts of ultraviolet absorbers to color photographic materials. In reflective color photographic materials, if a considerable amount of ultraviolet absorber is used, undesirable coloration occurs in uncolored areas. Furthermore, certain types of ultraviolet absorbers have the disadvantage that they themselves are not durable against ultraviolet rays, and uncolored areas rapidly become colored after a certain point. Furthermore, the use of a large amount of ultraviolet absorber deteriorates the physical properties of the gelatin film constituting the color photographic material, resulting in disadvantageous problems such as a decrease in hardness, sweating, and reticle formation. On the other hand, the coloring of uncolored areas due to heat and humidity is
This largely depends on the coupler used, but conventionally there has been a lack of effective means for improving the coloring of uncolored areas due to humidity and heat, as compared to light. [Object of the Invention] The present invention was made in view of the above-mentioned circumstances, and the first object of the present invention is to provide a color photographic material in which the coloring of uncolored areas due to light, humidity, and heat is largely controlled. It's about doing. A second object of the present invention is to provide a color photographic material that can prevent coloring of the resulting dye image due to light, humidity, and heat, and can maintain images with good hue for a long period of time during storage. It's about doing. [Specific Structure of the Invention] The above object of the present invention is to provide a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing at least one diffusion-resistant coupler on a support. At least one layer of the layer and/or its adjacent layer has the following general formula []
This can be achieved by a silver halide color photographic material containing an ether compound represented by (hereinafter referred to as the compound of the present invention). General formula [] R ₁ -O-R ₂ [In the formula, R ₁ represents an alkyl group or a cycloalkyl group, and R ₂ represents an alkenyl group. ] The alkyl group represented by R ₁ in the above general formula [] is preferably an alkyl group having 1 to 28 carbon atoms, and such alkyl groups include, for example,
Examples include methyl group, ethyl group, t-butyl group, t-octyl group, decyl group, tetradecyl group, octadecyl group, docosyl group, benzyl group, phenethyl group, and the like. The cycloalkyl group represented by R ₁ in the above general formula [] is preferably a cycloalkyl group having 5 to 10 carbon atoms, and examples of such cycloalkyl groups include cyclopentyl group, cyclohexyl group, adamantyl group, etc. Examples include groups. Any of the alkyl groups represented by R ₁ may have a substituent. Examples of substituents include alkoxy groups (methoxy, ethoxy, butoxy, octyloxy, octadecyloxy, etc.), aryloxy groups (phenoxy, etc.),
Halogen atoms (bromine, chlorine, fluorine, etc. atoms),
Aryl groups (phenyl group, naphthyl group, etc.), heterocyclic groups (furyl group, imidazolyl group, s-triazinyl group, etc.), trialkylsilyl groups (trimethylsilyl group, trismethoxyethylsilyl group, etc.),
Alkanesulfonyl groups (methanesulfonyl groups, octanesulfonyl groups, etc.), arylsulfonyl groups (benzenesulfonyl groups, naphthalenesulfonyl groups, etc.), alkylcarbonyloxy groups (methylcarbonyloxy groups, butylcarbonyloxy groups, etc.), hydroxyl groups, alkoxycarbonyl groups groups (methoxycarbonyl group, ethoxycarbonyl group,
octadecyloxycarbonyl group, etc.). Furthermore, the cycloalkyl group represented by the above general formula R ₁ can have a substituent, and in addition to the substituents possessed by the alkyl group represented by R ₁ above, the cycloalkyl group (methyl group, propyl group) , butyl group, octyl group, dodecyl group), alkenyl group (allyl group, octynyl group, octadecenyl group, etc.), and the like. The alkenyl group represented by R ₂ in the general formula [] is preferably an alkenyl group having 2 to 20 carbon atoms, and examples of such alkenyl groups include, for example,
Examples include a vinyl group, an allyl group, an octenyl group, an octadacenyl group, and among such alkenyl groups, a vinyl group or an allyl group is particularly preferred. Specific examples of the compounds of the present invention are shown below, but the present invention is not limited to these compounds. Exemplary compound (1) CH ₂ = CHCH ₂ -O-C ₁₀ H ₂₁ (n) (2) CH ₂ = CHCH ₂ -O-C ₁₂ H ₂₅ (n) (3) CH ₂ = CHCH ₂ -O-C ₁₄ H ₂₉ (n) (4) CH ₂ = CHCH ₂ −O−C ₁₈ H ₃₇ (n) (5) CH ₂ = CHCH ₂ −O−C ₁₈ H ₃₅ (n) (6) CH ₂ = CH− CH ₂ −O−C ₂₀ H ₄₁ (n) (12) CH ₂ = CH−CH ₂ −O−CH ₂ CH ₂ CH ₂ −
CCOC ₁₈ H ₃₇ (n) (15) CH ₂ = CH-O-C ₁₀ H ₂₁ (n) (16) CH ₂ = CH-O-C ₁₂ H ₂₅ (n) (17) CH ₂ = CH-O-C ₁₄ H ₂₉ (n ) (18) CH ₂ = CH-O-C ₁₈ H ₃₇ (n) Some of the compounds of the present invention are commercially available.
Furthermore, the compounds of the present invention can be easily synthesized according to known methods. For example, exemplified compounds
(1) and (13) synthesize 2-bromoethyl alkyl ether by a debromate reaction between 1,2-dibromoethane and an aliphatic alcohol, and then synthesize this 2-bromoethyl alkyl ether.
- A reaction in which bromoethyl alkyl ether is converted into vinyl ether by a debromate reaction in an alkaline solution, a dehydrohalogenation reaction between allyl alcohol and an alkyl halide, a dehydrochlorination reaction between a phenol or hydroquinone compound and chloroethyl vinyl ether, etc. Ether compounds of the invention can be synthesized. For details on such synthetic methods, see, for example, Experimental Chemistry Course 19, Synthesis of Organic Compounds (pp. 1-31) (edited by the Chemical Society of Japan, Maruzen Co., Ltd.).
(1957) and Dai Organic Chemistry 2, Aliphatic Chemicals (p. 339-343) (Asakura Shoten, 1957). The compound of the present invention is contained in the silver halide emulsion layer and/or its adjacent layer of a color photographic material,
In this case, the compound of the present invention may be contained in only one of these layers, or in two or more layers including these layers. Preferably, the compounds of the invention are contained in the silver halide emulsion layer. Further, the silver halide emulsion layer may be composed of a plurality of light-sensitive silver halide emulsion layers having substantially the same color sensitivity and different photosensitivity. The compound of the present invention can be contained in one or more layers of such a plurality of layers having different photosensitivity. The compounds of the present invention are generally oil-soluble, and when this compound is incorporated into a silver halide emulsion layer or a layer adjacent thereto, it is generally disclosed in US Pat. No. 2,322,027;
Same No. 2801170, Same No. 2801171, Same No. 2272191,
The compound of the present invention is dissolved in a high boiling point organic solvent and, if necessary, in combination with a low boiling point organic solvent, and dispersed in a hydrophilic colloid solution such as gelatin, according to the method described in the same specification No. 2304940. It is preferable to add At this time, if necessary, photographic additives such as couplers, hydroquinone derivatives, image stabilizers, and ultraviolet absorbers may be used in combination. Furthermore, there is no problem in using two or more of the compounds of the present invention in combination. Further, to explain in detail the method of adding the compound of the present invention, one or more compounds of the present invention may be added to a coupler, a hydroquinone derivative,
Along with photographic additives such as image stabilizers or ultraviolet absorbers, ethyl acetate is added to high-boiling organic solvents such as organic acid amides, carbamates, esters, ketones, hydrocarbons, and urea derivatives, if necessary. , butyl acetate, cyclohexanol, cyclohexane, or tetrahydrofuran. (These high-boiling organic solvents and low-boiling organic solvents may be used alone or in combination. ) This is then mixed into an aqueous solution containing an anionic surfactant such as alkylbenzene sulfonic acid, alkylnaphthalene sulfonic acid and alkyl succinate sulfonic acid, and/or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate. The resulting dispersion can be used by mixing with a hydrophilic colloid solution and emulsifying and dispersing it using a high-speed rotary mixer, a colloid mill, an ultrasonic dispersion device, etc., and adding the resulting dispersion to a hydrophilic colloid solution. The hydrophilic colloid solution thus obtained (when the hydrophilic colloid solution is a silver halide emulsion, it contains silver halide as described below) is coated on a photographic support by various known methods. A silver halide color photographic material is obtained. When the compound of the present invention is contained in a photosensitive silver halide emulsion layer, the content thereof is preferably 5 to 200% by weight, particularly preferably 10 to 100% by weight, based on the coupler used in the silver halide emulsion layer. When the compound of the present invention is contained in two or more silver halide emulsion layers, the total amount thereof may be within the above range. Further, when the compound of the present invention is contained in the non-photosensitive hydrophilic colloid layer adjacent to the photosensitive silver halide emulsion layer, the content of the compound of the present invention is preferably 0.02 to 2 g per 1 m ² of the color photographic light-sensitive material. is 0.05 to 1 g. The object of the present invention can be achieved even when the compound of the present invention is used in combination with a cyan coupler, a yellow coupler, or a magenta coupler, but it is particularly effective against coloring uncolored areas due to light, heat, and humidity. , the effect is great when the compound of the present invention is combined with a magenta coupler. Preferred magenta couplers used in the present invention are 5-pyrazolones and pyrazolinenobenztriazoles. Particularly preferred is a magenta coupler represented by the following general formula [] or []. General formula [] In the formula, R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group or an alkoxy group. Z is an alkyl group, -NH-L, -NHCO-L, -
NHCONH-L, -OR ₆ represents a group, where L represents a phenyl group (this phenyl group may have a substituent), and R ₆ represents an alkyl group or an aryl group (however, both are unsubstituted (can have a group). Q represents a hydrogen atom or a group that can be separated when coupled with an oxidized product of a color developing agent, and examples of such groups that can be separated include a halogen atom (e.g., chlorine atom, bromine atom, etc.), _-COR7 group, -OR ₈ groups, -OCOR ₉ groups, -OSO ₂ R ₉
group, −SR ₉ group,

[Formula] Group, or

[Formula] group, (However, D represents a hydrogen atom, an alkyl group, or a phenyl group. Z and R ₃ to _{R 5} are the same as those defined in the general formula []), where R ₇ is an alkyl group. , represents an alkoxy group, an aryl group, or an aryloxy group, and these groups may have a substituent. R ₈ represents an alkyl group, an alkenyl group, an aryl group, or a trialkylsilyl group, and these groups may have a substituent. R ₉ represents an alkyl group, an aryl group, or a heterocyclic group, and these groups may have a substituent. R ₁₀ to _{R 13} each independently represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), or an alkyl group, and this alkyl group may have a substituent. W represents a group of nonmetallic atoms necessary to form a 5-membered ring together with the nitrogen atom. General formula [] In the formula, R ₁₄ and R ₁₅ are each independently a hydrogen atom,
Alkyl group, aryl group, heterocyclic group, amino group,
It represents an acylamino group, a hydroxyl group, an alkoxy group, a carboxyl group, or an esterified carboxy group, and these alkyl groups, aryl groups, heterocyclic groups, and alkoxy groups can have a substituent. Furthermore, at least one of R ₁₄ and R ₁₅ is a group other than a hydrogen atom. . Q' represents a hydrogen atom or a group capable of leaving when coupled with an oxidized product of a color developing agent. Examples of such leaving groups include _-SO3H group, -COOH group, _R16 -O
- group, R ₁₆ -S- group, -N=N-R ₁₇ group, where R ₁₆ represents an aryl group (which may have a substituent), and R ₁₇ represents an amino group, an acyloxy group, a sulfonyloxy group, a thiocyano group, an imide group, or a benzotriazolyl group, and these groups may have a substituent. Specific examples of the magenta coupler represented by the above general formula [] or [] that are preferably used in the present invention are shown below, but the invention is not limited thereto. Exemplary magenta coupler The magenta couplers used in the color photographic material of the present invention may be used alone or in combination of two or more. In addition, some magenta couplers such as pyrazolinobenzimidazole and indazolone can be used in combination. The effect of preventing discoloration of uncolored areas and pixel image areas against light, heat, and humidity of the present invention is particularly large when the compound of the present invention is added to the magenta coupler-containing layer or a layer adjacent thereto. In the color photographic material of the present invention, yellow,
and cyan dye-forming couplers can be used. Among these, yellow dye-forming couplers are benzoylacetanilide type, pivaloylacetanilide type, or 2-equivalent couplers in which the carbon atom at the coupling position is substituted with a substituent that can be separated during the coupling reaction (so-called split-off group). The cyan dye-forming coupler is a phenol type, naphthol type, pyrazoloquinazolone type or a two-equivalent cyan dye-forming coupler having a split-off group. Among such dye-forming couplers, yellow dye-forming couplers are disclosed in, for example, U.S. Pat.
Same No. 2908513, Same No. 3227155, Same No. 3227550,
Same No. 3253924, Same No. 3265506, Same No. 3277155,
Same No. 3341331, Same No. 3369895, Same No. 3384657,
Same No. 3408194, Same No. 3415652, Same No. 3447928,
Same No. 3551155, Same No. 3582322, Same No. 3725072,
German Patent No. 1547868, German Patent No. 2057941, German Patent No.
No. 2162899, No. 2163812, No. 2213461, No. 2219917, No. 2261361, No. 2263875,
Special Publication No. 13576, No. 48-29432, No. 48-
No. 66834, No. 49-10736, No. 49-122335, No. 50-
No. 28834, No. 50-132926, No. 55-144240, No. 55-144240, No.
It is described in each publication No. 56-87041. Examples of cyan dye-forming couplers include U.S. Pat. No. 2,369,929, U.S. Pat.
No. 2434272, No. 2474293, No. 2698794, No. 2706684, No. 2772162, No. 2801171, No. 2895826, No. 2908573, No. 3034892,
Same No. 3046129, Same No. 3227550, Same No. 3253294,
Same No. 3311476, Same No. 3386301, Same No. 3419390,
Same No. 3458315, Same No. 3476563, Same No. 3516831,
Same No. 3560212, Same No. 3582322, Same No. 3583971,
Same No. 3591383, Same No. 3619196, Same No. 3632347,
Same No. 3652286, Same No. 3737326, Same No. 3758308,
No. 3779768, No. 3839044, West German Patent No.
No. 2163811, No. 2207468, Special Publication No. 39-27563,
45-28836, JP-A No. 47-37425, 50-
No. 10135, No. 50-25228, No. 50-112038, No. 50
−117422, No. 50-130441, No. 53-109630,
No. 55-32071, No. 55-163537, No. 56-1938,
No. 56-13643, No. 56-29235, No. 56-65134,
No. 56-104333, Research Disclosure 1976, 14853, etc. can be used. When the compound of the present invention is added to a color photographic material using a high-boiling organic solvent, the preferred high-boiling organic solvent is an organic solvent that is immiscible with water and has a boiling point of about 170°C or higher; are phthalate esters (dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, diallyl phthalate, dinonyl phthalate, dilauryl phthalate, dibenzyl phthalate, diphenyl phthalate, etc.), phosphate esters (diphenyl phosphate, tricresyl phosphate, etc.) Phate, triphenyl phosphate, dioctyl butyl phosphate, trihexyl phosphate, trioctyl phosphate, etc.), citric acid esters (acetyl tributyl citrate, tributyl citrate, etc.), benzoic acid esters (benzoic acid butyl,
octyl benzoate, etc.), alkylamides (diethyl laurylamide, etc.), sebacic acid esters (diethylhexyl sebacate, etc.), stearic acid esters (butyl stearate, etc.), maleic acid esters (dinonyl maleate, etc.), succinic acid esters ( diethyl succinate, etc.), adipate esters (dioctyl adipate, etc.), pyrrolidone (N
-dodecylpyrrolidone, etc.), and the like. Examples of low boiling point (approximately 30 to 150°C) organic solvents used as auxiliary solvents together with such high boiling point organic solvents include lower acetyl acetate (ethyl acetate, butyl acetate, β-ethoxyethyl acetate, etc.), butyl alcohol, Methyl isobutyl ketone, chloroform, hexanone, cyclohexane,
Examples include ethylene glycol, acetone, ethanol, dioxane, dimethylformamide, and the like. When the compound of the present invention is contained in a silver halide color photographic light-sensitive material, it is preferably contained in a high boiling point organic solvent together with a photographic coupler as described above. In the color photographic material of the present invention, an anti-fading agent can be used in combination with the compound of the present invention. Among these anti-fading agents, those represented by the following general formulas [], [], [] or [] are particularly preferred. General formula [] In the formula, _R18 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an isopropyl group,
n-butyl group, n-octyl group, n-dodecyl group, benzyl group, etc.), aryl group (e.g., phenyl group, etc.), alkenyl group (e.g., allyl group, etc.)
Cycloalkyl group (e.g., cyclohexyl group, etc.), heterocyclic group (e.g., S-triazonyl group, etc.),
Trialkylsilyl groups (e.g., trimethylsilyl group, etc.), alkanesulfonyl groups having 1 to 20 carbon atoms (e.g., methanesulfonyl group, octanesulfonyl group, benzylsulfonyl group, etc.), arylsulfonyl groups (e.g., benzenesulfonyl group, naphthalene group, etc.) sulfonyl group, etc.), -CO-V group, or -SO ₂ -V group, where V has 1 to 1 carbon atoms.
20 alkyl groups (e.g., methyl group, t-butyl group, cyclohexyl group, octyl group, dodecyl group, benzyl group, etc.), aryl groups (e.g., phenyl group, p-methylphenyl group, etc.), carbon atoms of 1 to 20 Alkoxy groups (e.g. methoxy group, t
-butoxy group, dodecyloxy group, benzyloxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkyloxycarbonyl group (e.g.,
ethoxycarbonyl group, t-butoxycarbonyl group, benzyloxycarbonyl group, etc.) or aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.). R ₁₈ is preferably a hydrogen atom or an alkyl group. _R19 , _R20 , _R21
are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, t-butyl group, cyclopentyl group, octyl group, dodecyl group, benzyl group, etc.), an alkoxy group having 1 to 20 carbon atoms ( For example, methoxy group, t-butoxy group, octadecyloxy group, etc.), aryl group (e.g., phenyl group, etc.), aryloxy group (e.g., phenoxy group, p-methylphenoxy group, etc.), alkenyl group (e.g., allyl group, etc.) ). R ₁₉ is preferably a hydrogen atom, R ₂₀ is preferably an alkyl group,
R ₂₁ is preferably a hydrogen atom. Z ₁ represents a group of nonmetallic atoms (e.g., carbon atom, nitrogen atom, oxygen atom, sulfur atom, etc.) necessary to form a 5- or 6-membered ring, and this ring may further include an alkyl group, an alkoxy group, an aryl group, etc. may be substituted with a group, an aryloxy group, an alkenyl group, an alkenooxy group, a heterocyclic group, etc., or may be substituted with a residue forming a condensed ring. General formula [] In the formula, R ₂₂ and R' ₂₂ may be the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, t-
butyl group, n-octyl group, n-octadecyl group, etc.), alkenyl group (e.g. allyl group, octenyl group, etc.), cycloalkyl group (e.g. cyclohexyl group, etc.), aryl group (e.g. phenyl group,
p-methylphenyl group, etc.), heterocyclic group (e.g.,
imidazolyl group, furyl group, etc.), -CO-V' group, -
SO ₂ represents a −V′ group or −CONH−V′ group,
V' has the same meaning as V in the general formula [].
R ₂₃ is an alkyl group having 1 to 20 carbon atoms (for example,
methyl group, ethyl group, n-propyl group, i-amino group, n-octyl group, n-dodecyl group, n-octadecyl group, etc.), alkenyl group having 2 to 20 carbon atoms (e.g. allyl group, octenyl group) , oleyl group, etc.), aryl group (e.g., phenyl group, etc.),
It represents an alkoxy group (eg, methoxy group, t-butoxy group, n-dodecyloxy group, etc.) or an aryloxy group (eg, phenoxy group, etc.) having 1 to 20 carbon atoms. In addition, the above R ₂₂ or R′ ₂₂
When both R ₂₃ are alkyl groups, R ₂₂ or
R′ ₂₂ and R ₂₃ may be ring-closed to form a 5- to 7-membered ring. R ₂₃ is preferably an alkyl group. X and Y are each a hydrogen atom, a halogen atom (e.g., chlorine atom, fluorine atom, bromine atom, etc.), an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, i-propyl group, t -butyl group,
heptyl group, dodecyl group, benzyl group, etc.), alkoxy groups having 1 to 20 carbon atoms (e.g., methoxy group, ethoxy group, n-butoxy group, dodecyloxy group, etc.), alkenyl groups (e.g., allyl group, octenyl group) etc.), an aryl group (eg, phenyl group, etc.), or an aryloxy group (eg, phenoxy group, etc.). Preferably, X and Y are
It is a hydrogen atom. General formula [] In the formula, _R24 and _R25 each represent an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, t-butyl group, n-octyl group, n-decyl group, n-octadecyl group, benzyl group, phenethyl group, etc.), alkenyl group having 1 to 20 carbon atoms (e.g., allyl group, octenyl group, oleyl group, etc.), cycloalkyl group (e.g., cyclohexyl group, etc.), aryl group (e.g., phenyl group, etc.) )
It represents a trialkylsilyl group (eg, trimethylsilyl group, etc.) or a heterocyclic group (eg, imidazolyl group, furyl group, triazinyl group, etc.).
Moreover, when the _-OR25 group is at the ortho position with respect to the _-OR24 group, _R24 and _R25 may be closed to form a 5- to 6-membered ring. R ₂₄ and R ₂₅ are preferably an alkyl group, a cycloalkyl group, or an alkenyl group. R ₂₆ , R ₂₇ , R ₂₈ , and R ₂₉ are each a hydrogen atom, a halogen atom (e.g., a chlorine atom, a fluorine atom, a bromine atom, etc.), an alkyl group having 1 to 20 carbon atoms (e.g., a methyl group, ethyl group, t-butyl group, i-amino group, t-octyl group, n-octadecyl group, etc.), alkenyl group having 2 to 20 carbon atoms (e.g. allyl group, octenyl group, oleyl group, etc.), cycloalkyl group groups (e.g., cyclohexyl group, etc.), aryl groups (e.g., phenyl group, etc.),
Acyl groups having 2 to 12 carbon atoms (e.g., acetyl group, benzoyl group, octanoyl group, etc.), acylamino groups having 2 to 12 carbon atoms (e.g., acetylamino group, octanoylamino group, benzoylamino group, etc.), Alkylamino groups having 1 to 20 carbon atoms (for example, methylamino group, diethylamino group, di-n-octylamino group, etc.), alkoxycarbonyl groups having 2 to 20 carbon atoms (for example, methoxycarbonyl group, n-nonyl group) carbonyl group, etc.)
or represents a sulfonamide group (e.g., methylsulfonamide group, octylsulfonamide group, phenylsulfonamide group, etc.) (provided that R ₂₆ ,
R ₂₇ , R ₂₈ and R ₂₉ are never hydrogen atoms at the same time. ). General formula [] In the formula, R ₃₀ is an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, i-propyl group,
n-octyl group, n-dodecyl group, benzyl group, etc.) alkenyl group having 2 to 20 carbon atoms (e.g.
(allyl group, octenyl group, oleyl group, etc.), aryl group (e.g., phenyl group, etc.), heterocyclic group (e.g., pyrimidyl group, tetrahydropyranyl group, etc.) -COR' ₃₀ group, -SO ₂ R' ₃₀ group, or −
CONHR' represents ₃₀ groups, and R' ₃₀ is a carbon atom number of 1 to
20 alkyl groups (e.g. methyl, ethyl,
i-propyl group, n-octyl group, n-dodecyl group, benzol group, etc.), alkenyl groups having 1 to 20 carbon atoms (e.g. allyl group, octenyl group, oleyl group, etc.), aryl groups (e.g. phenyl group) etc)
represents. Further, when R ₃₀ is an alkyl group, adjacent R _30s may be closed to each other to form a 5- to 6-membered ring. R ₃₀ is preferably an alkyl group.
R ₃₁ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, n-butyl group, benzyl group, etc.), an alkenyl group having 3 to 8 carbon atoms (e.g., allyl group, octenyl group, etc.) or an aryl group (eg, phenyl group, etc.). R ₃₁ is preferably a hydrogen atom or an alkyl group. R ₃₂ and R ₃₃ each represent a hydrogen atom, a halogen atom (e.g., chlorine atom, fluorine atom, bromine atom, etc.), an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, ethyl group, n-octyl group, etc.). base, n
-dodetecyl group, benzyl group, etc.), number of carbon atoms: 2
~20 alkenyl groups (e.g. allyl, octenyl, oleyl, etc.) or 1 to 20 carbon atoms
represents an alkoxy group (eg, methoxy group, ethoxy group, benzyloxy group, etc.). _R32 , _R33
Preferred are a hydrogen atom, an alkyl group, and an alkoxy group. Specific examples of the compound represented by the general formula [] used in the present invention are shown below, but the present invention is not limited thereto. Exemplary compound

【formula】

【formula】

【formula】 【formula】

【formula】

The compounds represented by the above-mentioned general formula []
No. 6208, No. 56-21142, JP-A-53-77526, No.
It can be synthesized according to the methods described in Publications No. 52-147433, No. 56-39541, No. 53-77527, No. 55-50244, and the like. Specific examples of the compound represented by the general formula [] used in the present invention are shown below, but the invention is not limited thereto. Exemplary compound The compounds represented by the above-mentioned general formula [ ] are listed in Japanese Patent Publication Nos. 56-52747, 57-19763, and 57-1976.
It can be synthesized by the methods described in JP-A No. 19765, JP-A No. 53-17729, and JP-A No. 55-70840. Specific examples of the compound represented by the general formula [] used in the present invention are shown below, but the compound is not limited thereto. Exemplary compound The compounds represented by the general formula [] exemplified above are disclosed in Japanese Patent Publication No. 56-24257, Japanese Patent Application Laid-Open No. 54-145530,
It can be synthesized based on the synthesis method described in Japanese Patent No. 56-52747 and Japanese Patent No. 56-39541. Specific examples of the compound represented by the general formula [] used in the present invention are shown below, but the compound is not limited thereto. Exemplary compound The compounds represented by the general formula [] exemplified above can be synthesized according to the methods described in JP-A-56-52747 and JP-A-56-159644. When the compound represented by the general formula [], [], [] or [] of the present invention is contained in the photosensitive silver halide emulsion layer together with the compound of the present invention, the amount to be added is relative to the coupler. 5～
200wt%, preferably 10-100wt%. Further, when the compounds represented by the general formulas [] to [] are contained in the non-photosensitive layer adjacent to the photosensitive silver halide emulsion layer, 0.01 to 1 g, preferably 0.02 to 1 g, per 1 m ² of the color photographic light-sensitive material. It is 0.5g. The compounds of the present invention can be expressed by the general formulas [] to []
When used in combination with the compound represented by, both can be contained in the same layer or in separate layers. Specifically, when the compound of the present invention and the compounds represented by the general formulas [] to [] are contained in the same photosensitive silver halide emulsion layer, the compound of the present invention is contained in the photosensitive silver halide emulsion layer. and when the compounds represented by the general formulas [] to [] are contained in the non-photosensitive layer adjacent to the photosensitive silver halide emulsion layer, both compounds are contained in the non-photosensitive layer adjacent to the photosensitive silver halide emulsion layer. When the compound of the present invention is contained in the non-photosensitive layer, the compound of the present invention is added to the adjacent non-photosensitive layer and the compound of the general formula [ ] ~
Examples include a case where the compound [] is contained separately in the photosensitive silver halide emulsion layer, and a case where both are contained in both the photosensitive silver halide emulsion layer and a layer adjacent thereto. When the compound of the present invention and the compound of the general formula [] to [] are used in combination, the ratio of the compound of the general formula [] to [] to the compound of the present invention is 0.05.
-10, preferably 0.1-5. In the color photographic material of the present invention, the compound of the present invention may be used together with the compounds represented by the above general formulas [] to [], or in place of this compound, a known anti-fading agent may be used in combination. Particularly preferred among such known anti-fading agents are, for example, Japanese Patent Publications No. 48-31256 and No. 48-31256 and No. 48-31256.
Bisphenols described in No. 31625, α-tocopherols and their acyl derivatives described in U.S. Pat. No. 2,360,290 and JP-A-51-27333, and U.S. Pat.
Examples include organometallic chelate compounds described in publications such as No. 62826, No. 54-62987, No. 54-82385, and No. 54-82386, and hydroxybenzoic acid esters described in JP-A-54-48535. It will be done. When these known anti-fading agents are used together with the compound of the present invention, one type or two or more types can be used. The silver halide contained in the silver halide emulsion layer of the present invention is any one of silver iodobromide, silver chlorobromide, silver bromide, silver chloroiodobromide, silver chloride, and silver chloroiodide. It may be. These silver halides may be produced by any of the ammonia method, neutral method, acidic method, etc., and may be produced by any of the simultaneous mixing method, forward mixing method, reverse mixing method, convergence method, etc. Furthermore, silver halide grains with or without boundaries between different halogen compositions can be effectively used in the present invention. As the binder used in the photographic constituent layers such as the photosensitive layer and the non-photosensitive layer of the silver halide color photographic light-sensitive material according to the present invention, gelatin such as alkali-treated gelatin or acid-treated gelatin is most commonly used. A part of this gelatin, derivative gelatin such as phthalated gelatin, phenylcarbamoyl gelatin, albumin, agar, gum arabic,
Alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used in combination. The silver halide emulsion used in the present invention includes salts of noble metals such as ruthenium, rhodium, palladium, inidium, platinum, and gold (for example, ammonium chloroparadate, potassium chloroplatinate,
Noble metal sensitization with potassium chloroparadite, potassium chloroaurate, etc.), activated gelatin,
It is possible to perform chemical sensitization such as sulfur sensitization using unstable sulfur compounds (e.g., sodium thiosulfate, etc.), selenium sensitization using selenium compounds, or reduction sensitization using stannous salts, polyamines, etc. and pAg conditions. can. Further, these silver halide emulsions can be optically sensitized using various sensitizers in order to impart photosensitivity in a desired wavelength range. Preferred sensitizing dyes that can be used at this time include, for example, US Pat.
Cyanine dyes, merocyanine dyes or Composite cyanine dyes can be used alone or in combination of two or more. These various optical sensitizers are used for purposes other than their original purpose, such as preventing fog, preventing deterioration of photographic performance during storage of silver halide color photographic materials, and controlling development (for example, gradation). It can also be used for purposes such as control, etc. The color photographic material of the present invention may further contain chemical sensitizers such as thioether compounds, quaternary ammonium salt compounds or polyalkylene oxide compounds, triazoles, imidazoles, azaindenes, and benzothiazolium compounds, if necessary. Stabilizers such as , zinc compounds, cadmium compounds, and mercabutanes can be used within the range that does not impair the effects of the present invention. Furthermore, the color photographic material of the present invention may contain various photographic additives, such as ultraviolet absorbers (e.g., benzophenone compounds and benzotriazole compounds), development accelerators (e.g., 1-aryl-3-
pyrazolidone compounds), surfactants (e.g.
sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkyl succinate sulfonate, polyalkylene compounds, etc.), water-soluble anti-irradiation dyes (for example, azo compounds, styryl compounds, oxonol compounds, anthraquinone compounds) and triphenylmethane compounds, etc.), hardening agents (e.g.,
halogen-substituted S-triazine compounds, active vinyl compounds, ethyleneimino compounds, epoxy compounds, water-soluble aluminum salts, etc.), membrane property improvers {e.g., glycerin, polyalkylene glycols, polymer aqueous dispersions (latex etc),
and solid or liquid paraffin, etc.). Supports used in the color photographic material of the present invention include supports such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, or, for example, a combination of paper and polyolefin (such as polyethylene and propylene). Depending on the purpose, a laminate of two or more substrates may be used as appropriate. This support can generally be subjected to various surface improvement treatments in order to improve its adhesion to silver halide emulsions. For example, it is also possible to use a material whose surface has been subjected to subbing treatment by methods such as roughening the surface mechanically or with an organic solvent, or providing a subbing layer. To coat the layer of the color photographic material of the present invention on this support, commonly known coating methods such as dip coating, roller coating, bead coating, curtain flow coating, etc. are used, and then dried. The method for processing color photographic materials of the present invention basically comprises the steps of color development, bleaching, and fixing. In this case, each process may be independent, or two or more of the processes may use processing liquids that have those functions, so that only one process is required. For example, a one-bath bleach-fix solution is an example. In addition, for each process, as necessary,
It is possible to perform the processing in two or more times, or it is also possible to perform the processing in combination, such as color development, first fixing, and bleach-fixing. In addition to the above steps, various steps such as a pre-hardening bath, neutralization bath, first development (black and white development), image stabilization bath, and water washing may be combined as necessary in the processing steps. The preferred processing steps used in the present invention are, for example, a series of sequential processing steps, each of which is exemplified below. (1) Color development treatment → bleach-fixing treatment → washing with water (2) color development treatment → bleaching treatment → washing with water → fixing treatment →
Washing with water (3) Color development processing → Stop → Bleaching processing → Washing with water → Fixing processing → Washing with water (4) Black and white development processing → Reverse exposure → Color development processing → Bleach and fixing processing → Washing with water (5) Black and white development processing → Stop → Add fogging agent The processing temperature of the color photographic material processing method of the present invention is set within a preferable range depending on the light-sensitive material and processing prescription. The color photographic material of the present invention is particularly suitable for processing at temperatures above 30°C, although generally from 20 to 60°C. The color developing agent used in the color developing solution includes known color developing agents that are widely used in various color photographic processes. A particularly useful color developing agent is N,N-dialkyl-P-
It is a phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful compounds include N,N-diethyl-P-phenylenediamine hydrochloride, N-methyl-P-phenylenediamine hydrochloride, and N,N-dimethyl-P-phenylenediamine hydrochloride.
Phenylenediamine hydrochloride, 2-amino-5-
(N-ethyl-N-dodecylamino)-toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-ethyl-N-β-hydroxylethylaminoaniline sulfate, 4-amino-3-methyl-N,N
-diethylaniline hydrochloride, N-methyl-N-β
-Hydroxyethyl-3-methyl-4-aminoaniline sulfate, 4-amino-N-(β-methoxyethyl)-N-ethyl-3-methylaniline-P
-Toluenesulfonate and the like can be mentioned. In particular, in the color photographic material of the present invention, the color developing agent is N-ethyl-N-β-sulfonamidoethyl-3-methyl-4-aminoaniline sulfate,
or 4-amino-N-(β-methoxyethyl)-N
In the case of -ethyl-3-methylaniline-P-toluenesulfonate, the effects of the present invention are remarkable. These color developing agents are preliminarily incorporated into the color photographic material of the present invention as color developing agents themselves.
Alternatively, it may be contained as its precursor. The color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, Examples include a Shugar amine reactant precursor and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are described, for example, in U.S. Pat.
No. 3342599, No. 2507114, No. 2695234, No. 3719492, British Patent No. 803783, Japanese Patent Application Publication No. 1973-
No. 135628, No. 54-79035, and Research Disclosure No. 15159, No. 12146, and No. 13924. In this case, the color developing solution according to the present invention used for color developing processing of a color photographic material containing a color developing agent or its precursor may be a conventionally known alkaline processing solution (so-called activation bath or activator solution). ) is used. These aromatic primary amine color developing agents or their precursors need to be added in an amount that will provide sufficient color development during color development processing. The amount varies depending on the type of color photographic material, but is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of photosensitive silver halide. These color developing agents or their precursors may be used alone or
They can also be used in combination. In order to incorporate the above compounds into color photographic materials, they can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can be added as an emulsified dispersion using a high-boiling organic solvent or by impregnating a latex polymer as described in Research Disclosure No. 14850. In addition to the aromatic primary amine color developing agent mentioned above, the color developing solution used in the present invention contains alkaline agents such as sodium hydroxide, potassium hydroxide, potassium carbonate, trisodium phosphate, boric acid, acetic acid, etc. of
PH buffer, thioethers, 1-aryl-3-
Known development accelerators such as pyrazolidones, N-methyl-P-aminophenols, and polyalkylene glycols; various organic solvents such as benzyl alcohol, ethanol, butanol, ethylene glycol, diethylene glycol, acetone, and N,N-dimethylformamide; Development inhibitors such as potassium bromide and nitrobenzimidazole, preservatives such as sulfites, hydroxylamine, glucose, alkanols and amines, and water softeners such as polyphosphoric acid compounds and nitritriacetic acid are included as necessary. The pH value of the color developer used in the present invention is usually
7.0 or more, preferably about 9.5 to 13.0. The temperature of the color development treatment used in the present invention is 30~
Preferably, the temperature is 40°C and the time is 2 to 5 minutes. In the processing method of the present invention, when a bleaching solution is used for the bleaching process, a fixing process is generally performed next using a fixing solution, and when a bleach-fixing solution is used, the bleaching process and the fixing process are performed using the same solution. done at the same time. Bleaching agents used in the bleaching solution or bleach-fixing solution include, for example, red blood salts, dichromates, aminopolycarboxylic acid iron salts, aliphatic polycarboxylic acid metal salts, persulfates, etc. In this case, it is preferable to use a metal complex salt of an organic acid. When a treatment solution containing such a metal complex salt of an organic acid is used, disadvantages such as precipitation of the composition and a decrease in bleaching ability during storage can be effectively prevented. The metal complex salt of the organic salt in the present invention has the effect of oxidizing the metallic silver produced by development and converting it into silver halide, and its structure is based on organic salts such as aminopolycarboxylic acid, oxalic acid, citric acid, etc. An acid is coordinated with a metal such as iron, cobalt, or copper. The most preferred organic acid used to form such a metal complex salt of an organic acid is, for example, an aminopolycarboxylic acid represented by the following general formula [] or []. General formula [] HOCO−A ₁ −Z−A ₂ −COOH General formula [] [In each of the above general formulas, A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , and A ₆ each represent a divalent hydrocarbon group such as an alkylene group, a cycloalkylene group, or an arylene group. Z is a divalent hydrocarbon group such as alkylene group, cycloalkylene group, arylene group, -O- group, -S- group, or N-A ₇ (A ₇ is an alkyl group, cycloalkyl group, aryl group, etc.) represents a monovalent hydrocarbon group or a lower aliphatic carboxylic acid group). ] These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Representative examples of the aminopolycarboxylic acids represented by the general formula [] or [] include the following. Ethylenediaminetetraacetic acid, diethylenetriaminepentaneacetic acid, ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, ethyliminodiacetic acid Acetic acid, hydroxymethyliminodiacetic acid, propyliminodiacetic acid, butyliminodiacetic acid, dihydroxyethylglycine, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt, Ethylenediaminetetraacetic acid tetrasodium salt, Diethylenetriaminepentaacetic acid pentasodium salt, Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt, Propylene diamine The metal in the metal complex salt of an organic acid used in the present invention, such as sodium tetraacetate, sodium nitrilotriacetate, sodium cyclohexanediaminetetraacetate, is a metal that can coordinate with an organic acid, such as chromium, manganese, iron, etc. , cobalt, nickel, copper, etc. Particularly preferred metal complex salts of organic acids for the present invention are second metal salts, such as ferric salts. The metal complex salt of an organic acid in the present invention can be any combination of the above-mentioned organic acid and metal, but particularly preferred are ferric salts of ethylenediaminetetraacetic acid, such as sodium iron() ethylenediaminetetraacetate, ethylenediaminetetraacetic acid () is ammonium. Further, metal complex salts of two or more organic acids having different structures may be used in combination.
The specific amount used is preferably in the range of 0.01 to 0.4 mol per treatment liquid. The bleaching solution used in the present invention contains the above-mentioned metal complex salt of an organic acid as a bleaching agent, and can also contain various additives. As additives, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.
In addition, PH buffers such as borates, oxalates, acetates, carbonates, and phosphates, solubilizers such as triethanolamine, ordinary bleaching solutions such as aminopolycarboxylic acids or their salts, alkylamines, and polyethylene oxides. It is possible to appropriately add substances that are known to be added to. The bleach-fix solution used in the present invention contains a metal complex salt of an organic acid (for example, an iron complex salt) as a bleaching agent, as well as a silver halide fixing agent such as a thiosulfate, a thiocyanate, or a thiourea. A liquid containing a composition is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to a bleaching agent and the above-mentioned silver halide fixer, or conversely, a composition in which a large amount of a halogen compound such as potassium bromide is added. Further, a special bleach-fix solution having a composition consisting of a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide can also be used. As the halogen compound, in addition to potassium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide, etc. can be used. The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as those used in normal fixing processing.
For example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate,
Typical examples include thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. The bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide,
PH buffering agents consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, organic chelating agents such as aminopolycarboxylic acids, or a type of stabilizer such as nitroalcohol nitrates, A solubilizer such as an alkanolamine, a stain inhibitor such as an organic amine, an organic solvent such as methanol, N,N-dimethylformamide, N,N-dimethylsulfoxide, etc. are appropriately contained. Further, when performing automatic development processing, the bleach solution or bleach-fix solution is usually replenished with a replenisher by an automatic replenishment system. That is, it supplements the components in the bleach solution or bleach-fix solution that are consumed depending on the amount of silver halide photographic light-sensitive material processed, and also compensates for the dilution caused by the solution brought in from color development processing, water washing processing, etc. The necessary components are replenished from the bleach or bleach-fix solution to compensate for those carried out by the processed silver halide photographic material.
Therefore, the replenisher is usually more concentrated than the bleach or bleach-fix solution, and the degree of concentration is appropriately selected depending on the amount of components to be replenished or the amount of the bleach or bleach-fix solution. be done. The processing time of the bleaching step and bleach-fixing step according to the present invention is preferably 0.5 to 2 minutes, more preferably 1 to 1.5 minutes. The processing temperature is usually 25 to 40°C. In the present invention, the water washing step usually takes about 25 to 35 hours.
℃ water for about 1 to 4 minutes, and the amount of water used varies depending on the type of silver halide photographic material to be processed, but is approximately 0.5 to 50 water per m ² of color photographic material. [Specific Examples of the Invention] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 On a paper support coated with polyethylene, the following layers were sequentially coated from the support side to produce eight types of color photographic materials. In addition, the amount added is shown in the amount per 1 m in all the following examples unless otherwise specified. Layer 1...2.1 g of gelatin, 0.35 g (in terms of silver) of green-sensitive silver chlorobromide emulsion (68 mol% silver bromide, average grain size 0.45 μm), and 0.58×10 ^-3 mol of exemplary magenta coupler M-8 and 0.0015 g of 2,5-di-t-octylhydroquinone (hereinafter HQ-1)
That's what it means. ) and a layer containing 0.3 g of dioctyl phthalate (hereinafter referred to as DOP) in which the ether compound of the present invention shown in Table 1 is dissolved. Layer 2...1.4g of gelatin 0.4g of the following UV absorber UV-1 and 0.4g of the following UV absorber UV-
Layer 3 containing 0.4 g of DOP dissolved in 2...1.3 g of gelatin and 0.04 g of 2,4
- Gelatin protective layer containing sodium dichloro-6-hydroxy-S-triazine (hardener) The eight color photographic materials thus obtained were subjected to optical wedge exposure and then processed in the following steps. Processing process Temperature Time Color development 33℃ 1 minute 30 seconds Bleach-fixing 33℃ 1 minute Washing 30-34℃ 1 minute Drying 60-80℃ 1 minute The compositions of the color developer and bleach-fix solution used are as follows. It is as follows. Color developer pure 800ml Ethylene glycol 15ml Benzyl alcohol 15ml Hydroxylamine sulfate 2g Potassium carbonate 32g Potassium bromide 0.65g Sodium chloride 1.0g Potassium sulfite 2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 -aminoaniline sulfate
4.5g Whitex BB (50% aqueous solution) (fluorescent whitening agent, manufactured by Sumitomo Chemical Co., Ltd.) 2ml 60% aqueous solution of 1-hydroxyethyrythene-1,1-diphosphonic acid 2ml Add pure to make 1, and 10% hydroxide Adjust the pH to 10.1 with potassium or dilute sulfuric acid. Bleach-fix solution pure 550ml Color developer A 200ml Iron () ammonium ethylenediaminetetraacetate
65g Ammonium thiosulfate 65g Sodium bisulfite 10g Sodium metabisulfite 2g Sodium ethylenediaminetetraacetate 12g Sodium bromide 10g Potassium chloride 1.0g Add pure to 1, and adjust to PH = 7.0 with dilute sulfuric acid or concentrated ammonia water. The obtained sample was divided into four parts and subjected to light resistance, heat resistance and humidity resistance tests. (Light resistance test): Light irradiation is performed for 400 hours using a xenon weather meter (model WEL-6X-HC) manufactured by Suga Test Instruments Co., Ltd. (Heat resistance test)...Stored in a constant temperature and humidity machine at 70℃ (without humidification) for 3 weeks. (Humidity resistance test)...Stored for 2 weeks in a constant temperature and humidity machine adjusted to 70°C and relative humidity 80%. The uncolored area of each test sample is shown as B (blue), G (green), and R (red).
The reflection density was measured using each monochromatic light (densitometer: Macbeth TR-924 model), and the results are shown in Table 1.
In the table, the numerical values are the values obtained by subtracting the reflection density of the uncolored area of the comparison sample (untested sample) from the reflection density of the uncolored area of the test sample.

【table】

[Table] From the results shown in Table 1, samples 5 to 8 to which the alkenyl ether compound of the present invention was added were compared to comparative sample 1.
It can be seen that coloration (especially yellow coloration) of uncolored areas due to light, heat, and humidity is suppressed compared to Samples 4 to 4. Example 2 A test similar to Example 1 was conducted. However, here M-4 was used as the magenta coupler in place of the exemplary coupler M-8, and the known anti-fading agents shown in Table 2 were also used in combination. The obtained image storage test results are shown in Table-2.

【table】 From the results shown in Table 2, the color photographic material of the present invention
Samples Nos. 13 to 21 all exhibited good properties, with little discoloration in the uncolored areas, which indicates that the use of a known anti-fading material improves the discoloration, especially against light. Example 3 After corona discharge was applied to a paper support coated on both sides with polyethylene, the following seven layers were sequentially applied from the support side to prepare a multilayer color photographic paper. Layer 1...1.5 g of gelatin, 0.33 g (in terms of silver) of blue-sensitive silver chlorobromide lactic acid (silver bromide 85 mol%, average particle size 0.65 μm), 0.6 × 10 ^-3 mol of the following yellow coupler ( Y-1) and 0.9×10 ^-3 mol of yellow coupler (Y-2) and 0.015 g of HQ-
Layer 2 containing 0.25 g of DOP dissolved in 1...1.0 g of gelatin and 0.09 g of HQ-1
was dissolved. Layer 3 containing 0.06 g DOP...1.3 g gelatin, 0.27 g - silver equivalent) green-sensitive positive silver chlorobromide emulsion (silver bromide 50 mol%, average grain size 0.45 μm) 0.59 x 10 -0.2 g DOP in which ³ moles of exemplified magenta coupler M-8 and 0.015 g of HQ-1 and 0.1 g of exemplified compound-12 were dissolved, 0.15
Layer 4 containing the following anti-irradiation dye AID-1 in g...1.5 g of gelatin, 0.8 g of ultraviolet absorber
0.6g of UV-1 and 0.04g of HQ-1 dissolved in
Layer 5 containing DOP...1.3 g of gelatin 0.3 g (in terms of silver) of red-sensitive silver chlorobromide emulsion (silver bromide 50 mol%, average grain size
0.35 μm), 0.25 x 10 ^-3 mol of the following cyan coupler C-1, 0.5 x 10 ^-3 mol of the following cyan coupler C-2, and 0.005 g of HQ-1 were dissolved.
Layer 6 containing 0.2g DOP...1.0g gelatin 0.4g UV absorber UV
-2 and 0.015g of HQ-1 dissolved in
Layer 7 containing DOP...1.0g gelatin, 0.015g polyvinylpyrrolidone and 0.015g filter dye as below:
Layer containing AID-2 In addition, the ether compound of the present invention was added to the magenta coupler-containing layer of layer 3 in the amount shown in Table 3. Further, in each sample, 2,4-dichloro-6-hydroxysodium was added as a hardening agent to layers 2, 4, and 7 in the following proportions. Layer 2 0.03g Layer 4 0.03g Layer 7 0.04g
After being heated and stored for a day, it was exposed to a light wedge using green monochromatic light and processed according to the following processing steps. Processing process Color development 33℃ 2 minutes 30 seconds Bleach-fixing 33℃ 1 minute Washing with water 30-34℃ 2 minutes Drying 70±10℃ 2 minutes Color developer and bleach-fix solution compositions are the same as those described in Example 1 I used the one from The obtained sample was subjected to an image preservation test according to the method described in Example 1. The results are shown in Table-3.

[Table] From the results shown in Table 3, it can be seen that the color photographic paper of the present invention prevents discoloration of uncolored areas without adversely affecting fading of magenta dye images.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing at least one diffusion-resistant coupler on a support, wherein the silver halide emulsion layer and/or its adjacent A silver halide color photographic material characterized in that at least one of the layers contains an ether compound represented by the following general formula []. General formula [] R ₁ -O-R ₂ [In the formula, R ₁ represents an alkyl group or a cycloalkyl group, and R ₂ represents an alkenyl group. ]