JP2717478B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material in which a dye image obtained by development processing is prevented from fading or discoloration. It is about materials.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material generally has silver halide emulsion layers sensitive to three primary colors of red, green and blue, and three types of color forming agents (couplers) in each emulsion layer are used for each layer. The color image is reproduced by a method of developing a color in a relationship between the color and the complementary color, which is felt by the so-called color reduction method. The color image obtained by photographic processing of the silver halide color photographic light-sensitive material is composed of an azomethine dye or an indoaniline dye formed by a reaction between an oxide of an aromatic primary amine color developing agent and a coupler. General. The color photographic images obtained in this way are not always stable to light and wet heat, and when exposed to light for a long period of time or stored under high temperature and high humidity, the dye images cause discoloration and discoloration, Deterioration of image quality.

[0003] Such fading or discoloration of an image is a disadvantage that can be said to be fatal to a recording material. As a method for eliminating these defects, there have been proposed various measures such as development of a coupler having high fastness of a dye obtained, use of an anti-fading agent, and use of an ultraviolet absorber to prevent image deterioration due to ultraviolet rays.

[0004] Above all, the effect of preventing image deterioration by the anti-fading agent is great. For example, hydroquinones, hindered phenols, catechols, gallic esters, aminophenols, hindered amines, chromanols,
It is known to add indans and ethers or esters obtained by silylating, acylating or alkylating the phenolic hydroxyl group of each of these compounds, as well as metal complexes.

Although these compounds are effective as an agent for preventing fading or discoloration of a dye image, they are insufficient to meet the demands of customers who have been demanding high image quality, and have a poor hue. However, they have not been able to exhibit the overall excellent effects for color photography because they change, cause fogging, cause poor dispersion, or form microcrystals after emulsion coating.

On the other hand, anti-fading agents having a spiro ring or condensed anti-fading agents have attracted attention because of their unique structures and the large effect of anti-fading performance, and are based on spirochromans (US Pat. No. 3,764,337). No. 4,174,
No. 220, JP-A-62-244045 and 60-26
2159), spiroindanes (US Pat. No. 4,36
No. 0,589, No. 4,895,793, No. 4,4
Nos. 16,978 and 4,385,111;
Nos. 7-204035 and 62-244046), spirobenzofurans (JP-A-62-273531, JP-A-1-197589, U.S. Pat. No. 4,868,101).
No.) are disclosed.

Further, as aminophenols, for example, JP-A-63-95439 and JP-A-63-95446.
Nos. 63-95440, 63-95448, 63-95449, 61-86750 and JP-A-63-95450. Further, phenylenediamines are disclosed in JP-A-62-157031.
No. 62-169161, No. 62-208048
Nos. 62-229148 and 63-163350
No. are disclosed. Further, aminophenols and phenylenediamines in which a specific substituent is substituted on the nitrogen atom are disclosed in JP-A-61-72246 and JP-A-61-164.
No. 89539, No. 61-189540, No. 62-81
No. 48, No. 63-271444, No. 63-16335
Nos. 1 and 63-16385 are disclosed. All of these compounds exhibited an anti-fading effect, but were insufficient to meet the strong demands for image fastness.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which does not discolor a color image for a long period of time and has a high storability.

Another object of the present invention is to provide a photograph which has a sufficient effect for preventing fading or discoloration of a color image without causing a change in hue or fogging, and which does not generate microcrystals after being applied. Another object of the present invention is to provide a silver halide color photographic light-sensitive material containing an additive.

Another object of the present invention is to provide a compound having excellent solubility in a high-boiling point organic solvent and the like, not producing microcrystals before and after coating, and having no adverse effect on other photographic additives. An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a photographic additive.

Another object of the present invention is to provide a photographic additive which has a sufficient effect for preventing discoloration and fading of a color image in a region having a low dye concentration (hereinafter referred to as a low concentration region) caused by coloring of a coupler. To provide a silver halide photographic light-sensitive material.

[0012]

As a result of various studies, the present inventors have found that the present invention provides a silver halide color photographic light-sensitive material containing at least one compound represented by the following general formula (A). It was found that the purpose was achieved.

[0013]

Embedded image

In the formula, R _a1 and R _a1 ′ represent a hydrogen atom or a substituent. R _a2 and R _a2 ′ represent a hydrogen atom, an aliphatic group, an aromatic group, an acyl group or a sulfonyl group, X represents —O—, —S— or —N (R _a5 ) —, and X ′ represents — Represents O-, -S- or -N (R _a5 ')-. Wherein R _a5 and R _a5 'represents an aliphatic group, R _a2
And R _a5 'and R _a2 ' and R _a5 'may be bonded to each other to form a 5- to 7-membered ring. _Ra3 , _Ra4 , _Ra3 'and R
_a4 ′ each represents an aliphatic group; R _a3 , R _a4 and R
_a3 'and _Ra4 ' may combine with each other to form a 5- to 7-membered ring. A represents a non-metallic atomic group forming a 5- to 7-membered spiro ring or bicyclo ring together with the benzene ring. a
n and an 'represent 0 or 1.

The aliphatic described in the present invention may be linear, branched or cyclic and may be saturated or unsaturated, such as alkyl, alkenyl, alkynyl, cycloalkyl,
Or cycloalkenyl, which may further have a substituent. The aromatic described in the present invention represents aryl, which may further have a substituent.

The substituent described in the present invention may be any substitutable group, for example, an aliphatic group, an aromatic group, a heterocyclic group,
Aliphatic acyl group, aromatic acyl group, aliphatic acyloxy group, aromatic acyloxy group, aliphatic acylamino group, aromatic acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group An aromatic oxycarbonyl group, a heterocyclic oxycarbonyl group, an aliphatic carbamoyl group, an aromatic carbamoyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an aliphatic sulfonyloxy group, an aromatic sulfonyloxy group, an aliphatic sulfamoyl group, Aromatic sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, aliphatic amino group, aromatic amino group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, mercapto group, Hydroxy group, cyano group, nitro group, hydroxyamino group, aliphatic carbamoy Amino group, an aromatic carbamoylamino group, an aliphatic sulfamoylamino group, an aromatic sulfamoylamino group, and a halogen atom.

The general formula (A) will be described in more detail. In the general formula (A), R _a1 and R _a1 ′ represent a hydrogen atom or a substituent, and preferred substituents include, for example, an alkyl group (preferably having 1 to 26 carbon atoms (hereinafter referred to as C number)) and a heterocyclic group (preferably Is a 3- to 8-membered ring), an alkylacylamino group (preferably having a C number of 1 to 26), an arylacylamino group (preferably having a C number of 30 to 30), an alkoxy group (preferably having a C number of 1 to 26), aryloxy Group (preferably 6 to 30 C), alkylsulfonamide group (preferably 1 to 26 C), arylsulfonamide group (preferably 6 to 30 C), alkylamino group (preferably C
Formulas 1-26), an arylamino group (preferably C 6-)
30), an alkylthio group (preferably having a C number of 1 to 26),
Examples thereof include an arylthio group (preferably having 6 to 30 carbon atoms), a hydroxy group, and a halogen atom. _Ra1 and _Ra1 '
Is preferably a hydrogen atom.

R _a2 and R _a2 ′ are a hydrogen atom, an aliphatic group (preferably an alkyl group which preferably has 1 to 26 carbon atoms and may have a substituent, for example, methyl, ethyl, octyl, methanesulfonylethyl, ethoxyethyl, Allyl, cyclohexyl, benzyl), aromatic group (preferably 6 to 30 carbon atoms)
And an optionally substituted aryl group such as phenyl and 4-methoxyphenyl), an acyl group (preferably C
An alkylacyl group which may have a substituent in Formulas 1 to 26 or an arylacyl group which may have a substituent in C6 to C30, for example, acetyl, pivaloyl, myristoyl, benzoyl), a sulfonyl group ( Preferably, an alkylsulfonyl group which may have a substituent having 1 to 24 carbon atoms or an arylsulfonyl group which may have a substituent having 6 to 30 carbon atoms, for example, methanesulfonyl, butanesulfonyl, octanesulfonyl, benzenesulfonyl , P-
Represents toluenesulfonyl).

R _a5 and R _a5 ′ are an aliphatic group (preferably an alkyl group having 1 to 26 carbon atoms which may have a substituent;
For example, methyl, ethyl, octyl, methanesulfonylethyl, ethoxyethyl, allyl, cyclohexyl, isopropyl, benzyl), R _a2 and R _a5 and R _a2 ′ and R _a5 ′ are bonded to each other to form a 5- to 7-membered ring (eg, (A piperidine ring, morpholine ring, piperazine ring, or thiomorpholine ring which may have a substituent outside the ring).

R _a3 , R _a4 , R _a3 ′ and R _a4 ′ are each an aliphatic group (preferably an alkyl group having 1 to 26 carbon atoms which may have a substituent, for example, methyl, ethyl, isopropyl, octyl) , Methanesulfonylethyl, dodecyl, hexadecyl, cyclohexyl, ethoxycarbonylmethyl, butoxycarbonylethyl, 2-ethylhexylcarbamoylethyl, trifluoromethyl, 2-fluoroethyl, 2-nitroethyl, allyl, benzyl)
And R _a3 and R _a4 and R _a3 ′ and R _a4 ′ are bonded to each other to form a 5- to 7-membered ring (for example, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a pyrrolidine ring,
An imidazolidine ring, a homopyrazine ring, or a 4-piperidone ring, which may have a substituent outside the ring).

A is a 5- to 7-membered spiro ring together with the benzene ring (for example, a 1,1'-spirobisindane ring,
A non-metal atom group forming a 2'-spiro bischroman ring, 3,3'-spiro bisbenzofuran ring) or a bicyclo ring (for example, a bicycloindane ring, a bicyclochroman ring, a bicyclobenzofuran ring). These rings may have a substituent.

[0022] In view of the effects of the present invention, it is preferable if the 'if is -O- or -S-, respectively R _a2 and R _a2' X Oyohi X is a hydrogen atom or an aliphatic group, an alkyl Particularly preferred is a group. In terms of the effect of the present invention, X and X ′ are each —N (R _a5 ) — and —N
When (R _a5 ′) —, R _a2 and R _a2 ′ are preferably an aliphatic group, an aromatic group, an aliphatic sulfonyl group, or an aromatic sulfonyl group, and are preferably an alkyl group, an alkylsulfonyl group, An arylsulfonyl group is more preferred, and an alkyl group is most preferred. From the viewpoint of the effects of the present invention, it is preferable that _Ra5 or _Ra5 'is an alkyl group, and it is also preferable that _Ra2 and _Ra5 and _Ra2 ' and _Ra5 'combine to form a 5- to 7-membered ring.

[0023] In view of the effects of the present invention R _a3, R _a4, R _a3 'and R _a4' is the alkyl group are preferred, R _a3 and R
One of _a4, and the one of the alkyl groups of R _a3 'and R _a4' alpha
An alkyl group having a substituent at any of the positions, β and γ, or R _a3 and R _a4 and R
More preferably, _a3 'and _Ra4 ' combine with each other to form a 5- to 6-membered ring. In terms of the effect of the present invention, R _a3 , R
_a4 , the α-position of all alkyl groups of R _a3 ′ and R _a4 ′,
In the case of an alkyl group having a substituent at either the β-position or the γ-position, or R _a3 and R _a4 and R _a3 ′ and R _a4 ′ are bonded to each other, and a —CO— group is contained in the ring. , -SO _2-
It is more preferable that the compound has a group, a —SO— group, a —CONH— group, or a —NH— group and forms a 5- to 6-membered saturated ring.

Preferred substituents to be substituted on the alkyl groups of R _a3 , R _a4 , R _a3 ′ and R _a4 ′ are _{alkylacyl, arylacyl} , alkoxy, aryloxy, and the like in view of the effects of the present invention. Alkylsulfonyl, arylsulfonyl, alkylcarbamoyl, arylcarbamoyl, alkylsulfamoyl, arylsulfamoyl, alkoxycarbonyl, aryloxycarbonyl, halogen, cyano, nitro, alkylthio, arylthio The group is more preferably an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkoxycarbonyl group, an alkylsulfamoyl group, or a fluorine atom. In terms of the effect of the present invention, _Ra3 , _Ra4 ,
The substitution position of the substituent of the alkyl group of R _a3 ′ and R _a4 ′ is preferably α-position or β-position, and most preferably β-position. From the viewpoint of the effect of the present invention, it is preferable that an and an 'are 1, and it is more preferable that X and X' be -O-.

From the viewpoint of the effect of the present invention, A preferably forms a 5- to 6-membered spiro ring or a bicyclo ring together with the benzene ring, more preferably a 5- to 6-membered spiro ring. 1,1′-spirobisindane ring,
Most preferably, it is a 3,3'-spirobisbenzofuran ring.

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

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

[0030]

Embedded image

[0031]

Embedded image

The compounds represented by the general formula (A) of the present invention are disclosed in JP-B-49-20977 and JP-A-3-37719.
No., J. Chem. Soc., P. 417 (1962), etc., and a conventional method such as alkylation, nitration and the like.

The following are synthesis examples of typical compounds. (Synthesis of Exemplified Compound (1)) To 42 g of bisphenol A was added 200 ml of 47% hydrobromic acid, and the mixture was heated under reflux for 8 hours. The reaction solution was cooled and extracted with 100 ml of ethyl acetate, and the ethyl acetate layer was washed twice with 100 ml of brine and dried over anhydrous magnesium sulfate. After filtering off magnesium sulfate, ethyl acetate was distilled off under reduced pressure, and crystallization was performed with 80 ml of benzene: n-hexane = 1: 3 to obtain white crystals. This crystal is 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobisindane by mass spectrum, NMR spectrum and infrared absorption spectrum. It was confirmed. Yield 15 g Yield 75% Melting point 185-186 ° C.

6,6'-dihydroxy-3,3,3 ',
20 ml of acetic acid was added to 8.5 g of 3'-tetramethyl-1,1'-spirobisindane, and 4.3 ml of concentrated nitric acid (specific gravity: 1.38) was slowly added dropwise with stirring at an internal temperature of 15 to 20 ° C. The mixture was stirred at an internal temperature of 15 ° C. for 30 minutes, and the precipitated crystals were filtered and washed with 20 ml of acetonitrile to obtain yellow crystals.
The crystals were analyzed by mass spectrum, NMR spectrum and infrared absorption spectrum to give 6,6'-dihydroxy-5,5 '.
-Dinitro-3,3,3 ', 3'-tetramethyl-1,
It was confirmed to be 1'-spirobisindane. 8 g, 72.8% yield, 200-204 ° C.

6,6'-dihydroxy-5,5'-dinitro-3,3,3 ', 3'-tetramethyl-1,1'-
30 g of dimethylformamide in 8 g of spirobisindane
l, 7.5 g of anhydrous potassium carbonate was added, and 8.2 g of butyl iodide was slowly added dropwise with stirring at an internal temperature of 90 ° C. Inner temperature 9
The mixture was stirred at 0 to 100 ° C. for 1 hour, poured into 100 ml of ice water, extracted with 100 ml of ethyl acetate, and the ethyl acetate layer was washed twice with 100 ml of brine and dried over anhydrous magnesium sulfate. After filtering off magnesium sulfate, ethyl acetate was distilled off under reduced pressure, separated by column chromatography, and crystallized with 30 ml of methanol to obtain pale yellow crystals. This crystal was analyzed by mass spectrum, NMR spectrum and infrared absorption spectrum for 6,6'-dibutoxy-5,5'-dinitro-3,3,3 ', 3'-tetramethyl-1,1'.
-It was confirmed to be spirobisindane. Yield 7.
0g yield 67.1% melting point 171-172 ° C.

To 5.1 g of 6,6'-dibutoxy-5,5'-dinitro-3,3,3 ', 3'-tetramethyl-1,1'-spirobisindane was added 100 ml of ethanol and a palladium-carbon catalyst (10%). %) And stirred in an autoclave at 50 ° C. for 3 hours with hydrogen gas (70 kg / cm ² ). The palladium carbon catalyst was filtered off from the reaction solution, the reaction solution was transferred to a flask, 2.4 g of divinyl sulfone was added dropwise with heating and stirring, and the mixture was further heated and stirred for 8 hours. After ethanol was distilled off under reduced pressure, the residue was separated by column chromatography and crystallized with 10 ml of methanol to obtain white crystals. This crystal was confirmed to be the exemplary compound (1) by mass spectrum, NMR spectrum and infrared absorption spectrum. Yield 2.0 g Yield 29.4% Melting point 250 ° C. or higher.

(Synthesis of Exemplified Compound (11)) In the same manner as in Exemplified Compound (1), commercially available 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-2,2'- 7,7'-dibutoxy-6,6'- from spirobischroman
Dinitro-4,4,4 ', 4'-tetramethyl-2,
2'-Spirobischroman was obtained. Iron powder for reduction 26.2
2.8 g of ammonium chloride and 22 ml of water were added to the resulting mixture, and the mixture was heated and stirred for 30 minutes. Under heating and stirring, 220 ml of isopropyl alcohol was gradually added, and 7,7'-dibutoxy-6,6'-dinitro-4,4,4 ', 4'-tetramethyl-2,2'-spirobischroman was added. 5 g to 30
And heated and stirred for an additional 4 hours. Iron powder was removed by filtration through celite, and the solvent was distilled off under reduced pressure. 80 ml of ethanol was added to the residue, 10.6 g of divinyl sulfone was added dropwise with heating and stirring, and the mixture was further heated and stirred for 8 hours.
After ethanol was distilled off under reduced pressure, the residue was separated by column chromatography and crystallized from 100 ml of methanol to obtain white crystals.
This crystal was confirmed to be the exemplified compound (11) by mass spectrum, NMR spectrum and infrared absorption spectrum. Yield 8 g Yield 29.1% Melting point 157-159
° C.

The compound represented by formula (A) of the present invention may be contained in at least one layer on a support. From the viewpoint of the effects of the present invention, the case where the compound is added to the photosensitive emulsion layer is preferable, and the case where the compound is co-emulsified with the dye-forming coupler and coated is more preferable. The compound represented by formula (A) of the present invention may be used in combination with a known anti-fading agent,
In that case, the fading prevention effect is further increased. Similarly, two or more compounds represented by the general formula (A) may be used in combination.

The compound represented by the general formula (A) of the present invention is preferably used in combination with a magenta coupler or a pyrazoloazole-based coupler from the viewpoint of the effects of the present invention. (III),
No. 2-2088653, Formula (II) and No. 2-2178
No. 45, a hindered amine compound represented by the general formula (III) or JP-A-1-287564, a compound represented by the general formula (A)
-1), phosphorus compounds represented by the general formula (II) of JP-A-3-25438, or the general formulas (I) and (II) of JP-A-1-137254 and the general formula (A) of JP-A-137258. The general formula (III) and 2-
General formula (II) of JP 51846, General formula (II) of JP-A-3-53247 and General formula (A) of JP-A-3-233448
Or a phenolic compound represented by the formula:
A cyclic sulfur compound represented by the general formula (III) of the formula (01239) or the general formula (A) of JP-A-3-279949;
When used in combination with at least one selected from the hydrazine-based compounds represented by the formula (1), the effect of preventing discoloration is further increased, which is particularly preferable. The amount of the compound used in combination is preferably in the range of the amount described in each specification.

The compound of the formula (A) of the present invention varies depending on the type of the coupler, but is preferably 0.5 to 3 based on the coupler used (preferably, a coupler used in the same layer).
It is suitably used in the range of 00 mol%, preferably in the range of 1 to 200 mol%.

The compound represented by the general formula (A) and the coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, and are dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination). An oil-in-water dispersion method in which the emulsion is dispersed in an aqueous gelatin solution and added to the silver halide emulsion is preferred.
Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Also,
The steps and effects of the latex dispersion method as one of the polymer dispersion methods, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,
541,274, 2,541,230
No. 3-41091 and European Patent Publication No. 029104, and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 0072.
No. 3 is described in the specification.

Examples of the high-boiling organic solvents that can be used in the above-described oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2 , 4-di-ter
t-amylphenyl) isophthalate, bis (1,1-
(Diethylpropyl) phthalate), esters of phosphoric acid or phosphon (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate,
-Ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic esters (for example, 2-ethylhexyl benzoate, 2,4-dichloro) Benzoate, dodecyl benzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecaneamide, N, N-diethyllaurylamide), alcohols or phenols (such as isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic esters (for example, dibutoxyethyl succinate, Di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate,
Trioctyl tosylate), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (chlorine content 10% to
80% paraffins) trimesic esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,
4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl)
Phenol), carboxylic acids (for example, 2- (2,4-
Di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkyl phosphoric acids (for example, di-2
(Ethylhexyl) phosphoric acid, diphenyl phosphoric acid) and the like. As an auxiliary solvent, the melting point is 30 ° C or more and about 1
An organic solvent having a temperature of 60 ° C. or lower (eg, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination. The high boiling organic solvent is used in an amount of 0 to 5.0 times, preferably 0 to 5.0 times by weight the coupler.
It can be used up to 1.0 times.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) used in the present invention, and the processing methods and processing additions applied for processing the light-sensitive material As the agent, those described in the following patent publications, in particular, EP 0,355,660 A2 are preferably used.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5]

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used. It is preferable to use a silver chlorobromide or pure silver chloride emulsion having a silver chloride content substantially free of silver iodide of 90 mol% or more, more preferably 95% or more, particularly 98% or more.

The light-sensitive material according to the present invention may be coated with a hydrophilic colloid layer in order to improve the sharpness of an image, etc., in accordance with EP-A-0,337,490A2.
Dyes capable of being decolorized by treatment (among which are oxonol dyes) described on page 76 are added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, or the water-resistant resin layer of the support is used. In the dihydric alcohol (for example, trimethylolethane (e.g., titanium oxide surface-treated with 12% by weight or more (more preferably, 14% by weight or more))
It is preferable to include them.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in EP 0,277,589 A2 together with a coupler. In particular, combination use with a pyrazoloazole-based magenta coupler is preferable.

That is, EP 0,27 which forms a chemically inert and substantially colorless compound by chemically bonding with an aromatic amine developing agent remaining after color development processing.
7,589A2 and / or a chemical bond with an oxidized aromatic amine-based color developing agent remaining after color development to form a chemically inert and substantially colorless compound. European Patent EP 0,277,58
Simultaneous or sole use of the compound (B) described in No. 9A2 prevents the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidized product upon storage after processing, for example. Preferred above.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

As a support for use in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment was provided on a support having a silver halide emulsion layer for a display. A support may be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.3 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 5 to 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred. In the exposure, it is preferable to use a band and stop filter described in U.S. Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved.

In the present invention, it is preferable to apply a developing agent (paraphenylenediamine derivative) to a light-sensitive material which is not present in the light-sensitive material before the development processing. For example, a color paper, a color reversal paper, a direct positive color light-sensitive material, It can be applied to color negative films, color positive films, color reversal films and the like. Among them, color photosensitive materials having a reflective support (eg, color paper, color reversal paper)
And a color photosensitive material that forms a positive image (eg, a direct positive color photosensitive material, a color positive film, a color reversal film), and particularly preferably a color photosensitive material having a reflective support.

In practicing the present invention, the magenta dye-forming coupler and the yellow dye-forming coupler which are colored with magenta and yellow, respectively, are coupled with an oxidized aromatic primary amine color developing agent. Is preferred.

The couplers used in combination may be 4 equivalents or 2 equivalents to silver ions, and may be in the form of a polymer or an oligomer. Further, the couplers used in combination may be a single coupler or a mixture of two or more couplers. In the present invention, couplers which are preferably used in combination with the cyan coupler of the present invention will be described. Examples of cyan couplers include phenolic and naphthol couplers.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A and 333,185A2, U.S. Pat. No. 3,446,622.
No. 4,333,999, No. 4,775,61
No. 6, No. 4,451,559, No. 4,427,7
No. 67, No. 4,690,889, No. 4,254
No. 212, 4,296,199, JP-A-61-4
No. 2658 and the like are preferable. Further, JP-A Nos. 64-553, 64-554, 64-555.
Azole couplers described in U.S. Patent Nos. 4,818,672, and JP-A-2-33144.
Imidazole couplers described in JP-A No.
A cyclic active methylene type cyan coupler described in JP-A-32260 can also be used. Particularly preferred cyan couplers include general formulas (C-I) and (C-I) described in JP-A-2-139544, page 17, lower left column to page 20, lower left column.
II) couplers.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897, and European Patent 73,6.
No. 36, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984)
), JP-A-60-33552, Research Disclosure Magazine No. 24230 (June 1984), JP-A-60-43659, 61
-72238, 60-35730, 55-118034, 60-18595
No. 1, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 04795 are more preferable. Particularly preferred magenta couplers include pyrazoloazole-based magenta couplers of the general formula (I) described in JP-A-2-139544, page 3, lower right column to page 10, lower right column and JP-A-2-139544. 5-pyrazolone magenta couplers of the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferred are the aforementioned pyrazoloazole-based magenta couplers.

As the yellow coupler, for example, US Pat. Nos. 3,933,501, 4,022,620 and 4,326,024
No. 4,401,752, No. 4,248,961, No. 58-
10739, UK Patents 1,425,020 and 1,476,760
No. 3,973,968, U.S. Pat.No. 4,314,023, U.S. Pat.
4,511,649, European Patent No. 249,473A, JP-A-63-231
No. 45, No. 63-123047, JP-A No. 1-250944, No. 1-213648
Can be used in combination unless the effects of the present invention are impaired. Particularly preferred yellow couplers are the yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column.
3-179042, an acylacetamide yellow coupler characterized by an acyl group described in EP-A-0447969, and a yellow of the general formula (Cp-2) described in Japanese Patent Application No. 3-203545 and EP-A-0446863A2. Couplers.

Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers that release development inhibitors are described in the aforementioned RD Magazine No. 176
Patents described in 43, VII-F, JP-A-57-151944
No., No. 57-154234, No. 60-184248, No. 63-37346,
Those described in U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

As a coupler which releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,097,140
No. 2,131,188, JP-A-59-157638, JP-A-59-17084
Those described in No. 0 are preferred.

Other couplers that can be used in combination with the light-sensitive material of the present invention include competing couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,338,393.
No. 4,310,618, etc.
DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DI described in JP-A Nos. 0-185950 and 62-24252.
R redox releasing redox compounds, EP 173,30
Coupler releasing a dye that recolors after detachment described in 2A,
RD magazine No. 11449, the same magazine No. 24241, JP-A-61-20124
No. 7, bleaching accelerator releasing coupler, U.S. Pat.
Ligand releasing couplers described in 4,553,477, etc.
Examples thereof include a coupler releasing a leuco dye described in 3-75747 and a coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181.

The standard amount of the color couplers which can be used in combination in the present invention is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide. 0.01 to 0.5 mol, 0.003 to 0.3 mol for the magenta coupler, and 0.002 to 0.3 mol for the cyan coupler.

Next, examples of typical couplers used in the present invention will be described.

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

In the light-sensitive material of the present invention, various anti-fading agents can be used in combination. Hindered phenols such as hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols and bisphenols as organic fading inhibitors for cyan, magenta and / or yellow images , Gallic acid derivatives, methylenedioxybenzenes,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic discoloration inhibitor include US Pat. Nos. 2,360,290 and 2,418,613.
2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944, and 4 No. 1,430,425, British Patent No. 1,363,921.
No. 2,710,801, U.S. Pat.
No. 028 and the like; US Pat.
432,300, 3,573,050, 3,5
Nos. 74,627, 3,698,909, 3,76
6,337, 5-hydroxychromans, spirochromans described in JP-A-4,337 and JP-A-52-152225; U.S. Pat. No. 4,360,589.
Spiroindanes described in U.S. Pat.
No. 765, British Patent No. 2,066,975, JP-A-5
9-10539, JP-B-57-19765, etc .; p-alkoxyphenols; U.S. Pat.
Nos. 0,455 and 4,228,235,
No. 72224, JP-B-52-6623 and the like; hindered phenols; gallic acid derivatives described in U.S. Pat. No. 3,457,079; U.S. Pat. No. 4,332,88
Methylenedioxybenzenes described in No. 6;
Aminophenols described in U.S. Pat. No. 21,144; U.S. Pat. Nos. 3,336,135 and 4,268,593; British Patent Nos. 1,326,889 and 1,354,313.
No. 1,410,846, JP-B-51-1420
And JP-A-58-114036 and JP-A-59-53846.
And hindered amines described in JP-A-59-78344; U.S. Patent Nos. 4,050,938 and 4,241.
155 and British Patent No. 2,027,731 (A). These compounds are usually used in an amount of 5 to 10 for each corresponding color coupler.
The object can be achieved by adding 0% by weight to the photosensitive layer after co-emulsification with the coupler.

The light-sensitive material of the present invention comprises a hydroquinone derivative, an aminophenol derivative,
It may contain gallic acid derivatives, ascorbic acid derivatives and the like.

In order to prevent deterioration of the cyan dye image due to heat and particularly light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto. As an ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, US Pat.
No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681), and benzophenone compounds (for example, JP-A-46-2)
784), cinnamic acid ester compounds (for example, those described in U.S. Pat. Nos. 3,705,805 and 3,707,395), butadiene compounds (for those described in U.S. Pat. No. 4,045,229), and triazine compounds (for example, Showa 46-3335
Or benzoxazole compounds (for example, those described in U.S. Pat. Nos. 3,406,070 and 4,271,307). An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used.
These ultraviolet absorbers may be mordanted to a specific layer. Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

The light-sensitive material according to the present invention comprises the above-mentioned RD N
o. 17643, pages 28 to 29, and No. 18716, 615, left column to right column. For example, a color developing process, a desilvering process, and a washing process are performed. In the desilvering step, instead of the bleaching step using a bleaching solution and the fixing step using a fixing solution, a bleach-fixing step using a bleach-fixing solution can be performed. The bleach-fixing steps may be combined in any order. A stabilizing step may be performed instead of the water washing step, or a stabilizing step may be performed after the water washing step. Further, a monobath processing step using a one-bath development bleach-fix processing solution in which color development, bleaching and fixing are performed in one bath can also be performed. In combination with these processing steps, the pre-hardening processing step, its neutralization step,
A stop fixing treatment step, a post-hardening treatment step, an adjustment step, an intensification step and the like may be performed. An intermediate washing step may be optionally provided between the above steps. In these processes, a so-called activator process may be performed instead of the color development process.

[0078]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Example 1 11.5 g of a magenta coupler M-1 was weighed, 11.5 g of a high-boiling organic solvent dibutyl phthalate was added, and 24 ml of ethyl acetate was further added to dissolve the solution. 1.5 g of sodium dodecylbenzenesulfonate was added to this solution. The emulsion was emulsified and dispersed in 200 g of a 10 wt% aqueous gelatin solution containing the same.

The whole amount of this emulsified dispersion was added to the high silver chloride emulsion 24.
7 g (silver 70.0 g / Kg emulsion, silver bromide content 0.5 mol%), and coated on a triacetate film base provided with an undercoat layer so that the coated silver amount was 1.73 g / m ^2. A sample 101 was prepared by providing a gelatin layer as a protective layer on this coating layer so that the dry film thickness was 1.0 μm. In addition, 1-oxy-3,5 is used as a gelatin hardener.
-Dichloro-s-triazine sodium salt was used.

In preparing the above emulsified dispersion in the same manner as in Sample 101, as shown in Table A, the emulsion was co-emulsified with a combination of a coupler and a color image stabilizer (100 mol% added to the coupler). Samples were prepared and applied in the same manner as Sample 101, to prepare Samples 102 to 125.

Each of the samples thus obtained was exposed to wedges and then developed in the following processing steps. [Processing step] [Temperature] [Time] Color development 35 ° C. 45 seconds Bleach-fix 30-35 ° C. 45 seconds Rinse 30-35 ° C. 20 seconds Rinse 30-35 ° C. 20 seconds Rinse 30-35 ° C. 20 seconds Dry 70 ~ 80 ° C 60 seconds

The composition of each processing solution is as follows. [Color developing solution] Water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylene phosphonic acid 1.5 g Potassium bromide 0.015 g Triethanolamine 8 0.0 g sodium chloride 1.4 g potassium carbonate 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N-bis (carboxymethyl) hydrazine 5 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g Add water 1000 ml pH (25 ° C) 10.05

[Bleach-fixing solution] Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron (III) ethylenediaminetetraacetate ammonium dihydrate 55 g Disodium ethylenediaminetetraacetate dihydrate 5 g Ammonium bromide 40 g Water In addition, 1000ml pH (25 ° C) 6.0 [Rinse solution] Deionized water (Calcium and magnesium are each 3ppm or less)

The dye images 101 to 101 thus formed were
For each of the 125 samples, an ultraviolet absorption filter manufactured by Fuji Photo Film Co., Ltd., which cuts light of 400 nm or less, was attached, and 10 samples were applied using a xenon tester (illuminance 200,000 lux).
Irradiated for days. The yellow density (stain) of the unexposed portion of each sample was measured, and the density residual ratio at initial densities of 0.5 and 1.0 was determined.

The measurement was performed with a Fuji self-recording densitometer. The results obtained are shown in Table A.

[0086]

[Table 6]

[0087]

Embedded image

[0088]

Embedded image

From the results, it was found that the compound of the present invention was effective in preventing light fading of a color image and also in preventing yellowing of an unexposed portion. In addition, the results showed an unexpected inhibitory effect from known spiro compounds, aminophenol derivatives and phenylenediamine derivatives.

Example 2 Example 1 was repeated except that magenta coupler M-1 and 11.5 of Example 1 were replaced with 16.1 g of yellow coupler Y-1 and 16.1 g of dibutyl phthalate, a high boiling organic solvent, with 11.5 g. Sample 201 was prepared in the same manner as in 1. Sample 2
In preparation of the emulsified dispersion in the same manner as in Example 01, a sample was prepared by co-emulsifying with a combination of a coupler and a color image stabilizer (100 mol% added to the coupler) as shown in Table B. In the same manner as in the case of the sample 201, samples 202 to 210 were prepared.

Each of the samples thus obtained was subjected to exposure, development, and a discoloration test (the number of exposure days was 8 days) in the same manner as in Example 1. The evaluation was performed based on the residual ratio of yellow density at the initial density of 2.0. The results obtained are shown in Table B. The comparative compound is the same as in Example 1.

[0092]

[Table 7]

[0093]

Embedded image

From the results, the compound of the present invention was also effective in preventing light fading of a yellow color image, and the result showed an anti-fading effect which could not be expected from a known compound. Similarly, a xenon fading test was carried out in the same manner as in Example 1 except that the magenta coupler in Example 1 was replaced with C-5, and a xenon fading test was carried out. It was confirmed that the effect was excellent.

Example 3 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper having the layer configuration shown was produced. The coating solution was prepared as follows.

Preparation of Coating Solution for First Layer 19.1 g of yellow coupler puller (ExY), 4.4 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd)
-7) 0.7 g, color image stabilizer (Cpd-12) 1.86
g and 0.9 g of the color image stabilizer (Cpd-9), 27.2 cc of ethyl acetate, 4.1 g of a solvent (Solv-3) and 4.1 g of a solvent (Solv-7) were added and dissolved, and this solution was dissolved in 10% dodecylbenzene. Sodium sulfonate 8
An emulsified dispersion A was prepared by emulsifying and dispersing in 185 cc of a 10% aqueous gelatin solution containing cc. On the other hand, silver chlorobromide emulsion A (cubic, 3: 7 mixture of a large-sized emulsion having an average grain size of 0.88 μm and a small-sized emulsion having an average grain size of 0.70 μm (silver molar ratio). 0.08 and 0.10, and in each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the grain surface). In this emulsion, blue-sensitive sensitizing dyes A and B shown below were contained in an amount of 2.0 × 10 ^-4 mol per mol of silver per mol of silver, and each of the following blue-sensitive sensitizing dyes per mol of silver. 2.5 × 10 ^-4
Mole is added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

Further, each layer has Cpd-10 and Cpd-11.
Was added so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively.

The following spectral sensitizing dyes were used for the silver chlorobromide emulsion in each photosensitive emulsion layer.

[0100]

Embedded image

(Per mol of silver halide, 2.0 × 10 ⁻⁴ mol for large-size emulsion A and 2.5 × 10 ⁻⁴ mol for small-size emulsion A, respectively)

[0102]

Embedded image

(Each mole of silver halide is 4.0 × 10 ^-4 mole for large-size emulsion B and 5.6 × 10 ^-4 mole for small-size emulsion B), and

[0104]

Embedded image

(Per mol of silver halide: 7.0 × 10 ⁻⁵ mol for large-size emulsion B, 1.0 × 10 ⁻⁵ mol for small-size emulsion B)

[0106]

Embedded image

(Per mol of silver halide: 0.9 × 10 ^-4 mol for large-size emulsion C, and 1.1 × 10 ^-4 mol for small-size emulsion C)

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0109]

Embedded image

The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ⁻⁵ mol, 7.7 × 10 ⁻⁴ mol per mol,
2.5 × 10 ^-4 mol was added.

The blue-sensitive emulsion layer and the green-sensitive emulsion layer were treated with 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

[0113]

Embedded image

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The polyethylene on the first layer side contains white pigment (Tio ₂ ) and bluish dye (ultramarine)]

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv) -3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06 Color image stabilizer (Cpd-12) 0.08 Color image stabilizer (Cpd-9) 04

Second layer (color mixture prevention layer) Gelatin 0.64 Color mixture prevention agent (Cpd-5) 0.10 Additive (Cpd-14) 0.02 Solvent (Solv-1) 0.16 Solvent (Solv-4) ) 0.08

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (Ag mole ratio)) The variation coefficients of the grain size distribution were 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface in each emulsion. 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-3) 0.16 color image stabilizer (Cpd-4) 0.02 color image stabilizer (Cpd-9) 0 .02 Solvent (Solv-2) 0.40

Fourth layer (ultraviolet absorbing layer) Gelatin 1.41 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Additive (Cpd-14) 0.03 Solvent (Solv) -5) 0.24

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large-size emulsion having an average grain size of 0.58 μm and small-size emulsion of 0.45 μm (Ag molar ratio)) The variation coefficients of the grain size distribution were 0.09 and 0.11, and each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface.) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Additive (Cpd-13) 0.15 Solvent (Solv) -5) 0.08

Seventh layer (protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Additive (Cpd-15) 0.01 Liquid paraffin 0.03

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

First, each sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time is 2 seconds with an exposure time of 0.1 second.
The exposure was performed so that the exposure amount became 50 CMS.

The exposed sample was processed using a paper processing machine using the following processing steps and a liquid having a processing solution composition.
Continuous processing (running test) was carried out until replenishment was twice the tank capacity for color development. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ° C 45 seconds 161 ml 17 liter Bleach-fix 30-35 ° C 45 seconds 215 ml 17 liter Rinse 1 30-35 ° C 20 seconds −10 liter Rinse 2 30-35 ° C 20 sec - 10 l rinse 3 30 to 35 ° C. 20 seconds 350 ml 10 l drying 70 to 80 ° C. 60 seconds * replenishment rate is per photosensitive material 1 m ² (and the third tank countercurrent system to rinse 3 → 1.)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Fluorescent whitening agent (WHITEX 4B, manufactured by Sumitomo Chemical) 1.0 g 2.0 g Add water 1000 ml 1000 ml pH (25 ° C.) 10.05 10.45

[Bleach-fixing solution] (The tank solution and the replenisher are the same) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Iron (III) ethylenediaminetetraacetate ammonium dihydrate 55 g Disodium ethylenediaminetetraacetate -Dihydrate 5 g Ammonium bromide 40 g Add water 1000 ml pH (25 ° C) 6.0

[Rinse solution] (The tank solution and the replenisher are the same.) Deionized water (Calcium and magnesium are each 3 pp.
m or less)

The sample thus obtained was designated as 1A, and the magenta coupler in the third layer and the color image stabilizer (Cpd-
Other samples 2A to 13 were prepared in the same manner as in sample 1A except that 3) was replaced by an equimolar amount as shown in Table C and co-emulsified.
A was prepared. The comparative compound is the same as in Example 1.

Each sample on which a dye image was formed was subjected to a fading test. The evaluation of the anti-fading effect was obtained by measuring the residual ratio of magenta density at an initial density of 2.0 after exposure for 200 hours using a xenon tester (illuminance 200,000 lux). The results obtained are shown in Table C.

[0137]

[Table 8]

From the results shown in Table C, it can be seen that the compounds of the present invention show an excellent anti-fading effect even in a light-sensitive material having a multilayer structure.

Example 4 Sample 101 of Example 1 described in JP-A-2-854
In the third, fourth and fifth layer couplers
5 mol% of the compounds (1), (5), (11) of the invention
(14) or (19) was co-emulsified and added to each layer, and the sample was prepared in the same manner as sample 101 except for the above. 25 mol% based on the couplers of the seventh, eighth and ninth layers.
Compound (1), (5), (11), (14) or (19) of the present invention was co-emulsified and added to each layer, and the samples were prepared in the same manner as for sample 101 except for the above.

When these samples were exposed and developed and subjected to a fading test in the same manner as in Example 1 described in JP-A-2-854, the samples of the present invention showed an excellent anti-fading effect.
The photographic characteristics were also good. It has been found that the compounds of the present invention exhibit excellent effects even with this light-sensitive material.

Example 5 In the color photographic light-sensitive material of Example 2 described in JP-A-1-158431, compounds (1) and (5) of the present invention were used in place of Cpd-9 in the sixth and seventh layers. , (11), (1
4) Or replace (19) with Cpd-9 equimolar,
Otherwise, a sample was prepared in the same manner as in the color photographic light-sensitive material of Example 2 described in JP-A-1-158431.

In place of Cpd-6 in the eleventh and twelfth layers, compounds (1), (5), (11) and (1) of the present invention were used.
4) Or replace (19) with Cpd-6 equimolar,
Otherwise, a sample was prepared in the same manner as in the color photographic light-sensitive material of Example 2 described in JP-A-1-158431.

When these samples were exposed and developed in the same manner as in Example 2 described in JP-A-1-158431, the discoloration test and the photographic characteristics were examined. The sample of the present invention showed an excellent anti-fading effect. And photographic characteristics were also good. It has been found that the compounds of the present invention exhibit excellent effects even in this photosensitive material system.

[0144]

The compound represented by the general formula (I) of the present invention has an excellent light fastness improving effect.

Claims (1)

(57) [Claims] 1. A silver halide color photographic material comprising at least one compound represented by the following general formula (A). Embedded image (Wherein R _a1 and R _a1 ′ represent a hydrogen atom or a substituent. R _a2 and R _a2 ′ represent a hydrogen atom, an aliphatic group, an aromatic group, an acyl group or a sulfonyl group, and X represents —O
—, —S— or —N (R _a5 ) —, and X ′ represents —O
_Represents-, -S- or -N (R _a5 ')-. Where R _a5
And R _a5 ′ represent an aliphatic group, R _a2 , R _a5 and R _a5.
a2 'and _Ra5 ' may combine with each other to form a 5- to 7-membered ring. _{R a3, R a4, R a3} ' and R _a4' each represent a aliphatic group, R _a3 and R _a4 and R _a3 'and R _a4' may be bonded to form a 5- to 7-membered ring; . A represents a non-metallic atomic group forming a 5- to 7-membered spiro ring or bicyclo ring together with the benzene ring. an and an '
Represents 0 or 1. )