JPH0693093B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, particularly a silver halide color photographic light-sensitive material for printing, and more specifically, a color image is stable for a long period of time and Excellent image sharpness (hereinafter referred to as sharpness), and
The present invention relates to a high-sensitivity and low-fog silver halide color photographic light-sensitive material.

(Prior Art) Normally, a silver halide color photographic light-sensitive material is spectrally sensitized by adding a spectral sensitizer to silver halide according to the three primary colors of the subtractive method, and a yellow dye is contained in a blue-sensitive silver halide emulsion layer. Forming coupler, the green-sensitive silver halide emulsion layer contains a magenta dye-forming coupler, and the red-sensitive silver halide emulsion layer contains a cyan dye-forming coupler, and after the imagewise exposure, an aromatic primary amine type color developing agent is developed. And a bleach-fixing process to obtain a color image.

However, this color image is not always stable against light, heat, and humidity, and in particular, the cyan dye image has large dark fading due to heat and humidity compared to the yellow dye image and the magenta dye image, and therefore the color balance There were fluctuations and big problems for practical use (for example, reddish prints were made while saving the album).

As a coupler capable of solving such problems and forming a cyan image having high robustness, a benzene ring of a phenol is used.
The so-called 2,5-diacylaminophenol-based couplers in which the 2,5-position is substituted with an acylamino group are particularly excellent, and are disclosed in JP-A-56-80045, JP-A-56-104333, and JP-B-57- 37
No. 857, JP-A-58-105229 and JP-A-60-24547. Further, a phenol type cyan coupler having an alkyl group having 2 or more carbon atoms at the 5-position of the phenol also forms a cyan image with high fastness.

These phenol-based cyan couplers have high heat fastness and are extremely useful couplers for obtaining color photographic images with good storage stability, but not only that, photographic light-sensitive materials using these couplers can be processed. It is known that the stability, particularly the decrease in cyan density during the bleach-fixing process, is small and the so-called color restoration property is excellent.

Thus, the above-mentioned type of phenol-based coupler is a preferable compound for use as a cyan dye-forming coupler in a color photographic light-sensitive material.

Further, other standard conditions for selecting a cyan coupler include, for example, light resistance, spectral absorption characteristics of color forming dye, influence on photographic performance, and the like, and a cyan coupler satisfying all of these performances is desired. It will be.

On the other hand, image quality is another important characteristic required for color photosensitive materials for printing, and sharpness has a great influence on image quality.

Two techniques are commonly used to improve the sharpness of color images. One is that the light scattered during or after passing through the silver halide emulsion layer is reflected again at the interface between the silver halide emulsion and the support or at the surface of the light-sensitive material opposite to the silver halide emulsion layer, and then again. It is to prevent image blurring, i.e. halation, due to incidence on the silver halide emulsion layer, and the other is image based on light scattering on the silver halide surface in the silver halide emulsion layer. It is to prevent the blur, that is, the irritation.

The latter prevention of irradiation is generally used in a silver halide color photographic light-sensitive material for printing.

The silver halide emulsion layer is colored to prevent irradiation. These layers to be colored are often composed of hydrophilic colloids, so that for their coloring usually water-soluble dyes are included in the layers. This dye is required to satisfy the following conditions.

(1) It has a proper spectral absorption according to the purpose of use.

(2) Photochemically inactive. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as reduction in sensitivity, latent image regression, or fog.

(3) It should not be decolorized or dissolved and removed in the course of photographic processing to leave no harmful coloring on the photographic light-sensitive material after processing.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the dyes listed below are known. For example, British Patent Nos. 506,385, 1,177,429, and
1,311,884, 1,338,799, 1,385,371, 1,46
7,214, 1,433,102, 1,553,516, JP-A-48-8
5,130, 49-114,420, 55-161,233, 59-111,
640, U.S. Pat.Nos. 3,247,127, 3,469,985, and 4,0
Oxonol dyes having a pyrazolone nucleus or barbituric acid nucleus described in 78,933, U.S. Pat.No. 2,533,472,
No. 3,379,533, other oxonol dyes described in British Patent No. 1,278,621, British Patent Nos. 575,691, 68.
0,631, 599,623, 786,907, 907,125,
1,045,609, U.S. Pat.No. 4,255,326, JP-A-59-211,0
Azo dyes described in, for example, JP-A Nos. 50-100,116,
54-118,247, UK Patent No. 2,014,598, azomethine dyes described in the same 750,031, etc., anthraquinone dyes described in U.S. Patent No. 2,865,752, U.S. Patent No. 2,538,00
No. 9, No. 2,688,541, No. 2,538,008, British Patent No. 584,6
09, 1,210,252, JP-A-50-40,625, 51-3,623
No. 51, No. 51,927, No. 54-118,247, Japanese Patent Publication No. 48-3,286
No. 59-37,303 and the like, arylidene dyes described in
Styryl dyes described in Japanese Examined Patent Publication Nos. 28-3,082, 44-16,594, 59-28,898, etc., British Patent No. 446,583, 1,3
35,422, triarylmethane dyes described in JP-A-59-228,250 and the like, British Patent Nos. 1,075,653 and 1,153,341
No. 1,284,730, No. 1,475,282, No. 1,542,807, and other merocyanine dyes described in U.S. Pat.
And cyanine dyes described in No. 3,294,539 and the like.

Of these, oxonol dyes having two pyrazolone nuclei have the property of being decolorized in a developer containing sulfite, and are used for dyeing photographic materials as useful dyes with few adverse effects on photographic emulsions. Came.

(Problems to be Solved by the Present Invention) However, among oxonol dyes having two pyrazolone nuclei, a silver halide emulsion itself or a spectrally sensitized silver halide emulsion is spectrally separated into unnecessary regions. Many of them have drawbacks such as sensitization, reduction in sensitivity which is considered to be caused by desorption of a spectral sensitizer, and increase in fog.

In addition, there are some that remain after the processing due to the speeding up of the developing processing that has recently been performed. In order to solve this, it has been proposed to use a dye having a high reactivity with sulfite ion, but in this case, the stability in the dry film is not sufficient, and the concentration decreases with time, However, it has a drawback that the photographic effect of can not be obtained.

Further, when combined with the above-mentioned 2,5-diacylaminophenol-based coupler having particularly high heat fastness, the degree of decrease in sensitivity and increase in fog became large, which was a serious problem in practical use. JP-A-60-225155 has 2,5
-There is a description that a light-sensitive material in which a diacylaminophenol coupler is combined with a specific oxonol dye has excellent dark fading properties, good sharpness, and excellent latent image stability and whiteness (low fog). It has been found that the combination is not sufficient particularly in terms of sharpness and fog.

(Object of the Invention) Therefore, the object of the present invention is to exert no detrimental effect on the photographic characteristics of the silver halide emulsion layer, and excellent decolorization by processing,
A silver halide color photographic light-sensitive material having a red-sensitive emulsion layer with high sensitivity and low fog, which uses a new water-soluble dye that is stable over time to provide a stable color image for a long period of time with excellent sharpness. Is to provide.

(Means for Solving Problems) An object of the present invention is to contain a compound represented by the following general formula [I] on a support, and at least one compound represented by the following general formula [II]. And a silver halide color photographic light-sensitive material.

General formula [I] In the formula, R ₁ and R ₂ are each -COOR ₅ , Represents R ₃ and R ₄ each represent a hydrogen atom or an alkyl group, and R ₅ and R ₆ each represent a hydrogen atom, an alkyl group and an aryl group. R ₅ and R ₆ are linked to each other to form a 5- or 6-membered ring, and Q ₁ and Q ₂ each represent an aryl group. X ₁ and X ₂ represent a divalent linking group or bond, and Y ₁ and Y ₂ represent a sulfo group and a carboxyl group, respectively. L ₁ , L ₂ and L ₃ each represent a methine group or a substituted methine group. m ₁ and m ₂ are 1 or 2, n
Is 0, 1 or 2, p ₁ and p ₂ are 0, ₁ , ₂ , 3 or 4, s ₁ and s ₂ are 1 or 2, respectively.

General formula (II) In the formula, Y ₃ represents —NHCO— or —CONH—, R ₈ represents an optionally substituted aliphatic group, an aromatic group, a heterocyclic group or an arylamino group, and X ₃ represents a hydrogen atom or a halogen. Represents an atom, an alkoxy group or an acylamino group, R ₇ represents an alkyl group (having 2 or more carbon atoms) or an acylamino group, or X ₃
And R ₇ represent a non-metal atomic group forming a 5- to 7-membered ring, and Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a developing agent.

Next, the dye represented by the general formula [I] will be described in detail.

In the formula, R ₁ and R ₂ are each -COOR ₅ , Represents R ₃ and R ₄ each represent a hydrogen atom or an unsubstituted alkyl group (eg, methyl group, ethyl group), and R ₅ and R ₆ represent a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, isopropyl group, butyl group, etc.) ), A substituted alkyl group {a sulfo group (for example, a sulfomethyl group, a sulfoethyl group, etc.) as a substituent, a carboxyl group (for example, a carboxymethyl group,
Carboxyethyl group), hydroxy group (eg hydroxyethyl group, 1,2-dihydroxypropyl group etc.), alkoxy group (eg methoxyethyl group, ethoxyethyl group etc.), halogen atom {fluorine atom, chlorine atom, bromine atom ( For example, 2-chloroethyl, 2-bromoethyl-2,2,2-trifluoroethyl group), cyano group (for example, cyanoethyl group), sulfonyl group (for example, methanesulfonylethyl group), nitro group (for example, 2-nitrobutyl group, 2-nitro-2-methylpropyl group etc.), amino group (eg dimethylaminoethyl group, diethylaminopropyl group etc.), aryl group (eg benzyl group, p-chlorobenzyl group etc.)}, phenyl group,
Substituted phenyl group {As a substituent, a sulfo group (for example, p
-Sulfophenyl group, o, p-disulfophenyl group, etc.), carboxyl group (for example, p-carboxyphenyl group, m-carboxyphenyl group, etc.), hydroxy group (for example, p-hydroxyphenyl group, m-hydroxyphenyl group) Etc.), an alkoxy group (for example, p-methoxyphenyl group, m-ethoxyphenyl group, etc.), a halogen atom (for example, p-chlorophenyl group, p-bromophenyl group, p-fluorophenyl group, etc.), a cyano group (for example, p-cyanophenyl group, o-cyanophenyl group, etc.),
Nitro group (eg, p-nitrophenyl group, m-nitrophenyl group, etc.), amino group (eg, p-dimethylaminophenyl group, p-diethylaminophenyl group, etc.), alkyl group (eg, p-methylphenyl, o-methylphenyl group, etc.) )} Is represented.

When R ₁ and R ₂ represent --COOR ₅ , R ₅ is R when R ₅ is a hydrogen atom.
_{Although 1} and R ₂ represent a carboxyl group, they may form not only a free acid but also a salt (for example, Na salt, K salt, ammonium salt, quaternary ammonium salt, etc.).

Further, R ₅ and R ₆ may form a 5-membered ring or a 6-membered ring (eg, morpholino group, piperidino group, etc.). Q ₁ and Q ₂ are an unsubstituted aryl group (for example, a phenyl group, a naphthyl group), a substituted phenyl group (the substituent is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (chloro, Bromo, fluoro), carbamoyl group (eg, ethylcarbamoyl group), sulfamoyl group (eg, ethylsulfamoyl group), cyano group, nitro group,
Alkylsulfonyl group (eg methanesulfonyl group), arylsulfonyl group (eg benzenesulfonyl group), amino group (eg dimethylamino group), acylamino group (eg acetylamino group), sulfonamide group (eg methanesulfonamide) Group)). X ₁ and X ₂ each represent a divalent linking group.

More specifically, -O-, Or represents a bond, R ₇ is a hydrogen atom, an alkyl group having 5 or less carbon atoms, a substituted alkyl group having 5 or less carbon atoms (as a substituent, an alkoxy group having 3 or less carbon atoms, a sulfo group (eg, a sulfoethyl group, a sulfopropyl group) Etc.), carboxyl group (eg carboxyethyl group etc.), cyano group, hydroxy group, amino group (eg hydroxyethyl group etc.), sulfonamide group (eg methanesulfonamide group etc.), carbonamide group (eg acetylamino group etc.) ), A carbamoyl group (such as an ethylaminocarbonyl group), a sulfamoyl group (such as an ethylaminosulfonyl group), and the like}. Y ₁ and Y ₂ each represent a sulfo group or a carboxyl group, which may form not only a free acid but also a salt (for example, Na salt, K salt, ammonium salt, quaternary ammonium salt, etc.). L ₁ , L ₂ , and L ₃ are a methine group, a substituted methyl group, (a methyl group as a substituent,
Ethyl group, phenyl group, etc.). m ₁ and m ₂ are 1 each
Or 2, n is 0, 1 or 2, p ₁ , p ₂ is 0, 1, 2, 3 or 4, s ₁ , s ₂ is 1 or 2 respectively.
Represents

Of the substituents represented by the general formula (I), hydrogen atoms and methyl groups are preferred as R ₃ and R ₄ , hydrogen atoms, R ₅ and R ₆ are hydrogen atoms, alkyl groups having 4 or less carbon atoms, and substitutions having 6 or less carbon atoms. Alkyl group {As the substituent, a sulfo group, a carboxyl group, a hydroxy group, an alkoxy group having 2 or less carbon atoms, a chlorine atom, a cyano group, an amino group, or an alkylamino group having 4 or less carbon atoms is preferable. }, A phenyl group, a substituted phenyl group {as a substituent, a sulfo group, a carboxyl group, an alkoxy group having 4 or less carbon atoms, a chlorine atom, a cyano group, an alkyl group having 4 or less carbon atoms, an amino group, an alkyl having 4 or less carbon atoms. Amino groups are preferred. It is preferable that R ₅ and R _{6 form} a 5-membered ring or a 6-membered ring (for example, a morpholino ring, a pyrrolidine ring or a piperidine ring).

Q ₁ and Q ₂ are phenyl groups, substituted phenyl groups {substituents include alkyl groups having 4 or less carbon atoms, alkoxy groups having 4 or less carbon atoms, halogen atoms (chloro, bromo, fluoro),
A dialkylamino group having 4 or less carbon atoms is preferable. } Is preferred.

X ₁ and X ₂ are -O-, Alternatively, a bond is preferred, and as R ₇ , a hydrogen atom, an alkyl group having 5 or less carbon atoms, a substituted alkyl group having 5 or less carbon atoms (as a substituent, an alkoxy group having 3 or less carbon atoms, a cyano group, a hydroxy group, a carbon number 4) The following alkylamino groups and the like are preferable.

Further, among the dyes represented by formula (I), m ₁ = m ₂ = 1 is more preferable.

Next, specific examples of the compound of the general formula [I] used in the present invention are shown, but the present invention is not limited thereto.

The compound represented by the general formula (I) can be synthesized by various synthetic methods. For example, as shown in the following reaction formula, pyrazolone (II) and (IIIa), (IIIb), (IIIc),
It can be synthesized by condensation with a compound represented by (IIId) or (IIIe) in the presence of a base.

(IIIb) HC (OC ₂ H ₅ ) ₃ Where R ₁ , R ₃ , Q ₁ , X ₁ , Y ₁ , L ₁ , L ₂ , L ₃ , m ₁ , n, p ₁ ,
s ₁ has the same meaning as described above, and Z represents a hydrogen atom, a nitro group or a halogen atom (eg chloro or bromo).
R ₈ represents a hydrogen atom, an alkyl group (eg methyl, ethyl, etc.) or a phenyl group. X is an anion (eg chloride, bromide, iodide, perchlorate,
Methyl sulphate, ethyl sulphate, p-toluene sulphonate etc.).

The synthesis examples of the compound according to the present invention are described below, but the invention is not limited thereto.

Synthesis Example 1 (Compound 3) 3-Ethoxycarbonyl-1- (2-sulfobenzyl)
Pyrazolin-5-one (5.2 g) was added to ethanol (50 ml), triethylamine (4.2 ml) and malondialdehyde dianyl salt (1.5 g) were added, and the mixture was heated under reflux for 3 hours to give a homogeneous solution. A solution of 1.2 g of sodium acetate in 15 ml of methanol is added to this hot solution with stirring. Next, 25 ml of isopropanol is added to precipitate dark purple crystals. The crystals are washed with isopropanol and dried to give compound 3
2g was obtained.

Melting point 300 ° C or higher Synthesis Example 2 (Compound 8) 7.4 g of 3-carboxy-1- (2-sulfobenzyl) pyrazolin-5-one (intermediate B), 50 ml of methanol and 7.5 ml of triethylamine are mixed and cooled with ice. To this, 2.8 g of glutaraldehyde dianyl hydrochloride is added and stirred for 3 hours. Next, a solution of 4.2 g of sodium acetate in 50 ml of methanol was added, and further 25 ml of isopropanol was added to precipitate dark purple crystals. The crystals were collected, washed with isopropanol and dried to obtain 5.4 g of compound 8.

Melting point 300 ° C or higher Synthesis Example 3 (Compound 10) 3- (2-hydroxyethylcarbamoyl) -1- (2
-Sulfobenzyl) pyrazoline 8g, methanol 30ml, triethylamine 3.8ml are mixed and cooled. To this solution was added 3 g of glutaraldehyde dianyl salt, followed by 2 m of acetic anhydride.
add l After reacting at room temperature for 1 hour, 20 ml of isopropanol was added to precipitate black crystals. The crystals were washed with isopropanol and dried to obtain 6.1 g of compound 10.

Melting point 300 ° C. or higher λmax 633 nm ε8.8 × 10 ⁴ Synthesis example 4 (compound 18) 3-carboxy-1- {2- (4-sulfophenyl) ethyl} pyrazolin-5-one 6 g, methanol 50 ml, triethylamine 7 ml are mixed. Then, 1.6 g of N, N'-diphenylformamidine hydrochloride is added and heated for 2 hours to form a uniform solution. Add 4.5 g of sodium acetate to this solution in methanol.
ml and then 20 ml of isopropanol, yellow crystals are precipitated. The crystals were collected, washed with isopropanol, and dried to obtain 4 g of compound 18.

Melting point 300 ° C or higher Synthetic Example 5 (Compound 12) Compound 12 can be obtained by the same procedure as in Synthetic Example 2 using 3-ethoxycarbonyl-1- (2,4-disulfobenzyl) pyrazolin-5-one.

Melting point 300 ° C or higher Synthesis Example 6 (Compound 20) Synthesis Example 2 using 3-carboxy-1- {2- (4-sulfobutyloxy) benzyl} pyrazolin-5-one
Compound 20 is obtained by the same operation as the above.

Melting point 264-269 ℃ (decomposition) Next, the general formula [II] will be described in detail.

In the general formula [II], R ₈ is a linear or cyclic aliphatic group having 1 to 32 carbon atoms (eg, methyl group, butyl group, pentadecyl group, cyclohexyl group, etc.), aromatic group (eg, phenyl group) , A naphthyl group), a heterocyclic group (for example, a 2-pyridyl group, a 3-pyridyl group, a 2-furanyl group, a 2-oxazolyl group) or a substituted amino group, and these are an alkyl group, an aryl group, an alkyl or Aryloxy group (for example, methoxy group, dodecyloxy group, methoxyethoxy group, phenyloxy group, 2,
4-di-tert-aminophenoxy group, 3-tert-butyl-4-hydroxyphenyloxy group, naphthyloxy group, etc., carboxy group, alkyl or arylcarbonyl group (eg, acetyl group, tetradecanoyl group, benzoyl group) Etc.), alkyl or aryloxycarbonyl group (eg, methoxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, etc.), acyloxy group (eg, acetyl group, benzoyloxy group, phenylcarbonyloxy group, etc.), sulfamoyl group (eg, , N-ethylsulfamoyl group, N-octadecylsulfamoyl group, etc.), carbamoyl group (eg, N-ethylcarbamoyl group, N-methyl-dodecylcarbamoyl group, etc.), sulfonamide group (eg,
Methanesulfonamide group, benzenesulfonamide group, etc.), acylamino group (eg, acetylamino group, benzamide group, ethoxycarbonylamino group, phenylaminocarbonylamino group, etc.), imide group (eg,
It may be substituted with a substituent selected from a succinimide group, a hydantoinyl group and the like), a sulfonyl group (for example, a methanesulfonyl group and the like), a hydroxy group, a cyano group, a nitro group and a halogen atom.

In the present specification, the “aliphatic group” refers to a linear, branched or cyclic aliphatic hydrocarbon group, such as alkyl, alkenyl,
It may be saturated or unsaturated such as an alkynyl group.

In the general formula [II], R ₇ represents an alkyl group having 2 to 20 carbon atoms (eg, ethyl group, butyl group, pentadecyl group, etc.) or an acylamino group (eg, tetradecanoylamino group, benzoylamino group, 2- (2,4-diTERT-amylphenoxy) butanamide group and the like).

In the general formula [II], X ₃ is a hydrogen atom, a halogen atom, an aliphatic group (eg, methyl group, propyl group, allyl group, etc.), an alkoxy group (eg, methoxy group, butoxy group, etc.), or acylamino. Represents a group (for example, an acedamide group and the like).

In the general formula [II], R ₇ and X ₃ are connected to each other and are 5, 6, 7
May be a non-metal atomic group forming any ring of
Examples thereof include a benzene ring and a lactam ring.

In the general formula [II], Z represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (eg, ethoxy group, dodecyl). Oxy group, methoxycarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (for example, 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.),
Acyloxy group (eg, acetoxy group, tetradecanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, heptabutyi) Rylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group, etc.) , An aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide group (eg,
Examples include succinimide group, hydantoinyl group, N-heterocycle (eg, 1-pyrazolyl group, 1-benztriazolyl group, etc.), aromatic azo group (eg, phenylazo group, etc.), and the like. These leaving groups may include photographically useful groups.

In formula [II], R ₇ is preferably an alkyl group having 2 to 15 carbon atoms, and more preferably 2 to 4 carbon atoms.

Z in the general formula [II] is preferably a hydrogen atom or a halogen atom, and a halogen atom is particularly preferred.

In formula [II], preferred X ₃ is a halogen atom.

When R ₇ and X _{3 in the} general formula [II] are closed to form a ring, it is preferably a 5-membered oxindole ring.

Next, specific examples of the compound of the general formula [II] used in the present invention are shown, but the present invention is not limited thereto.

When the dye represented by formula (I) is used as a filter dye, an anti-irradiation dye or an antihalation dye, any effective amount can be used,
It is preferably used so that the optical density is in the range of 0.05 to 3.0. The addition time may be any step before coating.

The dye according to the present invention can be dispersed in a hydrophilic colloid layer such as an emulsion layer (intermediate layer, protective layer, antihalation layer, filter layer, etc.) by various known methods.

A method of directly dissolving or dispersing the dye of the present invention in an emulsion layer or a hydrophilic colloid layer, or a method of dissolving or dispersing it in an aqueous solution or a solvent and then using it in the emulsion layer or the hydrophilic colloid layer. Suitable solvent, for example, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, halogenated alcohol described in U.S. Pat. No. 3,756,830, acetone, water, pyridine, etc., or a mixed solvent thereof. It is also possible to add it to the emulsion in the form of a solution dissolved in

A method in which a hydrophilic polymer having a charge opposite to that of a dye ion is allowed to coexist in a layer as a mordant, and the dye is localized in a specific layer by interacting with the dye molecule.

The polymer mordant is a polymer having secondary and tertiary amino groups, a polymer having a nitrogen-containing heterocyclic portion, and a polymer having a quaternary cation group. Those having a molecular weight of 5000 or more are particularly preferably 10,000 or more. .

For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers described in US Pat. No. 2,548,564: vinyl imidazolium cationic polymers disclosed in US Pat. No. 4,124,386; disclosed in US Pat. No. 3,625,694 Polymer mordant capable of cross-linking with gelatin; US Pat. No. 3,958,995, JP-A-54-
Aqueous sol mordants disclosed in, for example, 115228 specification;
Water-insoluble mordants disclosed in U.S. Pat. No. 3,898,088; Reactive mordants capable of forming a covalent bond with dyes disclosed in U.S. Pat. No. 4,168,976; British Patent 68
Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in 5,475; products obtained by reaction of polyvinyl alkyl ketone with aminoguanidine as described in British Patent 850,281. Polymers derived from 2-methyl-1-vinylimidazole as described in U.S. Pat. No. 3,445,231 can be mentioned.

A method of dissolving a compound using a surfactant.

The useful surfactant may be an oligomer or a polymer.

Details of this polymer are described on pages 19 to 27 of the specification of JP-A-60-158437 (filed by Fuji Photo Film Co., Ltd. on January 26, 1984).

Further, a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained above.

The cyan coupler represented by the general formula [II] is 0. 0 per 1 mol of silver halide in the photosensitive silver halide emulsion layer to be introduced.
1 to 1 mol, preferably 0.2 to 0.5 mol is used.

The cyan coupler represented by the general formula (II) is dissolved in a high-boiling point organic solvent (eg, phthalic acid ester-based, phosphoric acid ester-based, fatty acid ester-based) and dispersed in a hydrophilic colloid medium to prepare a silver halide emulsion. Can be added to.

Further, in order to improve the storage stability, a benzotriazole-based ultraviolet absorber may be used together, or a substantially water-insoluble organic solvent-soluble polymer may be used together. In particular, the latter polymer combination is effective for improving the dark fading property. Particularly useful ones include those described in Japanese Patent Application Publication No. WO88 / 00723.

Gelatin is a typical hydrophilic colloid, but any of those conventionally known as those usable for photography can be used.

In the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide. Especially for the purpose of rapid processing, silver chlorobromide containing 90 mol% or more (preferably 98 mol% or more) of silver chloride is preferable. This silver chlorobromide may contain a small amount of silver iodide, but it is preferable that it does not contain silver iodide at all.

The silver halide grains used in the present invention have a regular crystal form such as a cube or an octahedron,
Those having an irregular (irregular) crystal form such as a sphere or a plate, or a compound form of these crystal forms. It is also possible to use a mixture of grains having various crystal forms, but it is preferable to use a regular crystal form.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Also, grains in which a latent image is mainly formed on the surface (eg, negative emulsion) may be used, and grains in which the latent image is mainly formed (eg, internal latent image type emulsion, pre-fogged direct reversal type emulsion) May be Preferably, the particles are such that a latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5 micron or less, preferably 0.3 micron or less and a diameter of preferably 0.6 micron or more, and grains having an average aspect ratio of 5 or more account for 50% or more of the total projected area. Or a monodisperse whose statistical coefficient of variation (value S / (standard deviation S divided by diameter in distribution represented by diameter when the projected area is approximated by circle) S /) is 20% or less. Emulsions are preferred. Further, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is P. grafchides (P.
Glafkides), Chimie er Physique Photographeque (Paul Montel, 1967), GFDuffin, Photographic Emulsion Chemistry
(Published by Focal Press, 1966) by VLZelikman et al., Making and Coating Photographic Emulsion (Making
and Coating Photograhic Emulsion) (published by Focal Press, 1964) and the like.

Further, in order to control the growth of grains during the formation of the silver halide grains, as a silver halide solvent, for example, ammonia, rodancali, rodanammon, and a thioether compound (for example, U.S. Pat.Nos. 3,271,157 and 3,574,628).
No. 3, No. 3,704, 130, No. 4,297, 439, No. 4,276, 37
No. 4, etc.), thione compounds (for example, JP-A-53-144319,
53-82408, 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) and the like can be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or iron complex salt may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Frieser ed., Die Grundlagen del Photography Sien Protese Mitt Silber Halden (Die Gr)
undlagen der Photographischen Prozesse mit Silberh
alogeniden) (Academisier Ferragus Gezerschact 1968) pp. 675-734.

That is, a sulfur-sensitizing method using a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (for example, first tin salt) , Amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); reduction sensitization methods; noble metal compounds (eg, gold complex salts, complex salts of Group VIII metals such as Pt, Ir, Pd) The noble metal sensitizing method to be used can be used alone or in combination.

The silver halide photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. it can. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; such as carboxyl group and sulfone group The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazoline thione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfone Many compounds known as antifoggants or stabilizers can be added, such as acids; benzenesulfinic acid; and the like.

The silver halide photographic emulsion of the present invention is a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler.
A coupler and a compound that disperses the coupler may be included.

That is, it may contain a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include:
Acyl acetamide couplers (for example, benzoyl acetanilides, pivaloyl acetanilides), and the like.

These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, it may be a colored coupler having a color correcting effect, or a coupler releasing a development inhibitor with development (so-called DIR coupler).

In addition to the DIR coupler, a colorless DIR coupling compound which is colorless in the product of the coupling reaction and releases a development inhibitor may be contained. Also cinnamic acid ester and 2
An ultraviolet absorber represented by-(2-hydroxyphenyl) benzotriazole or an anti-fading agent may be added.

These anti-fading agents include the compounds described in the following specific specifications: U.S. Patents 3,432,300, 3,573,045, 3,574,627.
Issue 3,700,455, Issue 3,764,337, Issue 3,935,016,
4,254,216, 4,268,593, 4,430,425, 4,4
65,757, 4,465,765, 4,518,679, British Patent 1,
347,556, British Patent Publication 2,066,975, JP-A-52-152,2
No. 25, No. 53-17,729, No. 53-20,327, No. 54-145,530
No. 55, No. 55-6321, No. 55-21,004, No. 61-72,246, No. 6
1-73,152, 61-90,155, 61-90,156, 61-14
No. 5,554 In the photographic emulsion of the present invention, for the purpose of increasing sensitivity, increasing contrast or promoting development, for example, polyalkylene oxide or its ether, ester, derivative such as amine, thioether compound, thiomorpholine, quaternary ammonium salt compound, A urethane derivative, a urea derivative, an imidazole derivative, 3-pyrazolidones and the like may be included.

In the silver halide photographic emulsion of the present invention, a known aqueous dye other than the dyes disclosed in the present invention (for example, oxonol dyes; hemioxonol dyes and merocyanine dyes) as a filter dye or for various purposes such as prevention of irradiation. You may use together with. The spectral sensitizer may be used in combination with a known cyanine dye, merocyanine dye or hemicyanine dye other than the dyes shown in the present invention.

The photographic emulsion of the present invention contains various surfactants for various purposes such as coating aid, antistatic property, sliding property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, hardening, sensitization). But it's okay.

Regarding the light-sensitive material of the present invention, with respect to anti-fading agent, hardener, anti-foggant, ultraviolet absorber, protective colloid such as gelatin, and various additives, specifically, Research Disclosure Vol. 176 ( 1978, XII) RD-17643 and the like.

The finished emulsion is coated on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

The silver halide photographic light-sensitive material of the present invention includes a color positive film, a color paper, a color negative film, a color reversal film (which may or may not contain a coupler), and a plate-making photographic light-sensitive material (for example, lith film, lith dupe). Films, etc., cathode ray tube display photosensitive materials (eg emulsion X-ray recording photosensitive materials, direct and indirect imaging materials using screens), silver salt diffusion transfer process photosensitive materials, color diffusion transfer Photosensitive material for process, die transfer process
Light-sensitive material, light-sensitive material used in silver dye bleaching method, light-sensitive material for recording printout image, photo-developing printout (Direct
Print image) Photosensitive materials, photothermographic materials, physical development photosensitive materials, and the like.

The exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (sunlight), tungsten lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. The exposure time is usually 1/1000 second to 30 seconds, but 1/10
An exposure shorter than 00 seconds, for example, a 1/10 ⁴ to 1/10 ⁶ second exposure using a xenon flash lamp or a cathode ray tube can be used, or an exposure longer than 30 seconds can be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed. Laser light can also be used for the exposure. It may also be exposed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray or the like.

For photographic processing of a light-sensitive material produced by using the present invention, for example, Research Disclosur
e) Any known method and known processing solution as described in No. 176, pages 28 to 30 (RD-17643) can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually chosen between 18 and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

The color photograph processing method is not particularly limited, and any method can be applied. For example, as a typical example thereof, after exposure, color development, bleach-fixing treatment is performed, and if necessary, further washing with water and stabilization treatment are performed.After exposure, color development, bleaching and fixing treatment are separately performed, A method of further washing with water and stabilizing treatment, if necessary, after exposure, developing with a developer containing a black-and-white developing agent, applying uniform exposure, then performing color development and bleach-fixing treatment, and further washing with water as necessary. , A stabilizing method or after exposure, development with a developing solution containing a black-and-white developing agent, further developing with a color developing solution containing a kasbrush agent (for example, sodium borohydride), and then bleach-fixing processing, There is a method of further washing with water and stabilizing treatment if necessary.

The aromatic primary amine type color developing agents used in the color developing solution in the present invention include known ones widely used in various color photographic processes. These developing agents include aminophenol-based and p-phenylenediamine-based derivatives. A preferred example is a p-phenylenediamine derivative, and representative examples are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D- 9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β-
Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β-
Butoxyethylaniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The above compounds are described in U.S. Pat.
No. 5, No. 2,552,241, No. 2,566,271, No. 2,592,364,
No. 3,656,950, No. 3,698,525, etc. The amount of the aromatic primary amine color developing agent used is the amount of the developing solution 1
The concentration is about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g.

The color developer used in the present invention may contain hydroxylamines as is well known.

Hydroxylamines are more commonly used in the form of acid salts of aqueous solutions, although they can be used in the form of free amines in color developers. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates and the like. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.

Addition amount of hydroxylamine is 0g per 1 color developer.
It is preferably 10 g, more preferably 0 to 5 g. If the stability of the color developer is maintained, it is preferable that the addition amount be small.

Further, it is preferable that the preservative contains a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct. The addition amount of these is preferably 0 g to 20 g / l, more preferably 0 g to 5
If it is g / l and the stability of the color developing solution is maintained, it is preferably as small as possible.

Other preservatives include JP-A Nos. 52-49828 and 56-47038.
No. 56-32140, No. 59-160142 and U.S. Pat. No. 37465.
Aromatic polyhydroxy compounds described in US Pat.
Hydroxyacetones described in 5,503 and British Patent 1,306,176; α-aminocarbonyl compounds described in JP-A-52-143020 and 53-89425; described in JP-A-57-44148 and 57-53749 Various metals of JP-A-52-10272
Various saccharides described in No. 7; hydroxamic acids described in No. 52-27638; α, α'-dicarbonyl compounds described in No. 59-160141; salicylic acids described in No. 59-180588; described in No. 54-3532 Alkanolamines; poly (alkyleneimine) s described in JP-A-56-94349; gluconic acid derivatives described in JP-A-56-75647 and the like. Also hydrazine-N,
N-diacetic acid is also preferred. Two or more kinds of these preservatives may be used in combination, if necessary. Especially 4,5-dihydroxy-
Addition of m-benzenedisulfonic acid, poly (ethyleneimine), triethanolamine, etc. is preferred.

The color developer used in the present invention preferably has a pH of 9 to
12, more preferably 9 to 11, and the color developing solution may contain other known developing solution component compounds.

For details of preservatives, buffers, chelating agents, development accelerators, antifoggants, and fluorescent whitening agents which can be added to the color developing solution, the details and types thereof are described in JP-A-63-229457. Page 4, upper left column to page 6, upper left column.

The processing temperature of the color developer of the present invention is preferably 20 to 50 ° C.
30-40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 4 minutes. The replenishment amount is preferably small, but it is 30 to 1000 ml, preferably 60 to 400 ml, per 1 m ^{2 of} the light-sensitive material.

Next, the desilvering process in the present invention will be described. As the desilvering step, generally, any step such as a bleaching step-fixing step, a fixing step-bleaching fixing step, a bleaching step-bleaching fixing step, a bleaching fixing step may be used. The desilvering step is 2 minutes or less, more preferably 15 seconds to 90 seconds.

Further, the bleaching solution, the bleach-fixing solution and the fixing solution used in the present invention, and the additives and the amounts thereof to these solutions can be applied, for example, those described in the above-mentioned application specification pages 20 to 25. .

Further, the matters described in the above-mentioned application specification, page 25 to page 29, line 12 can be applied to the washing and / or stabilizing treatment performed after the desilvering processing.

(Example) Next, the present invention will be described in more detail based on examples.

Example 1 A multilayer color print sample (1) having the following layer structure was prepared on a paper support laminated on both sides with polyethylene.

Layer composition The composition of each layer is shown below. Numbers represent coating amount (g / m ² ). However, the silver halide emulsion is shown in terms of silver equivalent coating amount, and the cyan coupler and dye are shown in mol / m ² .

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO2 and bluish dye (ultraviolet).] First layer (blue-sensitive silver halide emulsion layer) Spectral sensitizer (Sen-1) Monodispersed silver chlorobromide emulsion (EM-1) 0.16 Monodispersed silver chlorobromide emulsion (EM-2) with spectral sensitizer (Sen-1) 0.10 Antifoggant (Cpd-1) 0.004 Gelatin 1.83 Yellow coupler (ExY) 0.83 Dye stabilizer (Cpd-2) 0.03 Polymer (Cpd-3) 0.08 Solvent (Solv-1 and Solv-2 volume ratio 1: 1) 0.35 Hardener (Hd) 0.02 Second layer ( Anti-mixing layer) Gelatin 1.25 Anti-mixing agent (Cpd-4) 0.04 Solvent (Solv-3 and Solv-4 volume ratio 1: 1) 0.20 Hardener (Hd) 0.02 Third layer (Green-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-3) with spectral sensitizer (Sen-2,3) 0.05 Monodisperse silver chlorobromide milk with spectral sensitizer (Sen-2,3) (EM-4) 0.11 Antifoggant (Cpd-5) 0.001 Gelatin 1.79 Magenta coupler (ExM) 0.32 Color image stabilizer (Cpd-6) 0.20 Color image stabilizer (Cpd-7) 0.03 Color image stabilizer (Cpd-) 8) 0.03 Solvent (Solv-3 and Solv-5 volume ratio 1: 2) 0.65 Hardener (Hd) 0.01 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1 / 2/3 molar ratio 1 : 4: 4) 0.62 Color mixture inhibitor (Cpd-4) 0.05 Solvent (Solv-6) 0.34 Dye (Dy-1) 1.8 × 10 ^-5 mol Dye (Dy-2) 2.0 × 10 ^-5 mol Hardener ( Hd) 0.01 Fifth layer (red-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-5) 0.07 Spectral sensitizer (Sen-4) , 5) added monodispersed silver chlorobromide emulsion (EM-6) 0.15 antifoggant (Cpd-9) 0.0002 gelatin 1.34 cyan coupler Table 2 6.7 × 10 ^-4 mol UV absorber (UV-1 / 3 / 4 molar ratio 1: 3: 3) 0.17 polymer (Cp: -3) 0. 33 Solvent (Solv-1) 0.23 Hardener (Hd) 0.01 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1 / 2/3 molar ratio 1: 4: 4) 0.21 Solvent (Solv-6) ) 0.08 Hardener (Hd) 0.01 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.17 Liquid paraffin 0.03 The silver halide emulsion (EM-1) used in the above sample was prepared as follows.

(1st solution) H ₂ O 1000ml NaCl 5.5g Gelatin 25g (2nd solution) Sulfuric acid (1N) 20ml (3rd solution) The following compound (1%) 2ml (4 solution) KBr 2.80g NaCl 0.34g H ₂ O added 140ml (5 solution) AgNO ₃ 5g H ₂ O added 140ml (6 solution) KBr 67.20g NaCl 8.26g K ₂ IrCl ₆ (0.01%) 0.7 Add 320 ml of H ₂ O (7 solutions) AgNO ₃ 120 g NH ₄ NO ₃ (50%) Add ₂ ml of H ₂ O and heat 320 ml (1 solution) to 74 ° C to prepare (2 solutions) and (3 solutions) After that, (4 solution) and (5 solution) were simultaneously added by spending 9 minutes, and 10 minutes later, (6 solution) and (7 solution) were simultaneously added by spending 45 minutes, and 5 minutes after addition. Water, dispersed gelatin were added, pH was adjusted to 6.2, average particle size was 0.96 μm, coefficient of variation (standard deviation divided by average particle size; s /) 0.08, bromide A 80% mol silver monodisperse cubic silver chlorobromide emulsion was obtained, which was optimally chemically sensitized with sodium thiosulfate.

Other silver chlorobromide emulsions (EM-2) to (EM-6) were prepared in the same manner by changing the amount of chemicals, temperature and time.

The details are shown in Table 1 below.

(Sen-1) 6 × 10 ^-4 mol / Ag mol (Sen-2) 4 × 10 ^-4 mol / Ag mol (Sen-3) 8 × 10 ^-5 mol / Ag mol (Sen-4) 1.8 × 10 ^-4 mol / Ag mol (Sen-5) 3 × 10 ^-3 mol / Ag mol (ExY) (ExM) (Hd) (Cpd-1) (Cpd-2) (Cpd-3) (Cpd-4) (Cpd-5) (Cpd-6) (Cpd-7) (Cpd-8) (Cpd-9) (UV-1) (UV-2) (UV-3) (UV-4) (Solv-1) (Solv-2) O = POC ₉ H ₁₉ (iso)) ₃ (Solv-3) (Solv-4) (Solv-5) (Solv-6) (Dy-1) (Dy-2) Samples (2) to (7) in which the dye of the fourth layer and the cyan coupler of the fifth layer were changed from the above samples were prepared. The composition is shown in Table 2. The numbers of dyes and cyan couplers correspond to those given in the specific examples in the text. The following cyan cyan couplers (C) were used.

(C) Cyan coupler for comparison The samples (1) to (7) were subjected to gradation exposure for sensitometry through a red filter using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K). At this time, the exposure was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds. With respect to sharpness, exposure was performed through a sharpness optical wedge with a cyan density of 1.5.

After the exposure, the following processes including color development, bleach-fixing and washing with water were performed. Treatment process temperature Time Color development 33 ° C. 3 minutes 30 seconds Bleach fixing 33 ° C. 1 minute 30 seconds Water washing 24-34 ° C. 3 minutes Drying 70-80 ° C. 1 minute The composition of each processing solution is as follows.

Color developer Water 800 ml Diethylenetriaminepentaacetic acid 1.0 g Nitrilotriacetic acid 1.5 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 0.5 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4- aminoaniline sulphate 5.0g Hydroxylamine sulphate 4.0g Fluorescent brightener (WHITHX4B, Sumitomo Chemical Co., Ltd.) 1.0g 1000 ml pH (25 ℃) 10.20 bleach-fixer water 400 ml thio Ammonium sulfate (70%) 150 ml Sodium sulfite 18 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Disodium ethylenediaminetetraacetate 5 g Water was added to 1000 ml pH (25 ° C) 6.70 Development treatment, each of the above samples (1) to (7) Was evaluated for sensitivity, fog, sharpness and dark fading. The sensitivity was the relative sensitivity at concentration = 1.0. However, for convenience, the relative sensitivity of the sample (1) was set to 100. Regarding fog, the value of so-called push fog was also tested when the development time was 7 minutes. The sharpness is represented by the numerical value defined as follows.

Sharpness: CTF at spatial frequency of 15 lines / mm
(%) The higher the sharpness value, the better.

In addition, the dark fading property of the developed sample was measured at 80 ℃ -70% RH.
After leaving for one day, the density reached after standing was evaluated as a percentage with respect to the color density of 2.0 before the test. The results are shown in Table 3.

As is clear from the results shown in Table 3, the dye in which the cyan coupler of the present invention and the dye are combined has high feeling and low fog,
In addition, it can be seen that the light-sensitive material has excellent sharpness and dark fading.

Example-2 A sample (8) having the following layer structure was prepared in the same manner as in Example-1.

First layer (blue-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-7) with spectral sensitizer (Sen-6) added 0.27 Gelatin 1.86 Yellow coupler (ExY) 0.82 Solvent (Solv-4) ) 0.35 Hardener (Hd) 0.02 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.06 Solvent (Solv-3 and Solv-4 volume ratio 1: 1) 0.12 Hardener (Hd) 0.02 Third layer (green-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-8) with spectral sensitizer (Sen-7,3) 0.45 Gelatin 1.24 Magenta coupler (ExM) 0.35 color image Stabilizer (Cpd-6) 0.20 Color image stabilizer (Cpd-7) 0.03 Color image stabilizer (Cpd-8) 0.03 Solvent (Solv-3 and Solv-5 volume ratio 1: 2) 0.65 Hardener (Hd) 0.01 4th layer (UV absorbing layer) Gelatin 1.58 UV absorbing agent (UV-1 / 2/3 molar ratio 1: 4: 4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv-6) 0.34 Dye (Dy -1) 1.8 × 10 ^-5 Le Dye (Dy-2) 2.0 × 10 -5 mol hardener (Hd) 0.01 Fifth Layer (red-sensitive silver halide emulsion layer) spectral sensitizers (Sen-4, 5) monodisperse silver chlorobromide prepared by adding Silver halide emulsion (EM-9) 0.20 Gelatin 0.92 Cyan coupler (Table 5) 6.7 × 10 ^-4 mol Polymer (Cpd-3) 0.30 UV absorber (UV-1 / 3/4 mol ratio 1: 3: 3) 0.17 Solvent (Solv-4) 0.20 Hardener (Hd) 0.01 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1 / 2/3 molar ratio 1: 4: 4) 0.21 Solvent (Solv-6) ) 0.08 Hardener (Hd) 0.01 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.17 Liquid paraffin 0.03 The details of the silver halide emulsion used in the above sample are shown in Table 4.

Samples (8) to (12) in which the dye in the fourth layer and the cyan coupler in the fifth layer were changed from the above samples were prepared. The composition is shown in Table 5.

Samples (8) to (12) were exposed for evaluation in the same manner as in Example-1, and the following treatments were performed. Step Temperature Time color developing 35 ° C. 45 seconds blix 30 to 35 ° C. 45 sec Rinse 30 to 35 ° C. 20 sec Rinse 30 to 35 ° C. 20 sec Rinse 30 to 35 ° C. 20 sec Rinse 30 to 35 ° C. 30 seconds Drying 70 80 ℃ 60 seconds (Rinsing → 3 tanks countercurrent method) The composition of each processing solution is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N ', N'-Tetramethylenephosphonic acid 1.5 g Triethylenediamine (1,4 diazabicyclo (2,2,2) octane) 5.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N- Ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4- aminoaniline sulfate 5.0g N, N-diethylhydroxylamine 4.2g Fluorescent brightener (UVITEX CK Ciba-Geigy Co., Ltd.) 2.0g Water added 1000ml pH (25 ℃) 10.10 Bleaching tightening solution Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 18 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 3 g Ammonium bromide 40 g Glacial acetic acid 8 g Water is added 1000 ml pH (25 ° C) 5.5 Rinse solution Ion exchange water (Calcium and magnesium are each 3 ppm or less) The developed samples (8) to (12) were evaluated in the same manner as in Example-1. However, the sensitivity was a value when the relative sensitivity of the sample (8) was 100, and the pressing fog was a value when the developing time was 90 seconds. The results are shown in Table 6.

As is clear from the results shown in Table 6, the sample in which the cyan coupler of the present invention and the dye are combined is a light-sensitive material having high sensitivity / low fog and excellent sharpness and dark fading.

Example-3 In order to check the stability of the dye of the invention in a film, Example-1
And samples 2 (2), (4), (7), (9), (1
The residual ratio of the dye after leaving 1) at 35 ° C.-80% for 2 weeks was measured and evaluated. The results are shown in Table 7.

As is clear from the results, the dye of the present invention has excellent stability in the film.

(Effect of the Invention) According to the present invention, a hydrophilic colloid layer containing a novel dye, which does not adversely affect the photographic characteristics of a photographic emulsion, particularly sensitivity and fog, is excellent in decolorization by processing, and is stable over time is provided. It is possible to obtain a silver halide color photographic light-sensitive material having the same. Further, according to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material having a dark-fading and sharpness, a high-sensitivity and low-fog red-sensitive emulsion layer.

Claims (1)

[Claims] 1. A silver halide color photograph containing a compound represented by the following general formula [I] on a support and at least one compound represented by the following general formula [II]. Photosensitive material. General formula [I] In the formula, R ₁ and R ₂ are each -COOR ₅ , Represents R ₃ and R ₄ each represent a hydrogen atom or an alkyl group, and R ₅ and R ₆ each represent a hydrogen atom, an alkyl group and an aryl group. R ₅ and R ₆ may combine to form a 5- or 6-membered ring. Q ₁ and Q ₂ each represent an aryl group. X ₁ and X ₂ are 2
Represents a valent linking group or bond, and Y ₁ and Y ₂ represent a sulfo group and a carboxyl group, respectively. L ₁ , L ₂ and L ₃ each represent a methine group or a substituted methine group. m ₁ and m ₂ are 1 or 2, n is 0, 1 or 2, p ₁ and p ₂ are 0, 1, 2 and
3 or 4, s ₁ and s ₂ respectively represent 1 or 2. General formula (II) In the formula, Y ₃ represents —NHCO— or —CONH—, R ₈ represents an optionally substituted aliphatic group, an aromatic group, a heterocyclic group or an arylamino group, and X ₃ represents a hydrogen atom or a halogen. Represents an atom, an alkoxy group or an acylamino group, R ₇ represents an alkyl group (having 2 or more carbon atoms) or an acylamino group, or X ₃
And R ₇ represent a non-metallic atomic group forming a 5- to 7-membered ring, and Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a developing agent.