JP2717869B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and in particular, has excellent color reproducibility, high image sharpness, and rapid processing. It relates to an excellent silver halide color photographic light-sensitive material.

(Prior Art) In recent years, in silver halide color photographic light-sensitive materials, particularly in light-sensitive materials for printing, it has become more and more important to improve performance in order to respond to demands for rapid development processing or high quality. ing. In order to satisfy such demands, a new system has been developed to achieve a rapid processing step by using a silver halide emulsion containing a high content of silver chloride in a light-sensitive material, a so-called high silver chloride emulsion. It is being introduced. As the performance of a photosensitive material required to obtain a high-quality print, it is known that richness of color reproduction and excellent image sharpness are particularly important. Of the former, pyrazoloazole-based magenta couplers are known as magenta couplers other than 5-pyrazolone couplers which have been widely used in color papers and the like. It is known that couplers of this type not only have good spectral characteristics of coloring hue than 5-pyrazolone couplers, but also have high light fastness and little stain derived from the couplers themselves. There are many excellent points. U.S. Patent No.
Pyrazolo [1,5-b] [1,2,4] triazoles described in 4,540,654 can be preferably used.

On the other hand, the yellow coupler used together with the magenta coupler has a maximum absorption wavelength of the color-forming dye to be formed, which is generally located on the long wavelength side with respect to the preferable absorption characteristics from the viewpoint of color reproducibility, and has a long wavelength exceeding 500 nm. It has the disadvantage that the absorption in the wavelength range does not sharply decrease to zero.

Attempts to introduce a yellow coupler in which the maximum absorption wavelength of the color-forming dye to be formed is located at a shorter wavelength into a color print material are described, for example, in JP-A-63-123047 and JP-A-63-23.
Nos. 1451 and 63-241547, the use of yellow couplers described in the specification has been conventionally studied.However, the coating amount has to be greatly increased due to a decrease in color developing property and the like. However, problems such as a decrease in image sharpness or an increase in processing stain remain.

As described above, the knowledge for improving the sharpness of an image, which is suitable for rapid processing and excellent in color reproducibility, is still insufficient.

In order to improve the sharpness of an image, a photographic emulsion layer and other hydrophilic colloid layers are often colored for the purpose of absorbing light in a specific wavelength range. These hydrophilic colloid layers to be colored usually contain a dye. However, depending on the type and amount of the dye used, deterioration of photographic properties, for example, softening of gradation or increase in stain may cause a problem.

Many efforts have been made by those skilled in the art to minimize these problems, and oxonolpyrazolone dyes in particular have been studied as satisfying these properties. For example, British Patent Nos. 506,385 and 1,177,429
Nos. 1,311,884, 1,338,799, 1,385,371,
No. 1,467,214, No. 1,433,102, No. 1,553,516, JP-A-48-85,130, No. 49-114,420, No. 55-161,233,
No. 59-111,640; U.S. Pat.Nos. 3,247,127; 3,469,98
No. 5, 4,078,933, 2,533,472, 3,379,533,
Details thereof are described in British Patent No. 1,278,621.

However, it is easy to guess that it is effective to increase the amount of the dye used as much as possible in order to improve the sharpness of an image by using the dye belonging to this system, but it is easy to guess, but it is highly demanded recently that high quality is required. There is a limit to achieving the above, and in particular, radical improvement measures are required to remarkably improve the color reproducibility and to solve the deterioration of photographic properties (problems such as sensitivity reduction, softening or residual color). Had been.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material which can be rapidly processed, has excellent color reproduction, and has high image sharpness.

(Means for Solving the Problems) The object of the present invention has been found to be achieved by the following method.

(1) A silver halide color photographic material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support, wherein the blue-sensitive silver halide emulsion The emulsion layer contains at least one yellow coupler represented by the following general formula (I), and the optical reflection density at 680 nm of the photosensitive material is 0.70 to 2.0 and the optical reflection density at 550 nm is 680 nm or less. A silver halide color photographic light-sensitive material, characterized in that:

General formula [I] Wherein R ₁ is an aryl group or a tertiary alkyl group, R ₂ is a fluorine atom, an alkyl group, an aryl group, an alkoxy group,
An aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, R ₃ can be substituted on the benzene ring, and X can be removed by a coupling reaction with an oxidized aromatic primary amine developer. And a group represented by the following general formula [II], and l represents an integer of 0 to 4. However, when l is an integer, a plurality of R ₃ may be the same or different. (2) The support is a reflective support in which a support substrate is coated with a water-resistant resin layer, and the water-resistant resin layer on the side on which the silver halide photosensitive layer is coated contains 14 wt. %
(1) The silver halide color photographic light-sensitive material according to the above (1), which is contained at a density of not less than 60% by weight or less.

(3) The silver halide color photographic light-sensitive material as described in (2) above, wherein any of the constituent layers of the photographic light-sensitive material contains a fluorescent whitening agent.

The compound [I] used in the present invention will be described in more detail.

In the general formula [I], R ₁ preferably has 6 carbon atoms.
To 24 aryl groups (e.g., phenyl, p-tolyl, o-
Tolyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, 4-hexadecyloxyphenyl, 1-naphthyl)
Or a tertiary alkyl group having 4 to 24 carbon atoms (for example, t-
Butyl, t-pentyl, t-hexyl, 1,1,3,3-tetramethylbutyl, 1-adamantyl, 1,1-dimethyl-
2-chloroethyl, 2-phenoxy-2-propyl, bicyclo [2,2,2] octan-1-yl).

In the general formula (I), R ₂ is preferably a fluorine atom,
An alkyl group having 1 to 24 carbon atoms (eg, methyl, ethyl, isopropyl, t-butyl, cyclopentyl, n-
Octyl, n-hexadecyl, benzyl), aryl groups having 6 to 24 carbon atoms (for example, phenyl, p-tolyl, o
-Tolyl, 4-methoxyphenyl), having 1 to 24 carbon atoms
(E.g., methoxy, ethoxy, butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy), having 6 to 24 carbon atoms
Aryloxy groups such as phenoxy, p-tolyloxy, o-tolyloxy, p-methoxyphenoxy, p
-Dimethylaminophenoxy, m-pentadecylphenoxy), a dialkylamino group having 2 to 24 carbon atoms (for example, dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino), an alkylthio group having 1 to 24 carbon atoms ( For example, methylthio, butylthio, n-octylthio, n-hexadecylthio) or an arylthio group having 6 to 24 carbon atoms (eg, phenylthio, 4-methoxyphenylthio, 4-t-butylphenylthio, 4-dodecylphenylthio) Represents

In the general formula [I], R ₃ is preferably a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or an alkyl group having 1 to 24 carbon atoms (eg, methyl, t-butyl, n-dodecyl) An aryl group having 6 to 24 carbon atoms (e.g., phenyl, p-tolyl, p-dodecyloxyphenyl), an alkoxy group having 1 to 24 carbon atoms (e.g., methoxy, n-butoxy, n-octyloxy, n- Tetradecyloxy, benzyloxy, methoxyethoxy), an aryloxy group having 6 to 24 carbon atoms (for example, phenoxy, pt-butylphenoxy, 4-butoxyphenoxy), an alkoxycarbonyl group having 2 to 24 carbon atoms [ For example, ethoxycarbonyl, dodecyloxycarbonyl, 1- (dodecyloxycarbonyl) ethoxycarbonyl], C7-C24 Carbonyl groups (for example, phenoxycarbonyl, 4-t-octylphenoxycarbonyl, 2,4-di-t-pentylphenoxycarbonyl), carbonamido groups having 1 to 24 carbon atoms [for example, acetamide Pivaloylamino, benzamide, 2-ethylhexaneamide, tetradecaneamide, 1- (2,4-di-t-pentylphenoxy) butanamide, 3- (2,4-di-t-pentylphenoxy) butanamide, 3-dodecylsulfonyl-2-methylpropanamide], a sulfonamide group having 1 to 24 carbon atoms (for example, methanesulfonamide, p-toluenesulfonamide, hexadecanesulfonamide), a carbon atom of 1
To 24 carbamoyl groups (e.g., N-methylcarbamoyl, N-tetradecylcarbamoyl, N, N-dihexylcarbamoyl, N-octadecyl-N-methylcarbamoyl, N-phenylcarbamoyl);
(For example, N-methylsulfamoyl, N-phenylsulfamoyl, N-acetylsulfamoyl, N-propanoylsulfamoyl, N-hexadecylsulfamoyl, N, N-dioctylsulfamoyl) Moyl), an alkylsulfonyl group having 1 to 24 carbon atoms (eg, methylsulfonyl, benzylsulfonyl, hexadecylsulfonyl), an arylsulfonyl group having 6 to 24 carbon atoms (eg, phenylsulfonyl, p-tolylsulfonyl, p-dodecyl) Sulfonyl, p-methoxysulfonyl), a ureido group having 1 to 24 carbon atoms (for example, 3-methylureide, 3-phenylureido, 3,3-dimethyluredo, 3-tetradecylureide), and 0 to 24 carbon atoms
A sulfamoylamino group (e.g., N, N-dimethylsulfamoylamino), an alkoxycarbonylamino group having 2 to 24 carbon atoms (e.g., methoxycarbonylamino,
Isobutoxycarbonylamino, dodecyloxycarbonylamino), nitro group, heterocyclic group having 1 to 24 carbon atoms (for example, 4-pyridyl, 2-thienyl, phthalimide,
Octadecylsuccinimide), cyano group, acyl group having 1 to 24 carbon atoms (eg, acetyl, benzoyl, dodecanoyl), acyloxy group having 1 to 24 carbon atoms (eg, acetoxy, benzoyloxy, dodecanoyloxy), 1 carbon atom To 24 alkylsulfonyloxy groups (e.g., methylsulfonyloxy, heisadecylsulfonyloxy) or arylsulfonyloxy groups having 6 to 24 carbon atoms (e.g., p-toluenesulfonyloxy,
p-dodecylphenylsulfonyloxy).

In the general formula [I], l is preferably an integer of 1 or 2.

Next, examples of the above-mentioned substituents R ₁ , R ₂ , R ₃ and X which are particularly preferably used in the present invention will be described.

In the general formula [I], R ₁ is particularly preferably a 2 or 4-alkoxyaryl group (for example, 4-methoxyphenyl, 4-butoxyphenyl, 2-methoxyphenyl)
Or a t-butyl group, with a t-butyl group being most preferred.

In the general formula (I), R ₂ is particularly preferably a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dialkylamino group, and most preferably a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dimethylamino group. preferable.

In the general formula [I], R ₃ is particularly preferably an alkoxy group, a carbonamido group or a sulfonamido group.

 X is represented by the following general formula [II].

General formula (II) In the general formula [II], Z is Or Represents Here, R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R ₆ represents a hydrogen atom, Alkyl group, aryl group, alkylsulfonyl group,
Represents an arylsulfonyl group or an alkoxycarbonyl group.

The total number of carbon atoms of the heterocyclic group represented by the general formula [II] is 2 to 24, preferably 4 to 20, and more preferably 5 to 16. Examples of the heterocyclic group represented by the general formula [II] include 1
-Methyl imidazolidine-2,4-dione-3-yl group,
1-benzylimidazolidin-2,4-dione-3-yl group, 5,5-dimethyloxazolidine-2,4-dione-3-
Yl group, 5-methyl-5-propyloxazolidine-2,
4-dione-3-yl group, 5,5-dimethylimidazolidin-2,4-dione-3-yl group, 5-hexyloxy-1
-Methyl imidazolidine-2,4-dione-3-yl group,
There are a 1-benzyl-5-ethoxyimidazolidin-2,4-dione-3-yl group and a 1-benzyl-5-dodecyloxyimidazolidin-2,4-dione-3-yl group.

Among the above heterocyclic groups, an imidazolidine-2,4-dione-3-yl group (for example, 1-benzyl-imidazolidin-
2,4-dione-3-yl group) is the most preferred group.

The coupler represented by the general formula [I] has a substituent R ₁ , X or May form a dimer or a multimer which bonds to each other via a divalent or divalent or higher valent group.
In this case, the number of carbon atoms may not be within the range specified for each substituent.

When the coupler represented by the general formula [I] forms a multimer, an addition polymer ethylenically unsaturated compound having a yellow dye-forming coupler residue (yellow color-forming monomer)
A homo- or copolymer is a typical example. In this case, the multimer contains repeating units of the general formula [III], and one or more types of the yellow coloring repeating units represented by the general formula [III] may be contained in the multimer. It may be a copolymer containing one or more kinds of color-forming ethylene monomers.

General formula (III) In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene. A phenylene group or an aralkylene group, and L is -CONH-, -NHCONH-, -NHCOO
-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO
-, - CO -, - O -, - S -, - SO 2 -, - NHSO 2 - or represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q represents R ₁ , X or the compound of the formula (I) A yellow coupler residue from which a hydrogen atom has been further removed is shown.

As the polymer, a copolymer of a yellow coloring monomer represented by the coupler unit of the general formula [III] and a non-color-forming ethylene-like monomer described below is preferable.

Non-color-forming ethylene-type monomers that do not couple with the oxidation products of aromatic primary amine developing agents include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (eg, methacrylic acid) derived from these acrylic acids. Amide or ester (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, t-
Butyl acrylate, iso-butyl acrylate, 2-
Ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (for example, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile , Aromatic vinyl compounds (eg, ethylene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg, vinyl ethyl ether), Maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and -4-vinylpyridine and the like

In particular, acrylates, methacrylates, and maleates are preferred. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the general formula (II)
The ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to (I) may be a copolymer having physical and / or chemical properties such as solubility, binding of the photographic colloid composition. An agent such as gelatin can be selected so that its compatibility, flexibility, thermal stability, and the like are favorably affected.

The yellow polymer coupler used in the present invention is prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl monomer to give a coupler unit represented by the above general formula [III] in an organic solvent, in an aqueous gelatin solution. And may be prepared by emulsifying and dispersing in the form of, or directly by an emulsion polymerization method.

A method for emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in U.S. Pat.
No. 820, U.S. Pat.
The method described in 3,370,952 can be used.

Specific examples of yellow dye forming couplers R ₃ and X represented by formula (I) below, the present invention is not limited thereto.

 Specific examples of X are shown below.

Specific examples of R ³ are shown below.

Specific examples of the yellow dye-forming coupler represented by the general formula [I] are shown below.

The numbers in the () Table represents number assigned to the specific examples of the X and R _3, the numbers in [] represent the substitution positions on the anilide group.

The couplers of the present invention may be used alone or as a mixture of two to several types, or may be used as a mixture with known yellow dye-forming couplers.

The coupler of the present invention can be used in any layer of a light-sensitive material, but is preferably used in a light-sensitive silver halide emulsion layer or a layer adjacent thereto, and most preferably in a light-sensitive silver halide emulsion layer.

The coupler of the present invention can be synthesized by a conventionally known synthesis method.
There is a synthesis method described in 3047.

The amount of the coupler of the present invention used in the light-sensitive material is 1 × 10 ^-5 mol to 10 ^-2 mol, preferably 1 × 10 ^-4 mol per 1 m ^2.
Mol to 5 × 10 ^-3 mol, more preferably 2 × 10 ^-4 mol to 10 mol
^-3 mol.

The optical reflection density in the present invention is measured by a reflection densitometer generally used in the art, and is defined as follows. However, at the time of measurement, it is necessary to install a standard reflection plate on the back surface of the sample to prevent measurement errors due to light passing through the sample.

Optical reflection density = log ₁₀ (F ₀ / F) F ₀ : Reflected light flux of standard white plate F: Reflected light flux of sample The optical reflection density required in the present invention is required to be 0.70 or more at a measurement wavelength of 680 nm, and preferably 0.7 or more
It is 2.0 or less, more preferably 0.8 or more and 1.9 or less, and most preferably 1.0 or more and 1.8 or less. Further, the ratio between the optical reflection density at 550 nm and that at 680 nm needs to be 1 or less, more preferably 0.8 or less, further preferably 0.6 or less,
Most preferably it is 0.5 or less. Further, the optical reflection density at 470 nm is preferably 0.2 or more, and furthermore
It is preferably 0.3 or more and 1.0 or less.

In order to obtain the optical reflection density of the present invention, the amounts of the following dyes may be adjusted. These dyes may be used alone or in combination of two or more. There is no particular limitation on the layer to which these dyes are added, and a layer between the lowermost photosensitive layer and the support, a photosensitive layer, an intermediate layer, a protective layer, a layer between the protective layer and the uppermost photosensitive layer, and the like. Can be added.

Dyes for this purpose are selected from those which do not substantially sensitize silver halide.

As a method for adding these dyes, a conventional method can be applied. For example, they can be added by dissolving them in water or an alcohol such as methanol.

As the amount of the dye to be added, the following coating amount can be used as one standard.

Cyan dye: 20-100 mg / m ² (most preferred amount) Magenta dye: 0-50 mg / m ² (preferred amount) 0-10 mg / m ² (most preferred amount) Yellow dye: 0-30 mg / m ² (preferred amount) 5 to 20 mg / m ² (most preferable amount) A method in which the dye added to the above layer is present in such a manner that it is diffused in all layers during the period from application to drying of the light-sensitive material, and is fixed to a specific layer. This is preferable from the viewpoint of making the effect of the present invention more remarkable and preventing an increase in manufacturing cost due to the provision of a specific layer.

Dyes which can be used in the present invention are, for example, GB 506,38
No. 5, No. 1,177,429, No. 1,311,884, No. 1,338,799,
1,385,371, 1,467,214, 1,433,102, 1,5
No. 53,516, JP-A-48-85,130, JP-A-49-114,420, and
2-117,123, 55-161,233, 59-111,640, JP-B-39-22,069, 43-13,168, 62-273527,
U.S. Pat.Nos. 3,247,127, 3,469,985, 4,078,933
Oxonol dyes having a pyrazolone nucleus or a barbituric acid nucleus described in U.S. Pat. Nos. 2,533,472 and 3,3
79,533, other oxonol dyes described in British Patent No. 1,278,621, etc., British Patent Nos. 575,691 and 680,631
Nos. 599,623, 786,907, 907,125, 1,04
No. 5,609, U.S. Pat.No. 4,255,326, JP-A-59-211,043
Azo dyes described in JP-A-50-100,116,
Nos. 4-118,247, British Patent Nos. 2,014,598, Azomethine dyes described in 750,031, etc., U.S. Pat.No. 2,865,752, Anthraquinone dyes described in U.S. Pat.No. 2,538,00
9, 2,688,541, 2,538,008, UK Patent 584,6
No. 09, No. 1,210,252, JP-A-50-40,625, No. 51-3,6
No. 23, No. 51-10,927, No. 54-118,247, JP-B-48-
No. 3,286, the arylidene dyes described in JP-A-59-37,303, JP-B-28-3,082, JP-B-44-16,594, JP-A-59-28,
Styryl dyes described in No. 898, etc., UK Patent No. 446,583
No. 1,335,422, triarylmethane dyes described in JP-A-59-228,250, etc., UK Patent No. 1,075,653,
1,153,341, 1,284,730, 1,475,228, 1,5
No. 42,807, etc., merocyanine dyes, U.S. Pat.
And cyanine dyes described in 2,843,486 and 3,294,539.

Among these, the dyes that can be particularly preferably used in the present invention are the dyes represented by the following general formula (IV) or (V).

General formula (IV) Where Z₁, Z_TwoMay be the same or different, and
Represents a group of non-metallic atoms necessary to form a ring, L₁,
L_Two, L_Three, L_Four, L_FiveRepresents a methine group, n₁, N_TwoIs 0 or 1
And M Represents hydrogen or other monovalent cation
I forgot.

General formula (V) Ar ₁ -N = N-Ar _{2 In the} formula, Ar ₁ and Ar ₂ may be the same or different and represent an aryl group or a heterocyclic group.

 Hereinafter, each dye will be described in detail.

In the general formula (IV), the heterocyclic ring formed by the non-metallic atomic groups represented by Z ₁ and Z ₂ is preferably a 5- or 6-membered ring, and may be a single ring or a condensed ring. -Hydroxypyridone, pyrazolo [3,4-b] pyridine-3,6-dione, barbituric acid, pyrazolidinedione, thiobarbituric acid, rhodanine, imidazopyridine, pyrazolopyrimidine, pyrrolidone, pyrazoloimidazole and the like. No.

The methine group represented by L ₁ , L ₂ , L ₃ , L ₄ , L ₅ has a substituent (eg, methyl, ethyl, phenyl, chlorine atom, sulfoethyl, carboxyethyl, dimethylamino, cyano) Alternatively, the substituents may be linked to each other to form a 5- or 6-membered ring (eg, cyclohexene, cyclopentene, 5,5-
Dimethylcyclohexene).

 M The monovalent cation other than hydrogen represented by
Ba Na , K , HN (C_TwoH_Five)₃ Li And the like.

Among the dyes represented by the general formula (IV), particularly preferred are the dyes represented by the following general formulas (IV-a) and (IV-b).

General formula (IV-a) Where R₁, R_ThreeRepresents an aliphatic group, an aromatic group or a heterocyclic group
Represents, R_Two, R_FourIs an aliphatic group, an aromatic group, -OR_Five, -COO
R_Five, -NR_FiveR₆, -CONR_FiveR₆, -NR_FiveCONR_FiveR₆, -SO_TwoR₇, -C
OR₇, -NR₆COR₇, -NR₆SO_TwoR₇, A cyano group (where R_Five,
R₆Represents a hydrogen atom, an aliphatic group or an aromatic group, and R₇Is fat
Represents an aliphatic group or an aromatic group, R_FiveAnd R₆Or R₆And R₇Is concatenated
To form a 5- or 6-membered ring. )
L₁, L_Two, L_Three, L_Four, L_FiveAnd n₁, N_Two, M Is the general formula (IV)
Synonymous with the definition in

General formula (IV-b) Where R₁₁, R₁₄Represents a hydrogen atom, an aliphatic group, an aromatic group,
Ring group, -NR₁₇R₁₈, -NR₁₇CONR₁₇R₁₈, -NR₁₈COR₁₉,
Or -NR₁₈SO_TwoR₁₉And R₁₂, R_FifteenIs a hydrogen atom,
Aliphatic group, aromatic group, heterocyclic group, cyano group, sulfonic acid
Group, -NR₁₇R₁₈, -NR₁₈COR₁₉, -NR₁₈SO_TwoR₁₉, -NR₁₇CO
NR₁₇R₁₈, -COOR₁₇, -CONR₁₇R₁₈, −COR₁₉, -SO_TwoR₁₉
Or -SO_TwoNR₁₇R₁₈And R₁₃, R₁₆Is a hydrogen atom,
Aliphatic group, aromatic group, heterocyclic group, -OR₁₇, -COOR₁₇, −
COR₁₉, -CONR₁₇R₁₈, -NR₁₇R₁₈, -NR₁₈COR₁₉Or -NR
₁₈SO_TwoR₁₉, -NR₁₇CONR₁₇R₁₈, -SO_TwoR₁₉, -SO_TwoNR
₁₇R₁₈, -OR₇Or a cyano group (where R₁₇, R₁₈Is
Each represents a hydrogen atom, an aliphatic group or an aromatic group, and R₁₉Is
Represents an aliphatic group or an aromatic group, R₁₇And R₁₈Or R₁₈And R₁₉
May be linked to form a 5- or 6-membered ring. ).
L₁, L_Two, L_Three, L_Four, L_Five, N₁, N_Two, M Is the general formula (IV)
Has the same meaning as

 Next, the general formula (IV-a) will be described in detail.

The aliphatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be any of a straight-chain, branched or cyclic alkyl group, an aralkyl group, and an alkenyl group. , Ethyl, n-butyl, benzyl, 2-sulfoethyl, 4-
Examples include groups such as sulfobutyl, 2-sulfobenzyl, 2-carboxyethyl, carboxymethyl, trifluoromethyl, dimethylaminoethyl, and 2-hydroxyethyl.

Examples of the aromatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ include phenyl, naphthyl, 4-sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl,
-Carboxyphenyl, 5,7-disulfo-3-naphthyl, and the like.

When n ₁ = 1 or 2 and n = 0, R ₁ and
The phenyl group of R ₃ preferably has two or more sulfonic acid groups.

The heterocyclic group represented by R ₁ and R ₃ represents a 5- or 6-membered nitrogen-containing heterocyclic group (including a condensed ring), for example, 5-sulfopyridin-2-yl, 5-sulfobenzothiazole-2
-Yl and the like.

As the 5- or 6-membered ring formed by linking R ₅ and R ₆ , R ₆ and R ₇ , a pyrrolidine ring, a piperidine ring, a pyrrolidone ring,
Examples of the dye represented by the general formula (IV-a) are shown below, including a morpholine ring, but the present invention is not limited thereto.

These dyes are described in British Patent Nos. 506,385 and 1,177,429.
No. 1,338,799, No. 1,385,371, No. 1,467,214,
No. 1,433,102, No. 1,553,516, JP-A-48-85130,
No. 55-161233, No. 52-20330, No. 59-111640, No. 6
It can be synthesized by the method described in 2-273527.

Next, the dye represented by formula (IV-b) will be described in detail.

The aliphatic group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ or R ₁₉ is, for example, methyl, ethyl, isopropyl, 2-chloroethyl, trifluoromethyl, benzyl , 2-sulfobenzyl, 4-sulfophenethyl, carboxymethyl, 2-carboxyethyl, 2-sulfoethyl, 2-hydroxyethyl, dimethylaminoethyl,
And groups such as cyclopentyl.

The aromatic group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ or R ₁₉ is, for example, phenyl, naphthyl, 3
-Sulfophenyl, 4-sulfophenyl, 2,5-disulfophenyl, 4- (3-sulfopropyloxy) phenyl, 3-carboxyphenyl, 2-carboxyphenyl and the like.

Examples of the heterocyclic group represented by R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ or R ₁₆ include groups such as 2-pyridyl, morpholino, and 5-sulfobenzimidazol-2-yl.

5 or 6 formed by connecting R ₁₇ and R ₁₈ or R ₁₈ and R ₁₉
Examples of the member ring include a piperidine ring, a pyrrolidine ring, a morpholine ring, and a pyrrolidone ring.

Hereinafter, specific examples of the dye represented by Formula (IV-b) are shown, but the present invention is not limited thereto.

The dye represented by the general formula (IV-b) is disclosed in British Patent 1,278,
Compounds can be synthesized by the methods described in JP-A Nos. 621, 1,512,863 and 1,579,899.

Next, the dye represented by formula (V) will be described in detail.

Ar ₁ , the aryl group represented by Ar ₂ is preferably a phenyl group or a naphthyl group, a substituent (for example, a sulfonic acid group,
Carboxylic acid group, hydroxyl group, alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl), alkoxy group having 1 to 6 carbon atoms (eg, methoxy, ethoxy, butoxy), carbamoyl group, sulfamoyl Group, halogen atom (for example, F, Cl, Br), cyano group, nitro group, etc.].

The heterocyclic group represented by Ar ₁ or Ar ₂ is preferably a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, 1- (4-sulfophenyl) -3-carboxy-5-hydroxy-4-pyrazolyl, (4-sulfophenyl) -3-methyl-5-
Hydroxy-4-pyrazolyl, 1- (2,5-disulfophenyl) -3-carboxy-5-hydroxy-4-pyrazolyl, 1-carboxymethyl-3-carbamoyl-1,
2-dihydro-6-hydroxy-4-methyl-2-oxopyridine, 1- (2-sulfoethyl) -3-cyano-
Examples thereof include 1,2-dihydro-6-hydroxy-4-methyl-2-oxopyridine.

Hereinafter, specific examples of the dye represented by Formula (V) are shown.

The dye represented by the general formula (V) is disclosed in British Patent No. 575,691.
No. 907,125 and No. 1,353,525.

In any of the steps from development to washing with water, the dye used in the present invention is eluted from a silver halide photographic material or decolorized by a sulfite as described in British Patent No. 506,385. .

A feature of a preferable support in the present invention is that titanium oxide fine particles are dispersed in a water-resistant resin layer so as to have a density of more than 14% by weight, preferably about 15% by weight or more and 60% by weight or less. is there. The surface of the fine particles of the titanium oxide pigment may be combined with or separately from an inorganic oxide such as silica or aluminum oxide, for example, with dihydric or tetrahydric alcohols, for example, 2,4-dihydroxy- alcohol described in JP-A-58-17151.
It is preferable to use 2-methylpentane, trimethylolethane, or the like after surface treatment.

Water resistant resin containing titanium oxide fine particles is 2 to 20
0 μm, preferably between 5 and 80 μm.
In this case, the water-resistant resin layer containing the titanium oxide fine particles of the present invention is, for example, a plurality of water-resistant resin layers having different contents, or containing another white pigment, or containing no white pigment. And may be laminated. In such a case, the water-resistant resin layer of the present invention containing the fine titanium oxide particles is preferably provided at a position farther from the support (closer to the silver halide emulsion layer).

In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the white pigment in the water-resistant resin layer is preferably 0.20 or less, more preferably 0.15 or less, and particularly preferably 0.10 or less.

The dispersibility of the fine white pigment particles in the resin layer is such that the surface of the resin or a thickness of about 0.1 μm, preferably about 500 ° is scattered by the ion sputtering method using a glow discharge to remove the fine particles of the exposed pigment. Observation is performed with an electron microscope, the occupied area of the image is obtained, and evaluation can be made based on the variation coefficient of the occupied area ratio (%). The ion spattering method is described in detail in Yoichi Murayama and Kunihiro Kashiwagi, "Surface Treatment Technology Using Plasma," Machine Research, Vol. 33, No. 6, 1981.

To control the coefficient of variation of the white pigment particles to 0.20 or less,
It is preferable to sufficiently knead a white pigment in the presence of a surfactant, and it is preferable to use a pigment particle whose surface has been treated with a divalent to tetravalent alcohol as described above.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient of the occupied area ratio (%) is the ratio of the standard deviation s of R _i to the average value of R _i () s /
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

The water-resistant resin may contain a white pigment other than titanium oxide. For example, rutile-type titanium oxide, anatase-type titanium oxide, barium sulfate, calcium sulfate, silicon oxide, zinc oxide, titanium phosphate, aluminum oxide and the like are used as preferred white pigments.

The white support used in the silver halide photographic light-sensitive material according to the present invention is provided by coating a water-resistant resin layer on a substrate, and the substrate is obtained from natural pulp, synthetic pulp or a mixture thereof. Base paper or a plastic film such as a polyester film such as polyethylene terephthalate or polybutylene terephthalate, a cellulose triacetate film, a polystyrene film, a polypropylene film, or a polyolefin film can be used.

The base paper used in the present invention is selected from materials generally used for photographic printing paper. That is, natural pulp selected from conifers, hardwoods, etc. as the main raw material, if necessary, clay,
Salts such as talc, calcium carbonate, urea resin fine particles, rosin, alkyl ketene dimer, higher fatty acids, paraffin wax, sizing agents such as alkenyl succinic acid, polyacrylamide and other paper-strengthening agents, sulfate bands, cationic polymers, etc. What added a fixing agent etc. is used.
Especially using a reactive sizing agent such as epoxidized fatty acid amide, alkyl ketene dimer, alkenyl succinic acid,
pH 5-7 (Electrode is a flat GST made by Toa Denpa Kogyo Co., Ltd.
It is preferable to use neutral paper (measured with a pH meter using -5313F). Further, synthetic pulp may be used in place of the above natural pulp, or natural pulp and synthetic pulp may be mixed in an arbitrary ratio.

The surface of the pulp may be treated with a film-forming polymer such as gelatin, starch, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, or a modified polyvinyl alcohol.
In this case, examples of the modified polyvinyl alcohol include a modified carboxyl group, a modified silanol, and a copolymer with acrylamide. Further, when the surface sizing treatment is performed with the film-forming polymer, the coating amount of the film-forming polymer is adjusted to 0.1 to 5.0 g / m ² , preferably 0.5 to 2.0 g / m ² . Further, an antistatic agent, a fluorescent whitening agent, a pigment, an antifoaming agent and the like can be added to the film-forming polymer at this time, if necessary.

Further, the base paper is formed by using a pulp slurry described above, and a pulp slurry containing additives such as a salting agent, a sizing agent, a paper reinforcing agent, and a fixing agent, if necessary, with a paper machine such as a fourdrinier paper machine, and then drying. It is manufactured by winding. The surface sizing is performed either before or after the drying, and a calendering is performed after the drying and winding. If the calendering process is performed after drying the surface size treatment,
It can be performed either before or after the surface sizing.

Whether or not the base paper used for the support substrate of the present invention is neutral paper can be determined, for example, by measuring the pH value of the electrode using GST-5313F for flat surface manufactured by Toa Denpa Kogyo KK. The neutral paper has a pH value of 5 or more, preferably 5 to 9.

Further, the water-resistant resin layer according to the present invention may itself constitute a support like a vinyl chloride resin.

The water-resistant resin used in the present invention is a resin having a water absorption (% by weight) of 0.5, preferably 0.1 or less, for example, polyalkylene (polyethylene, polypropylene, or a copolymer thereof), vinyl polymer or a copolymer thereof (polystyrene, (Polyacrylate or copolymer thereof), polyester or copolymer thereof. Preferably, low density polyethylene, high density polyethylene, polypropylene and a blend thereof are used as the polyalkylene resin. If necessary, a fluorescent whitening agent, an antioxidant, an antistatic agent, a release agent and the like are added.

Further, for example, as described in JP-A-57-27257, JP-A-57-49946 and JP-A-61-262738, it is not possible to have one or more polymerizable carbon-carbon double bonds in one molecule. Saturated organic compounds such as methacrylate compounds,
Gintree or tetra-acrylate represented by the general formula in JP-A-62-262738 can be used. In this case, after being applied on the substrate, it is cured by electron beam irradiation to form a water-resistant resin layer. Titanium oxide and other white pigments are dispersed in the unsaturated organic compound.
Further, other resins can be mixed and dispersed.

The method of coating the water-resistant resin layer of the present invention is, for example, a lamination method described in, for example, "New Laminating Handbook" edited by Processing Technology Research Group, for example, dry lamination, solvent-free dry lamination, and the like are used. The gravure roll type, the wire bar type, the doctor blade type, the reverse roll type, the dip type, the air knife type, the calendar type, the kiss type, the squeeze type and the funtin type coating are used.

The surface of the support is preferably subjected to a corona discharge treatment, a glow discharge treatment, a flame treatment or the like to provide a protective colloid layer group of the silver halide photosensitive material.

The support has a total thickness of 30 to 350 g / m ² (about 30 to 4 g / m ² ).
00 μm), more preferably about 50 to 200 g / m
²

Next, the fluorescent whitening agent preferably used in the present invention is a substance that absorbs ultraviolet light and has an effect of emitting fluorescent light having a slightly bluish tint to make an object look whiter. Any compound may be used as long as it is used to increase the whiteness of the base after processing the photographic paper,
For example, K. Veen-Rataramann, ed.
The compounds described in Chemistry of Synthetic Dyes, Vol. V, Chapter 8, can be used. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given.

The water-soluble fluorescent whitening agent and the oil-soluble fluorescent whitening agent will be described separately according to their solubility.

Water-soluble optical brighteners are described, for example, in U.S. Pat.
And stilbene-based brighteners having a water-soluble group as listed in JP-B-48-30495 and JP-A-55-135833. Among them, a water-soluble diaminostilbene compound is particularly preferably used, and it is more preferable that the compound has a sulfone group as a water-soluble group.

In particular, fluorescent brighteners such as 4,4'-diaminostilbene disulfonic acid derivatives can be prepared by the usual method described in, for example, "Fluorescent Brightener" edited by the Chemical Industry Association of Japan (issued in August 1976). Can be synthesized.

The water-soluble fluorescent whitening agent used in the present invention may be added to the light-sensitive material as an aqueous solution as it is, or for the purpose of preventing the fluorescent whitening agent from flowing out of the layer at the time of processing, see JP-A-56-1981. -32547 and European Patent 0024380B1, the molecular structure of which may be improved so that it is less likely to flow itself, but most preferably as described in JP-B-34-7127 and Research Disclosure No. 17159, A method of adding to a photosensitive material together with a water-soluble polymer such as polyvinylpyrrolidone or polyvinyl alcohol is used.

As the oil-soluble fluorescent whitening agent used in the present invention, particularly, substituted stilbenes and substituted coumarins described in British Patent No. 786,234 and substituted thiophenes described in U.S. Patent No. 3,135,762 are useful. Kosho 45-3737
No. 6, JP-A-50-126732 can advantageously be used.

The method of adding an oil-soluble fluorescent whitening agent to a photosensitive material as an emulsified dispersion or a latex dispersion is mainly used. For example, as a method of emulsification and dispersion, it can be prepared by dissolving in a high boiling point organic solvent or a water-insoluble polymer and emulsifying and dispersing. Specifically, there is a method in which a fluorescent whitening agent is dissolved in a high boiling organic solvent as exemplified in British Patent No. 1072915, and this is emulsified and dispersed together with a surfactant in a hydrophilic colloid such as gelatin. As the high boiling point solvent, amide compounds, benzoic esters, substituted paraffins and the like can be used in addition to phthalic esters and phosphoric esters.

An emulsified dispersion can be prepared in the same manner as described above by using a water-insoluble polymer such as polyurethane or polyacrylate instead of the high boiling point organic solvent.

As a method for preparing a latex dispersion, an oil-soluble fluorescent whitening agent is dissolved in a monomer in advance and then polymerized to form a latex dispersion, or a latex is impregnated with a hydrophobic polymer using an auxiliary solvent. There is a method of making a dispersion, for example, these are disclosed in JP-A-50-126732,
JP-B-51-47043, U.S. Patent Nos. 3,418,127 and 3,359,
Nos. 102, 3,558,316 and 3,788,854.

Hereinafter, examples of the compound of the fluorescent whitening agent preferably used in the present invention are shown, but the present invention is not limited to these.

The amount of fluorescent whitening agent used preferably in the present invention is preferably added as 0.1 to 200 mg / m ² is present in the finished photosensitive material, is most preferably employed in the range of 1 to 100 mg / m ^2.

The fluorescent brightener used in the present invention may be added to one or more of a silver halide emulsion layer (photosensitive layer) and a non-photosensitive hydrophilic colloid layer (protective layer, intermediate layer, undercoat layer). it can.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [single or multiple layers] and a so-called stacked structure particle having a different halogen composition, or
Particles having a structure having a different halogen composition in a non-layered manner inside or on the surface of the particle (in the case of being on the surface of the particle, a structure in which different composition portions are bonded on the edge, corner or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver halide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
It is more preferably at least 95 mol%.

Such a high silver chloride emulsion preferably has a structure in which a silver bromide localized phase is formed in a layered or non-layered form inside and / or on the surface of silver halide grains as described above.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is a phase epitaxially grown at the corners of the grains.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in Chimi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7 years), Photographic Emulsion Chemistry by GFDuffin
(Focal Press, 1966), M by VLZelikman et al
aking and Coating Photographic Emuldion (Focal Pre
ss, published in 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds and the spectral sensitization method, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is either a so-called surface latent image type emulsion in which a latent image is mainly formed on the surface of a grain, or a so-called internal latent image type emulsion in which a latent image is mainly formed inside a grain. Is also good.

When the present invention is applied to a color light-sensitive material, the color light-sensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler which couple to an oxidized form of an aromatic amine-based color developing agent to form yellow, magenta, and cyan, respectively. Usually used.

The cyan coupler and magenta coupler preferably used in the present invention are represented by the following general formulas (C-I) and (C
-II), (MI) and (M-II).

General formula (C-I) General formula (C-II) General formula (MI) General formula (M-II) In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, the aryl group is substituted with a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In formula (C-II), R ₆ is preferably a hydrogen atom or a halogen atom, and particularly preferably a chlorine atom or a fluorine atom. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The permissible substituents for the aryl group (preferably a phenyl group) for R ₇ and R ₉ are the same as the permissible substituents for the substituent R ₁ , and when there are two or more substituents, they are the same. But they may be different. R ₈
Is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Desirable Y ₃ is of a type capable of releasing at any of a sulfur, oxygen or nitrogen atom, and particularly preferred is a type of releasing at a sulfur atom as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Za-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 is advantageous in terms of low yellow side absorption and light fastness of a coloring dye. Are preferred, US Pat.
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and an alkoxy group or aryloxy group at the 6-position as described in EP 226,849 and 294,785. Preference is given to using pyrazolotriazole couplers.

Specific examples of the couplers represented by formulas (CI), (C-II), (MI) and (M-II) are listed below.

The couplers represented by the above general formulas (CI) to (M-II) are usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
It is contained in an amount of 1 to 0.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called fish dispersion method. After removing the low-boiling organic solvent from the coupler dispersion by a method such as distillation, noodle washing or ultrafiltration, it may be mixed with a photographic emulsion.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used.

Wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and W ₄ represents W ₁ , OW ₁ or SW.
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat. UK Patent 2,0
No. 66,975, JP-A-59-10539, JP-B-57-19765, and the like, hindered phenols are disclosed in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.
No. 52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat.
No. 3,457,079, No. 4,332,886, JP-B-56-21144, etc., hindered amines are U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1-114036, 59-53846 and 59-78344, metal complexes are disclosed in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, a polymer of an ultraviolet absorber 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.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a secondary reaction rate constant k ₂ (in trioctyl phosphate at 80 ° C.) of from 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with p-anisidine. It is a compound that reacts. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in specifications such as European Patent Publication Nos. 298321 and 277589 are preferable.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development treatment is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Wuice, The Macromolecule Chemistry of Gelatin (Academic Press, 1964).

The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing, and washing (or stabilization). Bleaching and fixing may be performed separately, instead of in a single bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene 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 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylmethyl) 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 Among the above p-phenylenediamine derivatives, particularly preferred is 4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamido) ethyl] -aniline (Exemplary compound D-6).

Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, p-toluenesulfonates and the like may be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developer.

In the practice of the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, substantially not containing, preferably 2 ml / or less,
More preferably, the concentration of benzyl alcohol is 0.5 ml / or less, and most preferably, no benzyl alcohol is contained.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an effect is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics due to the continuous processing.
Here, substantially not containing, preferably 3.0 × 10 ^-3
It has a sulfite ion concentration of mol / or less, and most preferably contains no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

More preferably, the developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones,
Sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, and the like are particularly effective organic preservatives. These are disclosed in
−4235, 63−30845, 63−21647, 63−4465
No. 5, 63-53551, 63-43140, 63-56654,
63-58346, 63-43138, 63-146041, 63
-44657, 63-44656, U.S. Patent No. 3,615,503,
No. 2,494,903, JP-A-52-143020, JP-B-48-30496
No., etc.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 or the like may be contained as necessary. In particular, addition of alkanolamines such as triethanolamine, dialkylhydroxylamine such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the above organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides)
Are particularly preferred, and for details, see JP-A-62-2552.
No. 70, No. 63-9713, No. 63-9714, No. 63-11300 and the like.

It is more preferable to use the hydroxylamine derivative or the hydrazine derivative in combination with an amine in terms of improving the stability of the color developing solution, and further improving the stability during continuous processing.

Examples of the amines include cyclic amines described in JP-A-63-239447, amines described in JP-A-63-128340, and other amines disclosed in Japanese Patent Application No. 63-9713. 63
Amines as described in JP-11300.

In the present invention, 3.5 × 1 chloride ion in the color developer
The content is preferably 0 ^{-2 to} 1.5 × 10 ^-1 mol / mol. Particularly preferably, it is 4 × 10 ^-2 to 1 × 10 ^-1 mol /. When the chloride ion concentration is more than 1.5 × 10 ^-1 to 10 ^-1 mol / mol, it has a disadvantage of delaying the development, and is not preferable for achieving the object of the present invention of rapid and high maximum concentration. Further, if it is less than 3.5 × 10 ⁻² mol / mol, it is not preferable in preventing fog.

In the present invention, the bromine ion in the color developer is 3.0
The content is preferably from × 10 ⁻⁵ mol / to 1.0 × 10 ⁻³ mol /. More preferably, 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol /
It is. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / mol, the development is delayed, the maximum density and the sensitivity are lowered, and
If the amount is less than ^10-5 mol / m, fogging cannot be sufficiently prevented.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material into the developer during the development processing.

When directly added to the color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with the preferred ones being preferred. Are sodium chloride and potassium chloride.

Further, it may be supplied from a fluorescent whitening agent added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development processing, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salts, trishydroxyaminomethane salts, lysine salts, and the like. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate are soluble and have a high pH of 9.0 or more.
It is excellent in the buffering capacity in the H region, has no adverse effects on photographic performance (such as fog) even when added to a color developer, and has the advantages of being inexpensive, and it is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And the like. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.
For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid, transsilohexanediaminetetraacetic acid, 1 , 2-Diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'- Bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like can be mentioned.

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat. p-phenylenediamine compound, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826 and 5
Quaternary ammonium salts represented by 2-43429 and the like, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796,
No. 3,253,919, JP-B-41-11431, U.S. Pat.
Nos. 546, 2,596,926 and 3,582,346, amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-B-42-2388.
No. 3, US Pat. No. 3,532,501, etc., polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent whitening agent. 4,4 'as fluorescent whitening agent
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1 g-4 /.

Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added as needed.

The processing temperature of the color phenomenon liquid applicable to the present invention is 20 to
The temperature is 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Although the replenishment amount is preferably small, it is suitably 20 to 600 ml, preferably 50 to 300 ml, per m ^{2 of} the light-sensitive material. More preferably 60ml-200m
l, most preferably from 60 ml to 150 ml.

Next, the desilvering step applicable to the present invention will be described. As the desilvering step, generally, any steps such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step and a bleach-fixing step may be used.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be described below.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution, any bleaching agent can be used. In particular, organic complex salts of iron (III) (for example, ethylenediaminetetraacetic acid,
Preferred are aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like. .

Among these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropane. Examples thereof include tetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycol ether diaminetetraacetic acid. These compounds may be any of the sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.
An iron ion complex salt may be formed. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylate iron complexes are preferred, and the amount added is 0.01 to 1.0 mol /, preferably
0.05 to 0.50 mol /.

In the bleaching solution, the bleach-fixing solution and / or the prebath thereof,
Various compounds can be used as a bleaching accelerator.
For example, U.S. Pat.No. 3,893,858, German Patent No.
Compounds having a mercapto group or a disulfide bond described in 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July, 1978), JP-B-45-8506, JP-A-52-50 -20832, 53-327
No. 35, U.S. Pat. No. 3,706,561, and the like, thiourea-based compounds or halides such as iodine and bromine ions are preferred because of their excellent bleaching power.

Other bleaching solutions or bleach-fixing solutions applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodine. A rehalogenating agent such as an iodide (eg, ammonium iodide). One or more inorganic acids having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if necessary; Organic acids and their alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

Fixing agents used in the bleach-fixing solution or the fixing solution include known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid Thioether compounds such as 3,6-dithia-1,8-octanediol and water-soluble silver halide dissolving agents such as thioureas, which can be used alone or in combination of two or more. . Also, a special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per one is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 9.

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fixing solution and the fixing solution include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives, It preferably contains a sulfite ion releasing compound such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are converted to sulfite ions
The content is preferably 0.02 to 0.05 mol / mol, more preferably 0.04 to 0.40 mol /.

As a preservative, sulfite is generally added,
In addition, you may add ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, etc.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

After desilvering such as fixing or bleach-fixing, washing and / or stabilization are generally performed.

The amount of rinsing water in the rinsing process can vary widely depending on the characteristics of the photosensitive material (for example, the material used such as a coupler), the application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set. Among them, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers (Journa
l of the Society of Motion Picture and Television
Engineers), Vol. 64, pp. 248-253 (May, 1955). Usually, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 to 1 or less per 1 m ^{2 of the} photosensitive material is possible, and the effect of the present invention is remarkable. Problems occur. As a solution to such a problem, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, 61-12
Chlorinated fungicides such as chlorinated sodium isocyanurate described in JP-A No. 145, benzotriazole described in JP-A-61-26761, copper ions and others, written by Hiroshi Horiguchi, "Bactericidal and antifungal chemistry"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) And the bactericides described in (1) and (2).

Further, in the washing water, a surfactant as a draining agent and a chelating agent represented by EDTA as a hardening agent can be used.

It is possible to carry out the treatment with the stabilizing solution directly after the washing step or without the washing step. A compound having an image stabilizing function is added to the stabilizing solution, for example, an aldehyde compound represented by formalin, or a film suitable for stabilizing a dye.
Examples include a buffer for adjusting the pH, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, a fluorescent whitening agent and a hardening agent may be added. In the processing of the light-sensitive material of the present invention, when stabilization is directly performed without going through a washing step, a method disclosed in
Known methods described in JP-A Nos. 8543, 58-14834, 60-220345, etc. can all be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing liquid is also used as a washing liquid or a stabilizing liquid used after the desilvering treatment.

The preferred pH of the washing step or the stabilization step is 4 to 10, more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is desirable from the viewpoint of reducing the processing time. Preferably
15 seconds to 1 minute and 45 seconds, more preferably 30 seconds to 1 minute and 30 seconds.
It is preferable that the replenishing amount is small in view of running cost, reduction of discharge amount, handleability, and the like.

A specific preferable replenishing amount is 0.5 to 50 times, preferably 3 to 4 times the amount of light-sensitive material and the amount brought in from the previous bath per unit area.
It is 0 times. Alternatively, the amount is 1 or less, preferably 500 ml or less per 1 m ^{2 of the} photosensitive material. Replenishment may be performed continuously or intermittently.

The liquid used in the water washing and / or stabilizing step can be further used in the previous step. As an example of this, the overflow of the washing water is reduced by a multi-stage countercurrent method, and is allowed to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

(Examples) Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited to these.

Example 1 LBKP (hardwood bleached, sulfate pulp) 100 for photographic printing paper
% (Basis weight: 175 g / m ² , thickness: about 180 μ) A white pigment-containing resin layer made of water-resistant titanium oxide having the following composition was provided on the surface of white base paper.

To 85 parts by weight of a polyethylene composition (density 0.92 g / cc, melt index (MI) 5.0 g / 10 minutes), 15 parts by weight of an anatase-type titanium oxide white pigment having the following surface treatment was added and kneaded. After melt extrusion coating
A 30 μm water-resistant resin layer was obtained.

The titanium oxide powder was immersed in an ethanol solution of 2,4-dihydroxy-2-methylpentane, heated and evaporated to give a surface treatment. The alcohol was coated on the surface of particles equivalent to about 1% by weight of titanium oxide. On the other hand, only the polyethylene composition was coated on the back surface of the white base paper to obtain a 20 μm water-resistant resin layer.

As shown in Table 1, supports having different densities (% by weight) of titanium oxide were prepared. Each support was provided with an undercoat layer (gelatin layer) after corona discharge to produce a multilayer color photographic paper having the following layer structure. The coating solution was prepared as follows.

Preparation of First Layer Coating Solution 19.1 g of yellow coupler and color image stabilizer (Cpd
-1) 27.2 cc of ethyl acetate and 8.2 g of a solvent (Solv-1) were added to 4.4 g of the color image stabilizer (Cpd-7) and 1.4 g of the color image stabilizer (Cpd-7) to dissolve the solution, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average silver ratio) of 0.88μ and 0.70μ) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide 0.2
(Mol% is localized on the grain surface), and 2.0 × 10 ^-4 mol of the following blue-sensitive sensitizing dye is added per mol of silver to the large-size emulsion, and to the small-size emulsion,
After adding 2.5 × 10 ^-4 mol of each, sulfur-sensitized ones were prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating layers for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used. The following compounds were used as preservatives for each layer. (The numbers indicate the coating amount.) The following were used as spectral sensitizing dyes for each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, and each for small-size emulsion
2.5 × 10 ^-4 mol) (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mole) (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
Mol) The compounds shown in Table 1 were added to the red-sensitive emulsion layer.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

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

The following dyes were added to the emulsion layer to prevent irradiation.

(Yellow Dye) Exemplary Compound V-1 (Magenta Dye) Exemplary Compound IV-a-12 (Cyan Dye) A 2: 5 mixture (weight ratio) of Exemplary Compounds IV-a-18 and IV-a-17.

The amount of each dye added was necessary to obtain the optical reflection density shown in Table 1.

(Layer Configuration) 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 [Polyethylene on the first layer side contains titanium oxide and blue dye (ultra blue) shown in Table 1] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (Details are shown in Table 1.) Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor ( Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, having an average grain size of 0.55 μm and 0.39 μm) 1: 3 mixture (Ag molar ratio) Coefficient of variation in grain size distribution is 0.10 and 0.08, AgBr for each emulsion
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 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 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv) −5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 μm average and 0.45 μm average grain size (Ag mole ratio), fluctuation in grain size distribution) Coefficients are 0.09 and 0.11, AgBr for each emulsion
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 The photographic properties of the samples 101 to 127 based on the above layer structure and combining the support, the yellow coupler, the optical reflection density of the photosensitive material, and the optical brightener as shown in Table 1 were examined by the following methods. Was.

First, each sample was subjected to sensitometric gradation exposure through a color separation filter using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K). The exposure at this time was performed so that the exposure amount was 200 CMS in 1/10 second.

The exposed sample is subjected to continuous processing (running) until a sample obtained by separately applying imagewise exposure to the above-mentioned photosensitive material is replenished in the following processing step until the replenishment is twice the tank capacity of color development. Was developed.

The composition of each processing solution is as follows.

Rinse solution (same as tank solution and replenisher solution) Ion exchange water (3 ppm or less for calcium and magnesium, respectively) The concentration of the sample thus treated was measured, and the relative sensitivity and stain value of each layer were determined.

In addition, using a color negative film that has been separately photographed and processed (especially those with vivid colors such as yellow and green), print it with a enlarger, perform the same processing, and then perform color reproduction. Table 1 summarizes the results of the sensitivity evaluation by multiple people.

Further, a rectangular wave pattern for CTF measurement was subjected to close contact exposure for evaluation of image sharpness, and the above-mentioned development processing was performed. The obtained sample was measured with a microdensitometer and the relative resolution (50% CT
(Calculated from the spatial frequency at the F value). The results are shown in Table 1.

As can be seen from the table, the sample using the yellow coupler of the present invention exhibited excellent color reproducibility, and the amount of the dye adjusted to the optical reflection density within the range of the present invention showed that:
Image sharpness is greatly improved. Further, it was confirmed that the increase in stain was minimized, and that the present invention can sufficiently cope with the desired rapid processing property. From the above, the sample according to the present invention is excellent in color reproduction and high sharpness, and by increasing the titanium oxide density of the support, and further adding a fluorescent whitening agent, a color print with further excellent color reproduction and image sharpness can be obtained. It became clear that it could be obtained.

Example 2 On the same support as in Example 1, a multilayer color photographic paper having the following layer constitution was produced. The coating solution was prepared as follows.

Preparation of First Layer Coating Solution 60.0 g of yellow coupler described below and anti-fading agent (Cpd
-1) 150cc of ethyl acetate and solvent (Solv-3) in 28.0g
1.0 cc and 3.0 cc of a solvent (Solv-4) were added and dissolved. This solution was added to 450 cc of a 10% aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and then dispersed by an ultrasonic homogenizer. Was mixed and dissolved in 420 g of a silver chlorobromide emulsion (0.7 mol% of silver bromide) containing the following blue-sensitive sensitizing dye to prepare a coating solution for the first layer.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-
Bis (vinylsulfonyl) ethane was used.

The following were used as spectral sensitizing dyes for each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,3'-
Disulfoethyl thiacyanine hydroxide Green-sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide Red-sensitive emulsion layer; 3,3'-Diethyl- 5-methoxy-9,11-
Neopentylthiadicarbonanine iodide The following compounds were used as stabilizers for each emulsion layer.

The following anti-irradiation dyes were used in each emulsion layer so that the optical reflection densities were the same as those in Table 1.

(Yellow Dye) Exemplary Compound IV-a-41 (Magenta Dye) Exemplary Compound IV-a-15 (Cyan Dye) Exemplary Compound IV-a-27 (Layer Composition) 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 first layer side polyethylene contains the same titanium oxide and blue dye as in Table 1.] First layer (blue-sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr 0.7 mol%, Cube, average particle size 0.9 μm) 0.29 Gelatin 1.80 Yellow coupler [same as in Table 1] Antifading agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (Solv-4) 0.03 Second layer (color mixture prevention layer) ) Gelatin 0.80 Color mixture inhibitor (Cpd-2) 0.055 Solvent (Solv-1) 0.03 Solvent (Solv-2) 0.15 Third layer (green sensitive layer) Silver chlorobromide emulsion (AgBr 0.7 mol%, cube, Average particle size 0.45 μm) 0.18 Gelatin 1.86 Magenta coupler (ExM) 0.27 Anti-fading agent (Cpd-3) 0.17 Anti-fading agent (Cpd-4) 0.10 Solvent (Solv-1) 0.2 Solvent (Solv-2) 0.03 Fourth layer (Color mixture prevention layer) Gelatin 1.70 Color mixture prevention agent (Cpd-2) 0.065 UV absorber (UV-1 0.45 UV absorber (UV-2) 0.23 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.05 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (AgBr 4 mol%, cubic, average particle size 0.5) 0.21 Gelatin 1.80 Cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.12 Anti-fading agent (Cpd-1) 0.20 Solvent (Solv-1) 0.16 Solvent (Solv-2) 0.09 Color development accelerator (Cpd- 5) 0.15 6th layer (UV absorbing layer) Gelatin 0.70 UV absorber (UV-1) 0.26 UV absorber (UV-2) 0.07 Solvent (Solv-1) 0.30 Solvent (Solv-2) 0.09 7th layer (protection) Layer) Gelatin 1.07 (ExM) Magenta coupler 7-chloro-6-isopropyl-3- {3-[(2-butoxy-5-tert-octyl) benzenesulfonyl] propyl} -1H-pyrazolo [5,1-C] -1,2,4-triazole (ExC-1) cyan coupler 2-pentaful Robenzuamido 4-chloro-5 [2
-(2,4-di-tert-amylphenoxy) -3-methylbutylamidophenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6- [α- (2,4-di-te
rt-amylphenoxy) butyramide] phenol (Cpd-2) Color-mixing inhibitor 2,5-di-tert-octylhydroquinone (Cpd-3) Anti-fading agent 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-2,
2'-spirochroman (Cpd-4) anti-fading agent N- (4-dodecyloxyphenyl) -morpholine (Cpd-5) color-developing agent p- (p-toluenesulfonamide) phenyl-dodecane (Solv-1) solvent Di (2-ethylhexyl) phthalate (Solv-2) solvent Dibutyl phthalate (Solv-3) solvent Di (i-nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide-methoxy-2,4-di- t
-Amylbenzene (UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5-di) -Tert-butylphenyl) benzotriazole Based on the above layer composition, the sample was the same as in Table 1
When 201 to 227 were prepared and subjected to the same processing and evaluation as in Example 1, it was confirmed that the sample of the present invention was remarkably excellent in both color reproduction and image sharpness as in Table 1. did.

(Effect of the Invention) According to the present invention, it is possible to obtain a color print that can be processed quickly, has excellent color reproducibility, and has high image sharpness.

Claims (3)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support. The silver halide emulsion layer contains at least one yellow coupler represented by the following general formula [I], and the optical reflection density at 680 nm of the photosensitive material is 0.70 or more and 2.0 or less, and the optical reflection density at 550 nm is 680 nm. A silver halide color photographic light-sensitive material having a reflection density of not more than a reflection density. General formula [I] Wherein R ₁ is an aryl group or a tertiary alkyl group, R ₂ is a fluorine atom, an alkyl group, an aryl group, an alkoxy group,
An aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, R ₃ can be substituted on a benzene ring, and X can be removed by a coupling reaction with an oxidized aromatic primary amine developer. A group represented by the following general formula (II), and l represents an integer of 0 to 4, respectively. However, when 1 is plural, plural R ₃ may be the same or different. General formula (II) Where Z is The stands, R ₄ and R ₅ is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group,, R ₆ is a hydrogen atom , An alkyl group, an aryl group, an alkylsulfonyl group,
Represents an arylsulfonyl group or an alkoxycarbonyl group. ] 2. The support according to claim 1, wherein the support is a reflective support in which a support substrate is coated with a water-resistant resin layer, and titanium oxide particles are contained in the water-resistant resin layer on the side where the silver halide photosensitive layer is coated. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein said silver halide color photographic material is contained at a density of not less than 60% by weight. 3. A silver halide color photographic material according to claim 2, wherein said silver halide color photographic light-sensitive material contains a fluorescent whitening agent in one of the constituent layers of the photographic light-sensitive material. Photosensitive material.