JPS6232455A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the generation of a fog, without the deterioration of the sensitivity of the titled material by incorporating an oil drop dispersing first coupler and a fisher dispersing second coupler to the layer of the silver halide emulsion layer. CONSTITUTION:The first coupler having the oil drip dispersing property and the second coupler having the fisher dispersing property are incorporated in at least one of the photographic silver halide emulsion layers which are provided on a substrate and are selectively effected with a spectral sensitization. At least one of the compds. selected from the compds. shown by formulas I-III is incorporated to the photosensitive emulsion layers and the adjacent thereto contg. the first and second couplers respectively. In the formula, R1-R3, R5-R7 and R10 and R11 are each a hydrogen atom or an alkyl group, R4 is an hydrogen atom, an aliphatic, an aromatic or a heterocyclic group, R8 and R9 are each a hydrogen atom, an aliphatic or a heterocyclic ring, R8 and R9 together with each other may be formed a ring, R12 is a hydrogen atom, an alkyl group or a halogen atom. Thus, the effect of preventing the fog is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material. In more detail, it suppresses the occurrence of fog without reducing sensitivity,
Moreover, the present invention relates to a silver halide color photographic light-sensitive material which exhibits a small increase in fog during storage and which does not adversely affect graininess.

In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light, coated on a support. For example, in a color negative silver halide photographic light-sensitive material, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are generally coated in this order from the exposed side. Usually, a bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer in order to absorb the blue light that passes through the blue-sensitive silver halide emulsion layer. It is being Further, each emulsion layer is provided with other intermediate layers for various special purposes, and a protective layer as the outermost layer. It is also known that each of these photosensitive silver halide emulsion layers is provided in a different arrangement from the above, and each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a light-sensitive silver halide emulsion layer consisting of two layers having different properties and sensitivities. In these silver halide color photographic light-sensitive materials, exposed silver halide grains are developed using an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler.

In this method, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanocoupler couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanocouplers are typically used to form cyan, magenta and yellow dye images, respectively. The present invention uses an acetyl-based magenta coupler and an acylacetamide-based yellow coupler as a silver halide color photographic light-sensitive material in which these dye-forming couplers are made non-diffusive in advance and are contained in a silver halide emulsion layer. It is appropriate.

[Prior Art] In recent years, silver halide color photographic materials with high sensitivity and excellent graininess have been desired in this industry.

In other words, opportunities to take photographs under poor conditions with little light, such as indoors, or using telephoto lenses or zoom lenses, where camera shake is likely to occur, are increasing, and silver halide color photographic materials are becoming smaller format. Accordingly, there is a strong demand for the development of silver halide color photographic materials that are highly sensitive and have excellent graininess.

To improve the graininess, use a coupler with a fast coupling reaction (fast-reacting Kabuchi) in the high-sensitivity emulsion layer and a coupler with a slow coupling reaction in the low-sensitivity emulsion layer among two calendars with the same color sensitivity. (Slow reactive coupler) method (see U.S. Pat. No. 3,728,4181),
Method of combining fast-reacting couplers and fog inhibitors (
JP-A-58-156932, JP-A-59-9657, and JP-A-59-133544) are known. However, these techniques (1) and (2) use a large amount of fast-reacting couplers, so they have the disadvantage of being prone to fogging. Therefore, the present inventor attempted to use the technique (1) in combination with a fog suppressant as in the technique (2) above, but found that the fog suppressing effect was insufficient. Furthermore, it has been found that when a large amount of a fog suppressant is used to enhance the fog suppressing effect, a decrease in sensitivity is observed.

Furthermore, according to the research of the present inventor, the above-mentioned ■ and ■
It has been found that the above technique has the disadvantage that the storage stability (raw storage stability) of the silver halide color photographic light-sensitive material before exposure is poor and the increase in fog cannot be suppressed. It has also been found that using a large amount of fog suppressant to improve raw shelf life sacrifices sensitivity. Moreover, if a large amount of Fischer-dispersed fast-reactive coupler is used, it will cause a thickening phenomenon during the manufacturing coating process, making it impossible to coat quickly and uniformly.Furthermore, it will not only cause curling but also cracks during drying. It turned out that something happened.

Therefore, the present invention has developed a silver halide color that suppresses the occurrence of fog without reducing sensitivity, has a small increase in fog even when unexposed light-sensitive materials are stored for a long period of time, and has good graininess. Our first priority is to provide photographic materials.
The purpose of

A second object of the present invention is to provide a silver halide color photographic material which can be coated uniformly at high speed during production and which does not exhibit curls or cracks during drying.

[Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention which achieves the above object is a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support. At least one of the silver halide emulsion layers contains an oil droplet-dispersed first coupler and a Fischer-dispersed second coupler, and the silver halide emulsion layer and/or its adjacent layer has the following general formula (1), [■ ] or (fI[).

General formula (I) General formula (n) General formula (III) In the above formula, Rz "l'h, Rs ~ Ry, R
u+ and R■ each represent a hydrogen atom or an alkyl group, R4 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, Ri and R3 each represent a hydrogen atom, an aliphatic group, or a heterocyclic group represents, and includes the case where both Rs and R9 form a ring, provided that Rs and Rs do not have a hydrogen atom at the same time.

RLZ represents a hydrogen atom, an alkyl group or a halogen atom.

According to the present invention, by combining the above-mentioned first and second couplers with different dispersion methods, the object of the present invention can be more than fully realized.

In this case, the oil droplet-dispersing first coupler has a lipophilic group,
The Fischer-dispersed second coupler is soluble in high-boiling organic solvents (although an alkali-soluble group is not essential) and preferably has at least one acidic group, such as a sulfonic acid group or a carboxyl group; It is preferable that the coupler itself and the coloring dye do not diffuse in the wood-philic colloid (in this case, as a group to prevent diffusion, at least one organic group having 8 or more carbon atoms should be placed at a non-active site, that is, at a position that will not be released by the coupling reaction). It is desirable that this second coupler be 50 mol% or less of the total amount of couplers, since not only graininess but also sharpness can be maintained well.The ratio of the second coupler is 20 mol% or less is more preferable, and 10 mol% or less is particularly preferable.The total amount of couplers used in each emulsion layer may be selected as appropriate since the maximum concentration differs depending on the color forming properties of each coupler. , 0.01 to 1 mole of silver halide
It is preferable to use about 0.30 mol.

The first coupler uses a high boiling point organic solvent as described below,
The second coupler may be added in the form of a drop left, and an alkaline solution of the second coupler may be added before or after forming the drop left.

In order to disperse the second coupler in an alkaline aqueous solution, the method described in JP-A-59-80437 may be adopted. In this case, the coupler has an acid group such as carboxylic acid or sulfonic acid. Therefore, it is introduced into the woody colloid as an alkaline aqueous solution.

As mentioned above, when Fischer dispersion coupler is used, it causes a thickening phenomenon during the coating process, which impedes high-speed uniform coating, causes problems with curls and cracks during drying, and also has strong water absorption during image storage. However, the present invention eliminates all such problems because the amount of Fischer dispersion coupler used is small.

Moreover, according to a preferred embodiment of the present invention, this dual puller combination system of Fischer and oil droplet dispersion has DI.
It has been found that by adding an R coupler (DIR compound), sharpness can be sufficiently improved, and at the same time, color reproducibility can be improved by increasing the interlayer effect. The discovery of this effect was also quite surprising.

The present invention will be explained in more detail below.

The first coupler used in the present invention is of the oil droplet dispersion type, and may be a fast-reactive coupler with a fast coupling reaction rate or a slow-reactive coupler with a slow coupling reaction rate. .

Examples of fast-reactive couplers used in the present invention include:

Couplers of the following general formula are preferred.

General formula [■] (Cyan coupler) H In the formula, Xz is a hydrogen atom, a substituted alkoxy group, a substituted aryloxy group, and VL is an acylamino-substituted alkoxy group or a di-substituted phenyl group (for example, a mino group) , represents a halogen atom or an alkoxy group.

J2 represents a sulfo group, a toalkylsulfamoyl group, a carboxy group, an alkoxycarbonyl group, and x
When l is a substituted alkoxy group or a substituted aryloxy group, it represents a furkyl group or an aryloxyalkyl group.

General formula [V] (Magenta coupler) In the formula, xl represents a hydrogen atom or a hydroxyphenylazo group, Z! represents a substituted phenyl group that does not have a substituent at the 2-18-position; however, when Xz is a hydroxyphenylazo group, it may be a substituted phenyl group that has a substituent at the 2-58-position. .

Yl represents an alkyl group, an acylamino group, or a substituted phenylamino group.

General formula [■] (Yellow coupler) In the formula, x3 represents a hydrogen atom or a cyclic amide group,
Rn represents an alkyl group or an alkoxy group.

wl represents the following disubstituted phenyl group.

(Js represents a halogen atom or an alkoxy group, and J4 represents a sulfo group, a carboxy group, or an alkoxycarbonyl group. However, when x3 is a substituted amide group, it may be an acylamino group.) Specifications of particularly preferred fast-reactive couplers Examples include, but are not limited to, the following:

[Exemplary compounds]

(Cyan coupler) (''-s (Mazene coupler) %-3 l (Yellow coupler) CII3 As the slow-reactive coupler of the first coupler used in the present invention, couplers having the following general formula are preferred.

General formula [■] (Cyan coupler) H In the formula, v2 is an alkyl group, an aryloxyalkyl group [e.g. [pentylphenoxy]butyl group, etc.], and ×4 indicates a hydrogen atom or a nor\ogen atom.

General formula [■] (Magenta coupler) In the formula, Rzz represents a halogen atom, a lower alkyl group, or a lower alkoxy group, and R22 represents an alkyl group, an aryloxyalkylcarbonylamide group, or an alkylamide group.

General formula [■] (Yellow coupler) In the formula, R24 represents an alkyl group or an aryloxy group.

Specific examples of particularly preferred slow-reactive couplers include, but are not limited to, the following.

Below is the margin [Exemplary compounds] (Cyan coupler) (Magenta coupler) ? l'C-4 t OCr et Ct (yellow coupler) A specific example of a method for dispersing the first coupler of the present invention is as follows. That is, for example, U.S. Pat. No. 2,322.
No. 027, No. 2,801,170, No. 2,801
．． No. 171, No. 2,272,191 and No. 2.3
According to the method described in each specification of No. 04.940, the first coupler of the present invention is dissolved in a high boiling point solvent, optionally in combination with a low boiling point solvent, and dispersed in the form of fine particles to form a silver halide emulsion or the like. It is preferable to add other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc., if necessary.

Furthermore, two or more kinds of the first couplers of the present invention may be mixed and used.Moreover, in detail, the preferred method of adding the first couplers of the present invention in the present invention is as follows: 1 type or 2 types! ! The above-described first coupler of the present invention may be used together with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as needed, organic acid amides, carbamates, etc.
Esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, triresyl phosphate, triphenyl phosphate, di-ynoctyl azelate, di-n-butyl sebacate, tri-n- Hexyl phosphate, N.

N-di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol,
High boiling point solvents such as 3-pentadecyl phenylethyl ether, 2,5-di-5ec-amylphenylbutyl ether, monophenyl-di-0-chlorophenyl phosphate or fluoroparaffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate , butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, and other low boiling point solvents, alkylbenzenesulfonic acids and alkylnaphthalenesulfones. Mixed with an aqueous solution containing an anionic surfactant such as an acid and/or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate and/or a wood-philic binder such as gelatin, and mixed with a high-speed rotation mixer, It is emulsified and dispersed using a colloid mill or an ultrasonic dispersion device, and then added to a silver halide emulsion.

Next, the second coupler used in the present invention will be explained.

The second coupler used in the present invention is of the Fischer type.

The yellow coupler as the second coupler is preferably one having benzoylacetanilide as a core, and is particularly represented by the general formula (X) (wherein Rn, Rn, Rn and R34 are substituent components (substituents or atoms such as hydrogen atoms), x31 is a group or atom that can be separated by the reaction between the coupler of the general formula [X] and the oxidized product of the color developing agent.) A yellow coupler represented by the following formula is preferred.

In the above general formula (X), Rn, Rn, R4, and R34 may be the same or different, and each includes, for example, a hydrogen atom, a halogen atom, an alkyl group (such as a methyl group, an ethyl group, an isopropyl group, etc.), Alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g. phenoxy, etc.), acylamino groups (e.g. acetylamino, trifluoroacetylamine, etc.), sulfonamino groups (e.g. methanesulfonamino) carbamoyl group, sulfamoyl group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group, ureido group, carboxyl group, hydroxy group, sulfo group, cyano group, etc.

In the second coupler of the present invention, at least one of R to R34 has a diffusion preventing group (for example, a group having 8 or more carbon atoms such as a dodecyl group), and R11 to R34 and! Those in which at least one ht contains an acidic group (eg, carboxyl group, sulfo group, etc.) are used. Examples of Xn include hydrogen atoms, halogen atoms, and those represented by the following general formula.

General formula In this general formula, A represents an oxygen element or a sulfur atom,
B represents a nonmetallic atom necessary to form an aryl ring or a heterocycle, and E represents a nonmetallic atom necessary to form a 5- or 6-membered heterocycle with a nitrogen atom. may further be fused with an aryl ring or a heterocycle.

D represents an organic group (e.g. alkyl group, aryl group) or an atom (e.g. halogen atom), b represents O or a positive integer, and when b is plural, D may be the same or different. , D is 10-, -S-.

-COO-, -GONH-1-S02 NH-, -NH
CONH-1-5Oz --CO-1-NHCO-1-
It may contain a linking group such as 0CO- or -NHSOz -1-NH-.

Further, as the second coupler of the present invention, a yellow coupler having pivaloylacetanilide as a core is also preferable,
In particular, yellow couplers of the following general formula can be used.

General formula (Xr) R3 and R+z have the same meaning as the above-mentioned Ihs and R+z, and may be the same or different, such as a hydrogen atom, a halogen atom, an alkyl group (such as a methyl group, an ethyl group,
isopropyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), acylamino group (e.g., acetylamine group, trifluoroacetylamine group, etc.), sulfonamino group (eg, methanesulfonamino group, benzenesulfonamino group, etc.), carbamoyl group, sulfamoyl group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group, ureido group, carboxyl group, hydroxy group, sulfo group, cyano group, and the like.

As the second coupler, at least one of R3-Rx has a diffusion preventing group (for example, a group having 8 or more carbon atoms such as a dodecyl group), and at least one of R3, R3$ and X- has an acidic group (for example, a carboxyl group). , sulfo group, etc.) is used. x:+2 is synonymous with Xn, and the same thing is exemplified.

A preferable low-molecular magenta coupler as the second coupler used in the present invention is one having a pyrazolotriazole core, and particularly has the general formula [■] 3ff 3q (wherein Rrr, -J-Ru and R3 are all This is a magenta coupler represented by the above Rzt and Xn (synonymous with the above x). R1 and R1 are, for example, a hydrogen atom, an alkyl group that may have a substituent (
(e.g., methyl group, ethyl group, isopropyl group, propyl group, butyl group, etc.), aryl group (e.g., phenyl group, naphthyl group, etc.), or a heterocyclic residue; J is a bond;
For example, it represents -0-1-S-, -N-, Ru represents a hydrogen atom or an alkyl group, and Rn represents, for example, a hydrogen atom.

In the second coupler of the present invention, at least one of Rn-R+s has a diffusion preventing group (for example, a group having 8 or more carbon atoms such as a dodecyl group), and at least one of R37 to Ihs and Xn has an acidic group (for example, a carboxyl group, etc.). group, sulfo group, etc.) is used. As the x-abundance, a hydrogen atom, a halogen atom, and a group of the following general formula are preferable.

General formula % formula % In this general formula, R41 is a halogen atom, an alkyl group (e.g. methyl group, ethyl group, etc.), an alkoxy group (e.g. methoxy group, nidoxy group, etc.), an acylamino group (e.g. acetamide group, benzamide group, etc.) , an alkoxycarbonyl group (e.g. methoxycarbonyl group, etc.), anilino group (e.g. 2-chloroanili 7 groups, 5-7 cetamidoanili 7 groups, etc.), N-alkylcarbamoyl group (e.g. N-methylcarbamoyl group etc.), ureido group (e.g. N-methylureido group, etc.), cyano group, aryl group (e.g., phenyl group, naphthyl group, etc.), N,N-dialkylsulfamoyl group, nitro group, hydroxy group.

R41 is a group or atom selected from a carboxyl group, an aryloxy group, etc., and when 1g is 2 or more, R41 may be the same or different.

R42 represents a substituted or unsubstituted alkyl group (e.g., butyl group, methyl group, etc.), an aralkyl group (e.g., benzyl group, etc.), an alkenyl group (e.g., allyl group, etc.), or a cyclic alkyl group (e.g., cyclopentyl group, etc.), and Examples of groups include halogen atoms, alkoxy groups (butoxy groups, methyloxy groups, etc.), acylamide groups (e.g. acetamide groups, tetradecanamide groups, etc.), alkoxycarbonyl groups (e.g. methoxycarbonyl groups, etc.), toalkyl groups (e.g. N -methylcarbamoyl group, etc.),
Ureido group (e.g. ethylureido group etc.), cyano group,
Aryl groups (e.g., phenyl groups, etc.), nitro groups, alkylthio groups (e.g., methylthio groups, etc.), alkylsulfamoyl groups (e.g., ethylsulfamoyl groups, etc.), alkylsulfone groups, anilino groups, sulfonamide groups (e.g., ethylsulfone groups, etc.) amide group, etc.), toalkylsulfamoyl group, aryloxy group, and acyl group (for example, acetyl group, etc.).

In addition to the above, preferred magenta couplers include those having l-7enyl-5-pyrazolone or pyrazolobenzimidazole as a core, and those represented by the following general formulas and calendars are particularly preferred. It will be done.

General Formula [Employment] General Formula Of) Here, both R43 and R44 have the same meaning as the above-mentioned Rn, and X34 has the same meaning as the above-mentioned Xn.

In the above general formulas and calendars, R43 is, for example, an acylamino group (e.g. propanamide group, benzamide group, etc.), anilino group (e.g. 2-chloroanili7 group,
5-7 cetamidoanilino group, etc.) or ureido groups (e.g., phenylureido group, butaneureido group, etc.), and R44 is 1, for example, hydrogen atom, /X rogen atom, alkyl group, alkoxy group, hydroxycarbonyl group, Examples include an alkoxycarbonyl group, a nitro group, an aryloxy group, a sulfo group, a carboxyl group, a cyan group, and an acylamino group.

As the second coupler of the present invention, at least one of R43 and R44 is a diffusion preventing group (for example, a dodecyl group, etc., having 8 carbon atoms).
The above groups), and at least one of R4, R44 and X:14 contains at least one acidic group (for example, carboxyl group, sulfo group, etc.). X34
Examples include the same as the above-mentioned X32. f is O
is an integer of ~4, and when f is 2 or more, each R44 may be the same or different.

Cyan couplers that can be used as the second coupler of the present invention are preferably those having a phenol or naphthol core, particularly those represented by the following general formulas [Summer] and CX VI).

General Formula [Two] H General Formula (XVI) In this general formula, R45 to R5I are all the same as Rn described above, and Xs and Xs are synonymous with X21 described above.

R45 is, for example, a hydrogen atom, an aliphatic group (for example, an alkyl group such as an ethyl group, an isopropyl group, an acyl group, a cyclohexyl group, an octyl group, etc.), an alkoxy group (
For example, methoxy group, isopropoxy group, pentadecyloxy group, etc.), aryloxy group (for example, phenoxy group, β
-tert-butylphenoxy group, etc.), an acylamide group, a sulfonamide group, a ureido group, or a carbamoyl group represented by the following general formula.

General formula % formula % In the formula, G1 and G2 may be the same or different, and each is a hydrogen atom (however, G1 and G2 are not hydrogen atoms at the same time), an aliphatic group having 1 to 8 carbon atoms group, preferably a linear or branched alkyl group having 4 to 8 carbon atoms, a cyclic alkyl group (e.g., cyclopropyl group, cyclohexyl group, norbornyl group, etc.) or an aryl group (e.g., phenyl group,
naphthyl group, etc.), where the above alkyl group and aryl group represent a halogen atom (e.g. fluorine, chlorine, etc.), nitro group, cyano group, carboxyl group, sulfo group, hydroxy group, amino group (e.g. amine group, alkyl amine group, etc.). alkyl groups (e.g., those mentioned above): alkoxycarbonyl groups (e.g., butyloxycarbonyl groups, etc.), acyloxycarbonyl groups, amide groups (e.g., acetamido groups) , methanesulfonamide group, etc.), imide group (e.g., succinimide group, etc.), carbamoyl group (e.g., N
, N-diethylcarbamoyl group, etc.), sulfamoyl group (e.g., N,N-diethylsulfamoyl group, etc.), alkoxy group (e.g., ethoxy group, butyloxy group, octyloxy group, etc.), aryloxy group (e.g., phenoxy group, methyl phenoxy group, etc.).

In addition to the above-mentioned substituents, RAS may contain commonly used substituents.

R411 is selected from, for example, a hydrogen atom, an aliphatic group, especially an alkyl group, or a carbamoyl group represented by the above general formula.

Examples of R47, Rn, R4s, Rso and RfA include a hydrogen atom, a halogen atom, and an alkyl group, respectively.

Aryl group, alkoxy group, alkylthio group, heterocyclic group, amine group, carbonamide group, sulfonamide group,
Examples include sulfamyl group and carbamyl group.

Specific examples of R4T include the following.

That is, hydrogen atoms, halogen atoms (e.g. chloro, bromine, etc.), primary, secondary or tertiary alkyl groups (e.g. methyl, propyl, isopropyl, n-butyl, nibutyl, tert-butyl, etc.). hexyl group, 2-chlorobutyl group, 2-hydroxyethyl group, 2-phenylethyl group, 2-(2,4,8-)lichlorophenyl)ethyl group,
2-7minoethyl group, etc.), alkylthio group (e.g. octylthio group, etc.), aryl group (e.g. phenyl group, 4-
Methylphenyl group, 2,4.8-trichlorophenyl, l, 3.5-dibromophenyl group, 4-trifluoromethylphenyl group, 2-tolylfluoromethylphenyl group, 3-trifluoromethylphenyl group, naphthyl group, 2-chloronaphthyl group, 3-ethylnaphthyl group, etc.),
Heterocyclic groups (e.g. benzothiazolyl group, benzoxacylyl group, naphthoxacylyl group, pyridyl group, quinolinyl group, etc.), amide group (e.g. amino group, methylamine group, diethylamino group, phenylamino group, tolylamino group, 4 -cyanophenylamino group, 2-trifluoromethylphenylamino group, benzothiazolamide group, etc.), carbonamide group (for example, alkylcarbonamide group such as ethylcarbonamide group; phenylcarbonamide group, 2,4.8 - Trichlorophenylcarbonamide group, 2-ethoxycarbonamide group; such as thiazolecarbonamide group, benzothiazolecarbonamide group, oxacylylcarbonamide group, benzoxasilylcarbonamide group, imidazolylcarbonamide group, benzimidazolylcarbonamide group heterocyclic carbonamide group), sulfonamide group (e.g. alkylsulfonamide group such as butylsulfonamide group, phenylethylsulfonamide group; phenylsulfonamide group,
2.4.8-trichlorophenylsulfonamide group, 2
-Arylsulfonamide groups such as methoxyphenylsulfonamide group and 3-carboxyphenylsulfonamide group: thiazolylsulfonamide group, benzothiazolylsulfonamide group, imidazolylsulfonamide group, benzimidazolylsulfonamide group, pyridylsulfonamide group heterocyclic sulfonamide groups, etc.), sulfamyl groups (e.g., propylsulfamyl groups, alkylsulfamyl groups such as octylsulfamyl groups: phenylsulfamyl groups, 2,4.8-)lichlorophenyl Arylsulfamyl groups such as sulfamyl group and 2-methoxyphenylsulfamyl group: thiazolylsulfamyl group, benzothiazolylsulfamyl group, oxacylylsulfamyl group, benzimidazolylsulfamyl group, Heterocyclic sulfamyl groups such as pyridylsulfamyl groups, etc.)
and carbamyl groups (for example, alkylcarbamyl groups such as ethylcarbamyl group and octylcarbamyl group; arylcarbamyl groups such as phenylcarbamyl group, 2,4.8-trichlorophenylcarbamyl group, and thiazolylcarbamyl group) , benzothiazolylcarbamyl group.

(heterocyclic carbamyl groups such as oxasilylcarbamyl group, imodazolylcarbamyl group, benzimidazolylcarbamyl group, etc.).

R41, R4s, Rso and Rsx can also specifically include those listed for R4T, and J represents a nonmetallic atom necessary to form a 5- and/or 6-membered ring as shown below. That is, benzene ring, cyclohexene ring, cyclopentyl ring.

Examples include a thiazole ring, an oxazole ring, an imidazole ring, a pyridine ring, and a pyrrole ring. Among these, a benzene ring is preferred.

As the second coupler of the present invention, in the general formula [Summer], at least one of R4S, R4T to R4s has a diffusion preventing group (for example, a dodecyl group having 8 or more ring carbon atoms) L, KaR4%, R4? ~R41 and)hs(7
) Those containing at least one acidic group (eg, carboxyl group, sulfo group, etc.) are preferably used.

In the second coupler of the present invention, in the general formula (XVI), at least one of R4 to Rsx has a diffusion preventing group (for example, a group having 8 or more carbon atoms such as a dodecyl group), and R
Those in which at least one of 4@~Ru and x3s contains at least one acidic group (eg, carboxyl group, sulfo group, etc.) are preferably used.

X:IS,
Preferred examples of the group include an alkoxy group, an aryloxy group, an alkylthio group, and an arylthio group. These groups further include 10-, -S-,
-NH-, -CONH-2-COO-1-9Oz NH
-, -5o-, -3Oz -, -CO-1, etc. may have a substituent (for example, an alkyl group, an aryl group, a heterocyclic group, etc.) via a divalent group, and furthermore, these The group may have a carboxyl group, sulfo group, sulfamoyl group, hydroxy group, etc. as a substituent.

Preferred examples of the second coupler are shown below.

[Exemplary compounds]

ρI H ρl 00H OOH 18H37 I8H37 `` Y-10 M-4 t t ρI l7H35 03H M-10 at o3H C00C2H5 OOH M-22 COOH COOH 00H COOH 12H25 0CH2CH2COOH 0CH2CH2SCH2CO2H 0CH2CH2SCHC1Has CO□H SO 3 N a 0H O3H TITJ r o 3H m16 03H H The silver halide color photographic light-sensitive material of the present invention comprises the first
The photosensitive emulsion layer containing the coupler and the second coupler or its adjacent layer contains at least one compound selected from the following general formulas CI), (II) and (m) (hereinafter, compound (I),
(II) or (m)).

General formula CI) General formula (n) General formula [III] In the above formula, Ra ~ R3, Rs ” Ry, Rto, R
u represents a hydrogen atom or an alkyl group, R
4 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group; Ra and Ri each represent a hydrogen atom, an aliphatic group, or a heterocyclic group; when both R8゜R9 form a ring; However, R11 and R9 do not have hydrogen atoms at the same time.

Rzz represents a hydrogen atom, an alkyl group or a halogen atom.

In the present invention, the above compound (I), [■]
As a result of using or (m), an efficient fog prevention effect was obtained. Moreover, this compound CI), (II) or (
m) brings about this improvement in performance without causing the short-circuit phenomenon, which is something that has not been known at all in the past. Among these types of compounds, esters and amides of gallic soap are known to have a graininess-improving effect on certain couplers (Japanese Patent Application Laid-open Nos. 58-156932 and 59). -9657, No. 59-133544, etc.), when combined with the Fisher type coupler used in the present invention, fogging could be effectively suppressed and storage stability was improved.

Compounds (I), (n) or [m] according to the present invention may be one or more selected from each group of (I), (II) or (III); Group CI)
, (n) or (III) may be used in combination, the layer to be contained is preferably a light-sensitive emulsion layer containing the first and second couplers according to the invention, or a layer adjacent thereto, but Most preferred is a light-sensitive emulsion layer comprising first and second couplers according to the invention.

To explain these compounds CI), (II), or (m), first, in general formula (1), examples of the aliphatic group for R4 include an alkyl group, an alkenyl group, a cycloalkyl group, and an alkynyl group. be able to. Among these, the chain type may be straight chain or branched, and each group may have a substituent. Examples of alkyl groups include those having 1 to 30 carbon atoms. Preferably 1 to 2 carbon atoms
For example, methyl group, ethyl group, propyl group, n-butyl group, 5ec-butyl group,
t-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, t-octyl group, n-dodecyl group,
Examples include n-hexadecyl group, n-oxtadecyl group, instearyl group, and eicosyl group.

Examples of substituents that an alkyl group may have include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom,
Examples include a carboxy group, a sulfo group, a cyano group, an aryl group, an alkylamino group, an arylamino group, a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an acyl group, a sulfonyl group, an acyloxy group, and an acylamino group. Examples of the alkenyl group include those having 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as allylbutenyl group, prenyl group, octenyl group, dodecenyl group, and oleyl group. Examples of the alkynyl group include those having 3 to 30 carbon atoms, preferably 3 to 22 carbon atoms, such as a butyl group. Alkenyl groups and alkynyl groups may also have the same substituents as alkyl groups. As the cycloalkyl group, a 3- to 12-membered, preferably 5- to 7-membered group can be used. Examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclododecyl group. . Examples of the aromatic group for R4 include phenyl and naphthyl groups. Examples of the heterocyclic group for R4 include a thiazolyl ring group, an oxacylyl ring group, an imidazolyl ring group, a furyl ring group, a chenyl ring group, a tetrahydrofuryl ring group, a piperidyl ring group, a thiadiazolyl ring group, an oxadiazolyl ring group, and a penzothiazolyl ring group. , a benzoxasilyl ring group, a benzimidazolyl ring group, and the like.

These cyclic groups may have the substituents exemplified for alkyl groups, and may also have other alkyl groups, alkenyl groups, and the like.

It is preferable that at least one of R~R3 in the general formula (I) is a hydrogen atom.a The alkyl group of Rt~R3 has 1 to 10 carbon atoms, preferably 1 to 1 carbon atoms.
5, more preferably those having 1 to 3 carbon atoms can be used.

The compounds represented by the general formula CI) will be specifically exemplified below, but are not limited to these examples, provided that R1 to R4 in the general formula CI) are specified.

In the following margin, in the general formula (n), the aliphatic group, aromatic group, and heterocyclic group of R8 and Ri are as follows.

The same examples as those mentioned in the explanation of general formula CI) above can be used for each. The substituents that each of these groups may have are also the same as those mentioned above. The ring that forms a ring with Rw and Rg has 3 to 12 members, preferably 5 to 12 members.
Examples include ethylene group, tetramethine group, pentamethine group, hexamethylene group, and dodecamethylene group.

It is preferable that at least one of 25 to 2 in the general formula (II) is a hydrogen atom. e The alkyl group of Rs to R7 has 1 to 10 carbon atoms, preferably 1 carbon atom.
to 5 carbon atoms, more preferably 1 to 3 carbon atoms.

The compounds represented by the general formula (II) are specifically illustrated below, but are not limited to these examples, however, the compounds are illustrated by specifying R5 to R9 in the general formula (n).

Next, the alkyl group of R11l-R12 in the general formula ([) has 1 to 105 carbon atoms, preferably 1 to 5 carbon atoms.
can be used.

The compounds represented by the general formula (III) are specifically illustrated below, but are not limited to these examples, however,
An example will be given in which Ru+ to RL2 in the general formula (m) are specified.

In recent years, silver halide color photographic materials with high sensitivity and good graininess and color reproducibility have been desired. It is also effective when applied to photographic materials; rather,
more effective.

The following are known layer structures for achieving high sensitivity, etc. For example, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer coated sequentially on a support. In the above-mentioned order layer structure of each light-sensitive silver halide emulsion layer of the blue-sensitive silver halide emulsion layer, for some or all of the light-sensitive silver halide emulsion layers, substantially the same color-sensitive layer,
A high-sensitivity silver halide emulsion layer (hereinafter referred to as "high-sensitivity emulsion layer") and a low-sensitivity silver halide emulsion layer (hereinafter referred to as "low-sensitivity emulsion layer") containing diffusion-resistant couplers that develop substantially the same hue as each other. There is a layered structure in which these are separated and layered adjacently. Note that this layer configuration will hereinafter be referred to as a high-sensitivity W4 layer configuration.

On the other hand, the following technology is known as an inverted layer structure that achieves high sensitivity.

[A] First, JP-A-51-49027 discloses (a) each low-sensitivity emulsion layer (RG low-sensitivity layer unit) of a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer in order from the support side. Painted.

(b) On the RG low-sensitivity layer unit, each high-sensitivity emulsion layer (RG high-sensitivity unit) of a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer is coated in order from the support side, c) On the RG high-speed layer unit, high-speed and low-speed emulsion layers (B
[B] Also, in JP-A-53-97424, the above-mentioned [A
In a silver halide color photographic light-sensitive material having one structure, R
A configuration is described in which each of the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer of the G low-speed layer unit is coated separately into medium-speed and low-speed layers, [C] Furthermore, this document Japanese Patent Application No. 58-52115 filed by the applicant describes a structure in which an RGB low-sensitivity layer unit and an RGB high-sensitivity layer unit are sequentially coated on a support.

The silver halide color photographic light-sensitive materials having these [A], [B] and [C] structures (hereinafter referred to as high-sensitivity reverse layer structure) are:
In either case, at least a highly sensitive red-sensitive silver halide emulsion layer is provided between a green-sensitive silver halide emulsion layer having high sensitivity and a green-sensitive silver halide emulsion layer having a sensitivity lower than that of the high-sensitivity green-sensitive silver halide emulsion layer. It is an effective means to achieve the objectives of high sensitivity and high image quality.

The present invention is effective when applied to either the above-mentioned silver halide color photographic material having a high-sensitivity reverse layer structure or a high-sensitivity reverse layer structure; in fact, it is more effective.

The silver halide grains used in the present invention may be obtained by any conventionally known preparation method such as an acid method, a neutral method, or an ammonia method.

Alternatively, for example, seed grains may be produced using an acidic method, and then grown using an ammonia method, which has a fast growth rate, to grow to a predetermined size.When growing silver halide grains, the PH, PAg, etc. in the reaction vessel may be It is preferable to simultaneously implant and mix silver ions and l\ride ions in amounts commensurate with the growth rate of silver halide grains under controlled conditions, for example, as described in JP-A No. 54-48521.

The silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions contain active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.: Noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium glorooleate, 2-aurothiol-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (consisting of these Depending on the amount, these substances act as sensitizers or fog suppressants. It may also be chemically sensitized by using a combination of agents, etc.).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, the silver halide emulsion contains at least 1N hydroxytetrazaindene and a nitrogen-containing heterozygous compound having a mercapto group. It may contain at least one kind of ring compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 x 10-8 to 3 x 1 per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
Optical sensitization can be achieved by adding 0-3 mol. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more types. Examples of the sensitizing dyes that can be advantageously used in the present invention include the following: I can list kimono.

That is, examples of sensitizing dyes used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Pat. No. 2,231,858, US Pat.
, No. 503.778, No. 2,519.001, No. 2,
No. 912,329, No. 3.858,959, No. 3.
No. 872,897, 3. [i94, 217, same 4,
Examples include those described in Japanese Patent Publication No. 025,349, British Patent No. 4.048.572, British Patent No. 1.242,588, Japanese Patent Publication No. 14030/1982, and Japanese Patent Publication No. 52-24844. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 2.945,783, British Patent No. 505,979, and red-sensitive silver halide emulsions. Examples of sensitizing dyes used in
, No. 234, No. 2.270.378, No. 2,442,
No. 710, No. 2,454,829, No. 2.778.2
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 80 and the like. Furthermore, U.S. Patent 2.213
．． No. 895, No. 2,493,748, No. 2,519,
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 001 and West German Patent No. 929,080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
No. 59-116647 and the like.

Further, regarding combinations of carbocyanine having a benzimidazole nucleus with other cyanines or merocyanines, for example, Japanese Patent Publications Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-1
No. 15820, No. 51-135528, No. 52-10
No. 4916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
-18107, No. 47-8741, JP-A-59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a wood-friendly organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Dyes, hemioxonol dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent Nos. 584,809 and 1,277.
, No. 429, JP-A-48-85130, JP-A No. 49-9
No. 9620, No. 49-114420, No. 49-129
No. 537, No. 52-108115, No. 59-2584
No. 5, U.S. Patent No. 2,274,782, U.S. Patent No. 2.533,
No. 472, No. 2,958,879, No. 3,125,
No. 448, No. 3,148,187, No. 3,177.0
No. 78, No. 3,247.127, No. 3.540.88
No. 7, No. 3.575.704, No. 3.853,90
No. 5, No. 3,718,472, No. 4,071,312
No. 4,070,352.

It is more effective to fix these water-soluble dyes by converting them into mordants.For techniques related to mordant formation, see U.S. Pat. Reference may be made to the descriptions in Japanese Patent Publications No. 49-15820, No. 59-33899, etc.

Next, DIR compounds preferably used in the present invention will be explained.

A typical DIR compound that can be used in the present invention is a DIR coupler in which a group capable of forming a compound having a development-inhibiting effect when separated from the active site is introduced into the active site of the coupler. 935,454
No. 3,227,554, U.S. Pat. No. 4,095,9
No. 84, No. 4,149,888 JP 57-1519
It is described in No. 44, etc. The above DIR coupler is
When subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor.

Further, the present invention is disclosed in US Pat. No. 3,852,345 and US Pat.
No. 928.041, No. 3,958,993, No. 3,9
No. 81,959, No. 4.052,213, Japanese Unexamined Patent Publication No. 1973
-110529, 54-13333, 55-1
Also included are compounds that release a development inhibitor when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 61237, but do not form a dye.

Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Or so-called timing D, which is a compound that releases a development inhibitor through an elimination reaction.
IR compounds are also included in the invention.

Also, JP-A No. 58-160954, No. 58-16294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
It also includes R compounds.

Typical specific examples of DIR compounds are described below, but the present invention is not limited thereto.

Below margin (D [Exemplary compounds] N=N No.

(D-6) 0,H.

CD-7) L -N -N (D-f3) 2H5 (D-16) 02H5 (D-17) H These DIR compounds preferably used in the present invention are:
Although it may be contained in any of the photographic constituent layers, it is preferably added to the photosensitive silver halide emulsion layer, and it is also preferable to use it in the photosensitive layer containing the i11 coupler and second coupler of the present invention. be. Two or more such DIR compounds may be included in the same calendar, or the same DIR compound may be included in two or more different calendars.

These DIR compounds are generally preferred in amounts of 2 X IQ = ~L X 1 G'' moles per mole of silver in the emulsion layer;
More preferably, IX+o-3 to 2X10-2 mol is used.

In order to incorporate these couplers, DIR compounds, etc. into the silver halide emulsion or other photographic constituent layer coating solution according to the present invention, reference can be made to the method for adding the first coupler and second coupler of the present invention.

In the silver halide emulsion layer of the present invention and other photographic constituent layers, couplers such as non-diffusible couplers and polymer couplers that react with the oxidized form of the developing agent to form a diffusible dye that bleeds appropriately may be used. Regarding a good non-diffusible coupler that reacts with a non-diffusible DIR compound converted into an image developing agent to form a diffusible dye that bleeds moderately, the present applicant has disclosed a patent application filed in 1973.
For polymer couplers, reference can be made to the description in Japanese Patent Application No. 1987-172151 filed by the present applicant. The total amount of Kabuchi used in each layer can be selected as appropriate since the maximum concentration differs depending on the coloring property of each coupler, but it is recommended to use about 0.01 to 0.30 mol per 1 mol of silver halide. preferable.

To incorporate these couplers and the like into the silver halide emulsion and other coating solutions for photographic constituent layers according to the present invention, reference can be made to the above description of the method for incorporating the compounds of the present invention into photographic constituent layers.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as the prevention of color staining described in JP-A No. 46-2128 and U.S. Pat. No. 2,728,859. antifoggants, stabilizers, ultraviolet absorbers, one-color stain inhibitors, color image fading inhibitors, antistatic agents, hardeners, and surfactants other than those of the present invention described in Research Disclosure Magazine No. 17843. agent, plasticizer,
In the silver halide color photographic light-sensitive material of the present invention, the parent colloid used to prepare the emulsion includes gelatin, derivative gelatin, and grafts of gelatin and other polymers. Polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, synthesis of single or copolymers such as I powder, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, etc. Anything is included.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, a glass plate, cellulose acetate, There are transparent supports such as polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films, and these supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the emulsion layer and other constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2.781,791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941,898.

There are no particular restrictions on the method of processing the photographic material according to the present invention, and any processing method can be used6. Alternatively, a method of performing stabilization treatment, a method of performing bleaching and fixing separately after color development, and further washing with water and/or stabilization treatment as necessary: or a method of pre-hardening, neutralization, color development, stop-fixing, washing with water,
Method of bleaching, fixing, washing with water, post hardening, washing with water, color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water,
Any method may be used for processing, such as a method in which the developed silver produced by color development is subjected to halogenation bleaching and then color development is performed again to increase the amount of dye produced.

The color developing solution used in processing the silver halide color photographic light-sensitive material of the present invention preferably contains an aromatic primary amine developing agent.
H is preferably 8 or more, more preferably pH is 9 to 12
It is an alkaline aqueous solution of The aromatic primary amine developing agent used as the color developing agent is a compound that has a primary amino group on an aromatic ring and has the power to develop exposed silver halide. Precursors that form such compounds may also be added.

The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-Amino-N,N-diethylaniline, 4-7minor N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-aminoethylroot β-methoxyethylaniline, 3-methyl-4-amino-X-ethylroot β-methanesulfonamidoethylaniline, 3 −
Methoxy-4-aminoethylroot β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N, N-dimethylaniline, N -ethyl-N-β-[β-(β-methoxyethoxy)ethoxy]
Ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline, and salts thereof such as sulfates,
These include hydrochloride, sulfite, p-)luenesulfonate, and the like.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and the journal of Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951).
The ones described above are also listed as representative ones.

The amount of these aromatic primary amino compounds used depends on where the activity of the developer is set, but in order to increase the activity, it is preferable to increase the amount used, and the amount used is 0. It is used in a range from 0,002 mol/l to 0.7 mol/l. In addition, two or more compounds may be used in combination depending on the purpose. For example, 3-methyl-4-amino, todiethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfone. Amidoethylaniline, 3-methyl-4-amino-N-
Combinations such as ethyl root β-methanesulfonamide ethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline may be used in any combination depending on the purpose.

The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkaline earth metal halides, benzyl alcohol, water stoppers, thickeners, development accelerators, and the like may optionally be included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, l-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. The following are representative examples of the above aminopolycarbonate.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacetic acidethylenediaminetetrabrobionic acidethylenediaminetetraacetic aciddisodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltBleaching solutions can be used with various bleaching agents as mentioned above. It may contain additives, and when a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. In addition, the bleach-fix solution may further contain a halogen compound such as potassium bromide, and, as in the case of the above-mentioned bleach solution, various other additives such as pH buffering agents, antifoaming agents, surfactants, etc. An activator, preservative, chelating agent, stabilizer, organic solvent, etc. may be added or contained.

Examples of silver halide fixing agents include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, 1,000 urea, thioether, etc., which react with silver halide and dissolve in water. Compounds that form a silver salt can be mentioned.

Color development of the silver halide color photographic light-sensitive material of the present invention,
The processing temperature of bleach-fixing (or bleaching, fixing), and various processing steps such as washing with water, stabilization, and drying, which are carried out as necessary, is preferably carried out at 30° C. or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 5B-105145, 58-1
No. 34634 and No. 58-18631 and patent application 1'
A stabilization treatment as an alternative to washing may be performed as shown in 1g5B-2709 and 59-89288.

[Effects of the Invention] According to the present invention, the occurrence of fog is suppressed without reducing the sensitivity, and even if the unexposed photosensitive material is stored for a long period of time, the increase in fog is small, and the graininess is reduced. Moreover, during manufacturing, high-speed uniform application is possible, and no curling or cracking occurs during drying.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 To evaluate the effectiveness of the present invention, various types of coupler emulsions were first prepared. The second coupler was dissolved in aqueous IN caustic potassium solution, then added to a 10% aqueous gelatin solution, and the pH was adjusted to 7.0 with IN aqueous citric acid solution.

The first coupler was dissolved in a mixed solvent of tricresyl phosphate (referred to as TCP) and ethyl acetate, and then mixed with a 10% gelatin aqueous solution to which Alkanol XC (manufactured by DuPont) was added as a surfactant. It was emulsified and dispersed using a colloid mill.

The coupler emulsion obtained as described above was added to the silver halide gelatin emulsion, and then coated on a cellulose triacetate film support serving as a subbing layer, and each layer having the composition shown below was coated. Photosensitive material sample No. 1
It was created.

1 Green-sensitive silver halide emulsion layer Silver iodobromide containing 6 mol% silver iodide (average grain size o, a
1. The emulsion consisting of the eJL layer) was color sensitized to green sensitivity.
1 g/rn" (converted to i), the first exemplary coupler compound (m-6) 0.44 g/rn", the second exemplary coupler compound (M-18) 0.55 g/m'', and 0.8
Green-sensitive silver halide emulsion layer containing 1.8 g/m'' of TCP and 1.8 g/m'' of gelatin.

2 1M! 1.3/m'' of gelatin and 0.05 g/ml of 2.4
-dichloro-8-hydroxy-3-)riazine sodium salt.

Next, in light-sensitive material sample No. 1, the following additives A to E were added to the green-sensitive silver halide hole emulsion layer as shown in Table 1 to prepare light-sensitive material samples Nos. 2 to 7.

As the compound to be added, the following was first used as an example of a compound represented by the general formula CI).

Hereinafter, it will be referred to as additive A. This corresponds to the above Exemplified Compound 1-6.

IJ The following was used as another example of the compound represented by the general formula CI). Hereinafter, it will be referred to as additive B.

This corresponds to the above-mentioned exemplified compound 1-14.

The following compounds were used as examples of compounds represented by general formula (II). Hereinafter, it will be referred to as Additive C. This corresponds to the above-mentioned exemplified compound n-19.

The following compounds were used as examples of compounds represented by general formula (III). Hereinafter, it will be referred to as additive. This corresponds to the above-mentioned exemplified compound lll-4.

In addition, the following additives other than the compound of the present invention, which have been conventionally used to prevent fogging, were used for comparison. Hereinafter, it will be referred to as additive E.

lJ H In addition, photosensitive material sample No. 008 was prepared as shown in Table 1 by replacing the second coupler in photosensitive material sample No. 1 with exemplified compound (M-17) and adding additive A.

For comparison, photosensitive material sample No. 099 was prepared as shown in Table 1, in which the first coupler was used alone and additive A was added. That is, the coupler in the emulsion layer of the photosensitive material sample No. 001 was the following first coupler.

First coupler (m-6): per mole of silver.

0.49g/ba.

Furthermore, in photosensitive material sample No. 1, green sensitized silver iodobromide was applied to a core-shell type [core (silver iodide content 10 mol%)].
A photosensitive material sample No. 10 was prepared in which additive A was added in place of the shell (silver iodide content: 2 mol %), volume ratio 1:1, average grain size 0.48 pm.

Each of the photosensitive material samples obtained as described above was subjected to t,
After wedge exposure with ecMs (candelameter second), the following development process was performed.

Processing steps (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing 3 minutes 15 seconds fixing 6 minutes 30 seconds washing 3 minutes 15 seconds stabilization 3 minutes 30 seconds drying The composition of the processing solution used in each processing step is as follows. That's right.

(Color developer) 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline F&M salt 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2. 0g anhydrous potassium carbonate 37.5g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to make one sentence and adjust to p) I-ILO8.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100. g ethylenediaminetetraacetic acid 2 ammonium salt 10.0 g ammonium bromide 150.0 g glacial acetic acid
10. Add hJ1 water and add 1
Adjust the pH to 6.0 using aqueous ammonia.

[Concentrator] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.58 Sodium metasulfite 2.3g Add water to make 11, and adjust to pH = 8.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5m Konidax 7x (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5mM water to make 11.

Sensitometry was performed on each sample and the results obtained are shown in Table 1.

Zero 1... Numerical value per mole of silver (g/rn") Low 2... Amount of additive: per mole of silver, each listed value ra X50p
-ts indicates a value 1000 times the standard deviation of density, and indicates a relative value with photosensitive material sample No. 1 as 100.

For books 4...S, the sensitivity is expressed as the reciprocal of the exposure amount that gives the fog density +0.1, and is expressed as a relative value with Sample No. 001 as 100.

*5...Fog represents fog.

This 6*fist ΔFog indicates the amount of increase in fog after storage at 65° C. for 3 days.

As is clear from the results in Table 1, compared to photosensitive material sample N018 using only the first coupler,
An improvement in RMS can be seen by using a coupler together. In order to deal with the fog that occurs when the first coupler and the second coupler are used in combination, a photosensitive material sample N containing conventional additives was prepared.
o, 8, the effect of suppressing fog was small, and photosensitive material sample No. 097, in which the amount used was increased, suppressed fog, but the sensitivity decreased.Furthermore, an increase in fog was observed during storage.Photosensitive material without additives It can be seen that no significant effect can be obtained on the sample.

On the other hand, when the first coupler and the second coupler are used together and the additives A-D according to the present invention are added as in the present invention (photosensitive material samples No. 2 to 5, No. 8), the sensitivity decreases. The occurrence of fogging can be suppressed without any problems, and the degree of increase in fogging is small even during storage, and furthermore, there is no adverse effect on graininess.

Furthermore, as shown by photosensitive material sample No. 10 among all the samples, it can be seen that the effects of the present invention are most favorable when the silver halide is of the core-shell type.

Example 2 In the same manner as in Example 1, photosensitive material sample No. 11 consisting of each layer as shown below was prepared.

1 Red-sensitized silver halide emulsion layer Red-sensitized silver iodobromide emulsion (average grain size 0.48 pm) containing 6 mol% silver iodide 1.40 g/m' (in terms of silver)
and 0.54 g of the first coupler exemplified compound (c-8)
/go and second coupler exemplified compound (C-9) 0.0
8g/go and 0.71g/go TCP and 2.0g
/ Red-sensitive silver halide emulsion layer containing silver gelatin.

2 protective layer 1.3/rn' of gelatin and 0.05 g/rn' of 2
．． A protective layer consisting of 4-dichloro-6-hydroxy-3-triazine sodium salt.

Next, in the photosensitive material sample No. 11, the additive A of Example 1 was added to the red-sensitive silver halide emulsion layer in the same manner as in Example 1.
, E was added as shown in Table 2. Photosensitive material sample No. 12-1
4 was created.

Further, photosensitive material sample No. 15 was prepared as shown in Table 2 by replacing the second coupler in the emulsion layer of photosensitive material sample No. 11 with exemplary compound (C-7) and adding additive A.

For comparison, photosensitive material sample No. 18 was prepared as shown in Table 2, using the first coupler alone and adding additive A. That is, the coupler in the emulsion layer of the photosensitive material sample No. 11 was as follows.

First coupler (c-8): 0.80 per mole of silver
g/go.

Further, photosensitive material samples Nos. 17 to 19 were prepared in which the amounts of the first coupler and second coupler in the emulsion layer of photosensitive material sample No. 11 were changed as shown in Table 2.

These light-sensitive material samples were treated in the same manner as in Example 1 and subjected to sensitometry. The results are shown in Table 2.

Below is a small margin l-・Value per 1 mole of silver (g/m'') 2・・Amount of additive: per 1 mole of silver, each listed value , x 50 l, 1000 times the standard deviation of the density, and the relative value is shown with photosensitive material sample No. 11 as 100.

For trees 4...S, the sensitivity is expressed as the reciprocal of the exposure amount that gives the fogging depth +0.1, and is expressed as a relative value with Sample No. 11 set as 100.

House 5...Fog represents fog.

t6...ΔFog indicates the amount of increase in fog after storage at 85° C. for 3 days.

Photosensitive material samples Nos. 17 to 19 had a significant increase in viscosity and were quite difficult to prepare, and the photosensitive material samples that were prepared also had significant curls and cracks, so a fair evaluation could not be made.

As is clear from the results in Table 2, the RMS was improved by using the first coupler and the second coupler together compared to the photosensitive material samples No. and lEi using only the first coupler (photosensitive material sample No. , 12 and 15), and the fog that occurs when the first coupler and the second coupler are used together, photosensitive material sample No. 13 containing conventional additives does not sufficiently reduce the fog. In photosensitive material sample No. 14 with an increased amount of additive, although the fog is reduced, the sensitivity is significantly lowered, and the fog also increases significantly during storage, so that no significant effect can be obtained compared to the photosensitive material sample without additives.

When the first coupler and the second coupler are used together and additive A is added as in the present invention (photosensitive material samples No. 12 and 15
), the fog is sufficiently reduced without reducing sensitivity, the degree of increase in fog due to storage is small, and there is no adverse effect on graininess.

Example 3 The following layers were sequentially coated on a cellulose triacetate film support to form multilayer color film photosensitive material samples No.
20 were created.

1st layer Antihalation Wj (HC layer) Antihalation layer containing black colloidal silver 0.18g/m' and gelatin.

2nd layer 1st isolation layer (10 layers) 2.5-di-t-octylhydroquinone 0.14. /
rn', dibutyl phthalate (referred to as DBP) 0.0
7 g/m' and a separating layer containing gelatin.

3rd layer Low-speed layer (RL layer) of red-sensitive silver halide emulsion layer Average grain size (F) 0.48JL layer, emulsion (emulsion-■) consisting of AgB r I containing 8 mol% of Agl is spectroscopy to red sensitivity. 1.4 g/g of the sensitized product (in terms of silver, the same applies hereinafter) and 54 g/L of the first coupler exemplified compound (c-8)
Example: 0.08 g of second coupler exemplified compound (C-9)
/Go, colored cyan coupler compound (CC) 0.08
g/m', TCPo, 71 g/m'' and the slow layer of the red-sensitive silver halide emulsion layer containing gelatin.

4th F# High-sensitivity layer of red-sensitive silver halide emulsion layer (R
H layer) A containing average particle size (F) 0.48 mol%, Agl 8 mol%
gB r I emulsion (emulsion -■) spectrally sensitized to red sensitivity, 0.7 g/m'', and the first coupler exemplified compound (c-4) 0.21 g/m'', TCPo, 21
g/m' and a red-sensitive silver halide emulsion layer containing gelatin.

5th layer 2nd isolation layer (2C4) Same as second layer.

No. 67j Low-speed layer of green-sensitive silver halide emulsion layer (G
L layer) 1.1 g/rn' of the emulsion spectrally sensitized to green sensitivity and 0.44 g of the first coupler exemplified compound (m-6)
/go, second coupler exemplified compound (M-16) 0.05
g/ba, colored magenta coupler compound (CM) 0
．． 12 g/m'', TCPo, 8 g/rn' and gelatin.

7th layer High-sensitivity layer (GH layer) of green-sensitive silver halide emulsion layer Emulsion - 0.9 g/rn of spectrally sensitized green-sensitive silver halide emulsion layer
' and the first coupler exemplified compound (m-2) 0.188
/ml, colored magenta coupler compound (CM) 0
．． 05g/m'', T CP 0.24g/tn2
and a high-speed layer of a green-sensitive silver halide emulsion layer containing gelatin.

8th layer 3rd isolation layer (3G layer) Yellow colloidal silver 0.09g/m'', 2.5-Gt-
Octyl hydroxide/yo, 14g/rn”, D
Isolation layer 9th layer containing B Po, 07g/tn” and gelatin Low-speed layer of blue-sensitive silver halide emulsion layer (BLi
t) The emulsion was spectrally sensitized to blue sensitivity with a density of 0.7 g/m''.
First coupler exemplified compound (y-3) 1.17 g/g, second coupler exemplified compound (Y-6) 0.12 g/
TCPo, 12 g/m'' and gelatin.

10th layer High-speed layer of blue-sensitive silver halide emulsion layer (BH
Layer) 0.5 g/m'' of emulsion ■ spectrally sensitized to blue sensitivity and 0.75 g of the first coupler exemplified compound (y-4)
/ln'', T CP O,08g/m' and a high-speed layer of a blue-sensitive silver halide emulsion layer containing gelatin.

11th layer Protective layer (PL layer) Protective layer containing gelatin.

In the photosensitive material sample No. 20, additive A in Example 1 was added to the 3rd, 6th, and 9th layer at a concentration of 1.8% per mole of silver.
A photosensitive material sample No. 21 was prepared in which 2.5 mol of additive E was added, and a photosensitive material sample No. 21 was prepared in which 2.5 mol of additive E was added in the same manner.
Create 22.

Furthermore, the second coupler was replaced with the first coupler in the 3rd, 6th, and 9th layers of the photosensitive material sample No. 20, and the photosensitive material sample No. 23 was prepared in which the additive A in Example 1 was added.

These light-sensitive material samples were processed in the same manner as in Example 1, and the results are shown in Table 3.

Margin Table 3 Part 1: RMS indicates an aperture diameter of 5p x 50m, 1000 times the standard deviation of density, and photosensitive material sample No.
, 20 is expressed as a relative value as 100.

t2...S indicates the sensitivity as the reciprocal of the exposure amount that gives the fog density +0.1, and is expressed as a relative value with Sample No. 20 set as 100.

Yo3...Fog represents fog.

4.ΔFoz indicates the amount of increase in fog after storage at 65° C. for 3 days.

As is clear from the results in Table 3, the combination of the first coupler and second coupler of the present invention and the additive of the present invention (
Light-sensitive material sample No. 21) had good graininess, no decrease in sensitivity, sufficiently reduced fog, and little increase in fog due to storage.

A good silver halide color photographic material was obtained.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Agent
Patent attorney Nobuaki Sakaguchi (and 1 other person)

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers comprises an oil droplet dispersion first coupler and a Fischer dispersion. contains a second coupler, and the silver halide emulsion layer and/or its adjacent layer contains at least one compound selected from the group of compounds represented by the following general formula [I], [II] or [III]. A color photographic material containing silver halide. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the above formula, R_1 ~R_3, R_5~R_7, R_1_
0 and R_1_1 each represent a hydrogen atom or an alkyl group, R_4 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, R_8 and R_9 each represent a hydrogen atom,
Represents an aliphatic group or a heterocyclic group, including the case where both R_8 and R_9 form a ring, provided that R_8 and R_9 do not have a hydrogen atom at the same time. R_1_2 represents a hydrogen atom, an alkyl group or a halogen atom.