JP2949196B2 - Silver halide color photographic materials - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material containing a novel phenol type cyan dye-forming coupler.

(Prior Art) A silver halide photographic light-sensitive material is exposed to light and then color-developed to react with a dye-forming coupler (hereinafter referred to as a coupler) as an oxidized aromatic primary amine developer to form a color image. You. Generally, in this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and light, yellow, magenta, and cyan color images having complementary colors are formed. A phenol derivative or a naphthol derivative is often used as a coupler for forming a cyan image. In color photography, a color-forming coupler is added to a developer or incorporated in a light-sensitive photographic emulsion layer or other color image-forming layer to form an oxidized color developer formed by development. Reacts to form non-diffusible dyes.

The reaction between the coupler and the color developing agent is carried out at the active site of the coupler.
Equivalent couplers, i.e. those which require stoichiometrically 4 moles of silver halide with development nuclei to form 1 mole of dye. On the other hand, those having a group capable of leaving as an anion at the active site are 2-equivalent couplers, that is, couplers which require only stoichiometrically 2 moles of silver halide having a development nucleus to form 1 mole of dye. And
Therefore, in general, the amount of silver halide in the photosensitive layer can be reduced and the film thickness can be reduced with respect to the 4-equivalent coupler, so that the processing time of the photosensitive material can be shortened and the sharpness of the formed color image is further improved.

By the way, among the cyan couplers, the naphthol type coupler has a sufficiently long absorption of the formed dye image and a small overlap with the absorption of the magenta dye image at a long wavelength, and has a low coupling reactivity with an oxidized form of a color developing agent. Since it can be selected as high as possible, it has been widely used for photographic applications, mainly for color negative films. However, dye images obtained from naphthol type couplers tend to be reduced by divalent iron ions accumulated in a fatigued bleaching bath or bleach-fixing bath (referred to as reduction fading) and have poor heat fastness. , Improvement was strongly desired.

On the other hand, US Pat. No. 4,333,999 discloses that p-
A phenolic cyan coupler having a cyanophenylureido group and a carboxamide group at the 5-position, which is a ballast group (diffusion resistance-imparting group), is disclosed. These couplers are deeply shifted by the association of dyes in a film to give a dye image having an excellent hue, and since they are excellent in fastness, they are widely used as couplers in place of the naphthol type cyan coupler. Is starting to be.

(Problems to be Solved by the Invention) However, in recent years, the performance requirements for photographic light-sensitive materials are intense, and even with these couplers, higher coupling reactivity and higher dye absorption density are continuously required.

Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material containing a cyan coupler which gives high coupling reactivity and high dye absorption density.

(Means for Solving the Problems) The present inventors have conducted intensive studies to achieve the above objects (objects), and as a result, have found that the following objects can be achieved in the following silver halide color photographic materials. Was.

That is, a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, comprising at least one cyan dye-forming coupler represented by the following formula (I): Achieved by silver halide color photographic materials.

(In the formula, R ¹ represents a substituted or unsubstituted alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, R ²
Is a group that can be substituted on the benzene ring, R ³ is a substituted or unsubstituted aryl group, Z is a hydrogen atom or a coupling-off group, Q is an oxygen atom or —NR ⁰ , and R ⁰ is the same as R ¹ Represents an integer of 0 to 4, respectively. Hereinafter, the cyan coupler represented by formula (I) will be described in detail. In the plate type (I), R ¹ , R ⁰
Is preferably 1 to 36 carbon atoms (hereinafter referred to as C number).
(More preferably 6 to 24) linear or branched alkyl group, C 2 to 36 (more preferably 6 to 25) linear or branched alkenyl group, C 3 to 36 (More preferably 6 to 24) a 3- to 12-membered cycloalkyl group or an aryl group having a C number of 6 to 36 (more preferably 6 to 24), which is a substituent (for example, a halogen atom, a hydroxyl group, a carboxyl group) Group, sulfo group, cyano group, nitro group, amino group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group An acyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, A sulfamoyl group, a ureido group, an alkoxycarbonylamino group, a sulfamoylamino group, an alkoxysulfonyl group, an imide group or a heterocyclic group, which is referred to as a substituent group A). R ¹ is preferably linear, branched or substituted (alkoxy, alkylthio, aryloxy,
An alkyl group having an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group, an alkoxycarbonyl group, an epoxy group, a cyano group or a halogen atom (for example, n-octyl, n-decyl, n-dodecyl, n-hexadecyl, -Ethylhexyl, 3,5,5-
Trimethylhexyl, 3,5,5-trimethylhexyl, 2
-Ethyl-4-methylpentyl, 2-hexyldecyl,
2-heptylundecyl, 2-octyldodecyl, 2,4,
6-trimethylheptyl, 2,4,6,8-tetramethylnonyl, benzyl, 2-phenethyl, 3- (t-octylphenoxy) propyl, 3- (2,4-di-t-pentylphenoxy) propyl, 2 -(4-biphenyloxy) ethyl, 3-dodecyloxypropyl, 2-dodecylthioethyl, 9,10-epoxyoctadecyl, dodecyloxycarbonylmethyl, 2- (2-naphthyloxy) ethyl), unsubstituted or substituted An alkenyl group (e.g., a halogen atom, an aryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group or an alkoxycarbonyl group) (e.g., allyl, 10-undecenyl, oleyl, citronellyl, cinnamyl), unsubstituted or Halogen atom, alkyl group, cycloalkyl group, aryl group, alcohol A cycloalkyl group (e.g., cyclopentyl, cyclohexyl, 3,5-dimethylcyclohexyl, 4-t-butylcyclohexyl) or an unsubstituted or substituted group (halogen atom, alkyl group, alkoxy group, alkoxy group) An aryl group having a carbonyl group, an aryl group, a carbonamido group, an alkylthio group or a sulfonamido group [eg, phenyl, 4-dodecyloxyphenyl, 4-biphenylyl, 4-dodecanesulfonamidophenyl, 4-t-octylphenyl, -Pentadecylphenyl], particularly preferably the straight-chain,
It is a branched or substituted alkyl group.

R ² in the general formula (I) is a group capable of being substituted on a benzene ring, preferably a group selected from among the substituent group A, but when a plurality, R ² is optionally substituted by one or more identical You may. R ² is more preferably a halogen atom (F,
Cl, Br, I), an alkyl group having 1 to 24 carbon atoms (eg, methyl, butyl, t-butyl, t-octyl, 2-dodecyl), a cycloalkyl group having 3 to 24 carbon atoms (eg, cyclopentyl, cyclohexyl), A C1-24 alkoxy group (e.g., methoxy, butoxy, dodecyloxy, benzyloxy, 2-ethylhexyloxy, 3-dodecyloxypropoxy, 2-dodecylthioethoxy, dodecyloxycarbonylmethoxy), a C2-24 carboxyl An amide group (for example, acetamido, 2-ethylhexaneamide, trifluoroatomido) or a C1-24 sulfonamide group (for example, methanesulfonamide, dodecanesulfonamide, toluenesulfonamide).

In general formula (I), it is preferably an integer of 0 to 2, more preferably 0 or 1.

In the general formula (I), R ⁴ preferably represents an aryl group having a C number of 6 to 36, more preferably 6 to 15, and even if it is substituted with a substituent selected from the substituent group A, a fused ring It may be. Here, preferable substituents include a halogen atom (F, Cl, Br, I), a cyano group, a nitro group, an acyl group (eg, acetyl, zenzoyl), and an alkyl group (eg, methyl, t-butyl, trifluoromethyl, trichloro). Methyl), an alkoxy group (eg, methoxy, ethoxy, butoxy, trifluoromethoxy), an alkylsulfonyl group (eg, methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), an arylsulfonyl group (eg, phenylsulfonyl, p-tolylsulfonyl, p- Chlorophenylsulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butoxycarbonyl), sulfonamide groups (eg, methanesulfonamide, trifluoromethanesulfonamide,
Triene sulfonide), carbamoyl group (eg, N,
N-dimethylcarbamoyl, N-phenylcarbamoyl) or a sulfamoyl group (eg, N, N-diethylsulfamoyl, N-phenylsulfamoyl). R ³ is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group, and more preferably 4-cyano. Phenyl, 4-cyano-3-halogenphenyl, 3-cyano-4-halogenphenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-
3-halogenophenyl, 4-alkylsulfonyl-3-
Alkoxyphenyl, 3-alkoxy-4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-
Dicyanophenyl, 3-cyano-4,5-dihalogenophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl, 3-cyano-4-halogenophenyl, 4-cyano -3-halogenophenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula (I), Z represents a hydrogen atom or a coupling leaving group (including a leaving atom; the same applies hereinafter). Preferred examples of the coupling-off group include a halogen atom,-
OR ⁴ , −SR ⁴ , -OSO ₂ R ⁴ , -NHCOR ⁴ , An arylazo group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms and bonding to a coupling active site (position to which Z is bonded) with a nitrogen atom (for example, succinimide, phthalimide,
Hydantoinyl, pyrazolyl, 2-benzotriazolyl) and the like. Here, R ⁴ is an alkyl group having 1 to 36 C, an alkenyl group having 2 to 36 C, a cycloalkyl group having 3 to 36 C, an aryl group having 6 to 36 C, or a C having 2 to 36 C.
And these groups may be substituted with a substituent selected from the group A. Z is more preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group or an alkylthio group, particularly preferably a hydrogen atom, a chlorine atom, a group represented by the following general formula (II) or a group represented by the following general formula (III) It is a group represented.

(Wherein, R ⁵ is a halogen atom, a cyano group, a nitro group, an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamide group, a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group Or a carboxyl group, and m represents an integer of 0 to 5. When m is plural,
R ⁶ may be the same or different. ) (Wherein, R ⁶ and R ⁷ are each a hydrogen atom or a monovalent group, and Y is Or R ⁸ and R ⁹ are a hydroxyl group, an alkyl group,
An aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group or a substituted or unsubstituted amino group is represented by n
Represents an integer of 1 to 6. Here, when n is plural May be the same or different. In the general formula (II), R ⁵ is preferably a halogen atom, an alkyl group (eg, methyl, t-butyl, t-octyl, pentadecyl), an alkoxy group (eg, methoxy, n-butoxy, n-octyloxy, benzyl) Oxy, imethoxyethoxy), a carbonamide group (eg, acetamido, 3-carboxoxypropanamide) or a sulfonamide group (eg, methanesulfonamide, toluenesulfonamide, p-dodecyloxybenzenesulfonamide), and particularly preferably. It is an alkyl group or an alkoxy group. m is preferably an integer of 0 to 2,
More preferably, it is an integer of 0 or 1.

In the general formula (III), when R ⁶ and / or R ⁷ represents a monovalent group, preferably an alkyl group (for example, methyl, ethyl, n-butyl, ethoxycarbonylmethyl,
Benzyl, n-decyl, n-dodecyl), aryl group (eg, phenyl, 4-chlorophenyl, 4-methoxyphenyl), acyl group (eg, acetyl, decanoyl,
Benzoyl, pivaloyl) or a carbamoyl group (eg, N-ethylcarbamoyl, N-phenylcarbamoyl), and R ⁶ and R ⁷ are more preferably a hydrogen atom, an alkyl group or an aryl group. In the general formula (III), Y is preferably And more preferably It is. In formula (III), R ⁸ is preferably an alkyl group, an alkoxy group, an alkenyloxy group, an aryloxy group or a substituted or unsubstituted amino group, and more preferably an alkoxy group or a substituted or unsubstituted amino group.

In the general formula (III), n preferably represents an integer of 1 to 3, and more preferably 1.

Q represents an oxygen atom or -N- ^R0 .

Hereinafter, in the general formula (I) The following shows a specific example.

Examples of R ³ in formula (I) are shown below.

Examples of Z in the general formula (I) are shown below.

When Z is a coupling-off group, it preferably does not contain a photographically useful group (for example, a development inhibitor residue, a dye residue).

The cyan coupler of the present invention represented by the general formula (I) can be synthesized by various synthesis routes, and typical synthesis routes are shown below.

Here, R is a methyl group or an ethyl group.

Compound Is an anthranilic acid ester Can be synthesized by the diazotization reaction (New Experimental Chemistry Lecture Vol.
14, p.1564, Maruzen). Subsequently, sulfur dioxide is allowed to act in the presence of a catalytic amount of cupric chloride. Is obtained. The reaction solvent includes water and acetic acid. The reaction temperature is preferably around 0 ° C.

Reaction with alcohol or amine Can be synthesized. At this time, it is preferable to use a base such as pyridine, triethylamine, diazabicycloundecene and diazabicyclononane. Examples of the reaction solvent include pyridine, triethylamine, water, acetone, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, and N, N-dimethylimidazolin-2-one.

Lead to. In general, an aqueous solution of an inorganic base such as an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, or an aqueous solution of sodium carbonate is used. As the reaction solvent, a water-miscible solvent such as water, methanol, ethanol, or tetrahydrofuran is selected. The reaction temperature is usually 20 ° C to 100 ° C, preferably 0 ° C to 80 ° C.

For induction of the reaction, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, oxalyl chloride and the like are used. The reaction is carried out without solvent, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N, N-dimethylformamide, N, N
-In a solvent such as dimethylacetamide. The reaction temperature is generally -20C to 150C, preferably -10C to 80C.

Compound Are U.S. Pat.No.4,333,999, JP-A-60-35731, and JP-A-61-35731.
It can be synthesized by the synthesis methods described in JP-A Nos. 2757, 61-42658 and 63-208562.

Reaction without solvent or in a solvent such as acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolin-2-one, usually at -20 ° C to 150 ° C
C., preferably in the temperature range from -10.degree. C. to 80.degree. As a result, a weak base such as pyridine, imidazole, N, N-dimethylaniline may be used.

The cyan coupler represented by the general formula (I) is 4 Can also be synthesized by a direct dehydration condensation reaction of As the condensing agent, N, N'-dicyclohexylcarbodiimide, carbonyldiimidazole and the like are used.

Hereinafter, specific examples of the coupler of the present invention are shown, but the present invention is not limited thereto.

In the present invention, the cyan coupler is usually used in an amount of 0.002 to 2 mol, preferably 0.01 to 1 mol, per 1 mol of the photosensitive silver halide. The coating amount per square meter is from 0.01 to 5 mmol, preferably from 0.1 to 2 mmol.

The cyan coupler of the present invention can be introduced into a light-sensitive material by an oil-in-water dispersion method. A high boiling organic solvent having a weight ratio of 2.0 to zero with respect to the coupler can be used. Preferably 1.0
A low to high boiling organic solvent can be used, and even a small amount of high boiling organic solvent of 0.1 to zero can be dispersed stably as compared with other similar-structure cyan couplers. A feature of the color photographic light-sensitive material of the present invention is that a stable dispersion can be obtained without using a high boiling point organic solvent.

In the present invention, the following solvents can be used as the coupler solvent. For the cyan coupler, phthalic acid esters (for example, dibutyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, ethyl phthalyl ethyl glycolate and the like) can be used. ), Fatty acid ester agents (eg, 2-ethylhexyl tetradecanoate, di-2
-Ethylhexyl adipate, di-2-ethylhexyl sebacate, 2-ethylhexyl-9,10-epoxystearate, benzoates (eg, 2-ethylhexyl benzoate, dodecyl benzoate, hexadecyl-4-hydroxybenzoate, etc.), phenol (E.g., 2,4-di-t-bentylphenol, 2,4-dinonylphenol, 2,4-dodecylphenol, etc.),
And chlorinated paraffins (for example, having a chlorine content of 40 to 70)
High boiling organic solvents, such as (wt.% Paraffins) are preferred.

The cyan coupler of the present invention can be used in any of a photosensitive emulsion layer, a non-photosensitive emulsion layer, and an intermediate layer.
It is preferable to use it by adding it to the photosensitive emulsion layer, and it is more preferable to use it by adding it to the red-sensitive emulsion layer.

The cyan coupler of the present invention may be used alone as a cyan coupler, or may be used in combination with another cyan coupler. Preferred cyan couplers that can be used in combination include a 1-naphthol type cyan coupler and a 5-amide-1-naphthol type cyan coupler (US Pat. No. 690,89).
No. 9, described in JP-A-64-78252), 2-ureidophenol type cyan coupler (described in JP-A-64-2044), and the like.

The coupler of the present invention can be applied to, for example, color paper, color reversal paper, color positive film, color negative film, color reversal film, and color direct positive photosensitive material. Particularly, application to a color negative film is preferable.

The silver halide emulsion of the light-sensitive material used in the present invention,
Any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride can be used.

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 distribution of the halogen composition 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. (Shell) [Layer-sided or multi-layered] grains having a so-called laminated side structure having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface (edges of grains when present on the grain surface, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is free to use one of the latter two particles rather than particles having a uniform structure, which 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, the boundary may be 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.

The halogen composition varies depending on the type of photosensitive material to be applied. For example, a silver chlorobromide emulsion system is mainly used for a printing material such as color paper, and a silver iodobromide emulsion system is mainly used for a photographic material such as a color negative. A system is 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%.

4. Such a high silver chloride emulsion preferably has a structure in which a silver bromide localized layer 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%. And these localized layers
It can be inside the grain, at the edge of the grain surface, at the corner or on the plane. One preferred example is that grown at the corner of the grain by epitaxial growth.

The average grain size of the silver halide grains used in the present invention (in the case of spherical or nearly spherical grains, the grain diameter is used; in the case of cubic grains, the ridge length is used as the grain size, and the average is based on the projected area. Is also expressed in terms of sphere.) Is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. Although the grain size distribution may be narrow or wide, the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation) is within 20%, particularly preferably 15%. % Of the so-called monodispersed silver halide emulsion is preferably used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in an emulsion layer having substantially the same color sensitivity (the monodispersity is defined as (Preferably those having a variation rate) can be mixed in the same layer or tandemly applied to another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The shape of the silver halide grains used in the present invention is regular such as cubic, octahedral, rhombodecahedral, and tetradecahedral.
It may have a crystalline form or coexist with them, may have an irregular crystalline form such as a sphere, or may have a complex form of these crystalline forms. Further, tabular grains may be used.

The silver halide photographic emulsion that can be used in the present invention is described, for example, in Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparatio
n and types) ”, and No. 18716 (November 1979), 64
8 pages, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et Phisique Photograh
ique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Daffin, published by Focal Press (GFDuffin, Photograhic).
Emulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikuman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photo).
grahic Emuldion. Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gatoff, Gutoff, Photographic Science and Engineerin.
g), 14, 248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure.Also, silver halides having different compositions are joined by epitaxial bonding. And it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives which can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,428,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 3,968, 4,314,023, 4,511,649, and EP 249,473A.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-35
No. 730, No. 51-118034, No. 60-185951, U.S. Pat.
Particularly preferred are those described in 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795.

As the cyan coupler that can be used in combination in the present invention,
Phenol type and naphthol type couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, and 4,228,23
No. 3, 4,296,200, 2,369,929, 2,801,1
No. 71, No. 2,772,162, No. 2,895,826, No. 3,772,
No. 002, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication No. 3,329,729, European Patent No. 121,
No. 365A, No. 249,453A, U.S. Pat.No. 3,446,622, No. 4,333,999, No. 4,775,616, No. 4,451,559,
No. 4,427,767, No. 4,690,889, No. 4,254,212
And Nos. 4,296,199 and JP-A-61-42658 are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No.17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye precursor capable of forming a dye by reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having a group as a leaving group.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, UK Patent No. 2,
No. 102,173, etc.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents described in JP-A-57-151944 and JP-A-57-154234
No., No. 60-184248, No. 63-37346, No. 63-37350,
Those described in U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

Others, couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427 and the like, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
185950, JP-A-62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR
Coupler releasing redox compounds or DIR redox releasing redox compounds, EP 173,302A, EP 31
3,308A, couplers for releasing dyes that recolor after release, RD Nos. 11449, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, U.S. Pat.No. 4,553,477
And the like, and a ligand releasing coupler described in JP-A-63-75747.
US Patent No.
Couplers that release a fluorescent dye described in 4,774,181 are exemplified.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. Also, a latex dispersion method as one of the polymer dispersion methods,
Specific examples of effects and latexes for impregnation are described in U.S. Pat.
No. 9,363, West German Patent Application (CLS) Nos. 2,541,274 and 2,541,230, etc., the dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO / 00723.

Examples of the high boiling point organic solvent used in the above-described oil-in-water dispersion method include alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate) and phosphates (such as diphenyl phosphate, triphenyl phosphate, and tricresyl phos- phate). Phosphate, dioctyl butyl phosphate, citrate (eg, tributyl acetyl citrate), benzoates (eg,
2-ethylhexyl benzoate, 2-ethylhexyl 2,4-dichlorobenzoate, alkylamides (eg, diethyl laurylamide), fatty acid esters (eg, dibutoxyethyl succinate, di-2-ethylhexyl succinate, tetradecanoic acid 2) Hexyldecyl, tributyl citrate, diethyl azelate), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic esters (for example, tributyl trimesate), etc., or a boiling point of about 30 ° C. to 150 ° C. Organic solvents, for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate and the like.

The standard amount of the color coupler that can be used in combination is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, and preferably 0.01 to 1 mol for the yellow coupler.
0.5 mol, 0.003 to 0.3 mol for magenta coupler,
Alternatively, the amount is 0.002 to 0.3 mol for a cyan coupler.

In the color light-sensitive material of the present invention, JP-A-63-25774
1, 2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro, 3,5-dimethylphenol described in JP-A-62-272248 and JP-A-1-80941. It is preferable to add various preservatives or fungicides such as 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The photographic light-sensitive material used in the present invention is coated on a rigid support such as a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), flexible support such as paper or glass. For details on the support and coating method, see Research Day Closure, Vol. 176, Item 17643, Section XV (p.2
7) It is described in Section XVII (p.28) (December 1978).

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

Specific examples of organic brown inhibitors are described in the following patent specifications.

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 52-152225, etc. 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.
Nos. 52-6623 and the like, gallic acid derivatives, methylenedioxybenzenes and aminophenols are disclosed in U.S. Pat.Nos. 3,457,079 and 4,332,886, respectively, and JP-B-56-21144.
No. 3,336,135 U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,
Nos. 354,313, 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846, and JP-A-59-78344, and metal complexes are disclosed in U.S. Pat.Nos. 4,050,038 and 4,241,5
No. 5, British Patent No. 2,027,731 (A), and the like. 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 in 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 cinnamic acid ester 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.
3,700,455) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin can be used freely, 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 developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as this color developing agent, but p-
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N, -diethylaniline and 3-methyl-4-amino-N-ethyl-.
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxyamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazites, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Preservatives such as phenols, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, sodium boron hydride and the like. Fogging agent, 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone and 1-phenyl-3-.
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 2. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the photographic material, and 500 ml by reducing the bromide ion concentration in the replenishing solution.
It can also be: When the replenishment amount is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing before bleach-fixing or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (VI) and copper (II), persalts, quinones, nitro compounds and the like are used.
Typical bleaching agents are pheiliocyanide; dichromic hydrochloric acid; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropane. Aminopolycarboxylic acids such as tetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; and nitrobenzenes can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid, such as iron (III) complex salt of ethylenediaminetetraacetate, and persulfate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fix obtained using these aminopolycarboxylic acid iron (III) complex salts is usually
5.5 to 8, but lower p for faster processing
H can also be processed.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleaching accelerators are described in the following specification: U.S. Pat. No. 3,893,959, West German Patent 1,290,812, JP-A-53-1983.
No. 95630, Research Disclosure No. 17,129 (July, 1978); compounds having a mercapto group or a disulfide bond; thiazolidine derivatives described in JP-A-50-10129; U.S. Pat. No. 3,706,561 Described thiourea derivatives; iodide salts described in JP-A-56-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; Can be used. Of these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are compounds described in U.S. Pat. No. 3,893,858, West Patent No. 1,290,812, and JP-A-53-95630. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fixing, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Also, isothiazolone compounds, thiabendazoles, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A-57-8542, Hiroshi Horiguchi, "Bactericidal and antifungal chemistry," 1986
Year) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antimicrobial and Antifungal Society, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) A bactericide can also be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but are generally 20 seconds to 10 minutes at 15 to 45 ° C, and preferably 30 to 25 minutes at 25 to 40 ° C.
A range from seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Publication No.
All known methods described in JP-A Nos. -8543, 58-14834, and 60-220345 can be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can be added to the stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.Nos. 3,342,597, 3,342,599, Schiff base type compounds described in Research Disclosure 14,850 and 15,159, aldol compounds described in 13,924, and U.S. Pat. And urethane compounds described in JP-A-52-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

EXAMPLES Next, the effects of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 On an undercoated cellulose triacetate support, monochromatic photosensitive materials (samples 101 to 128) comprising an emulsion layer and a protective layer were prepared with the following composition. Values are expressed in g / m ² except for couplers. (Silver halide is expressed in terms of silver.) Emulsion layer Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.3 μm) Silver 0.8 Gelatin 1.2 Coupler (see Table 1) mol / m ² unit 0.001 Dibutyl phthalate 0.3 Protective layer Gelatin 0.9 Polymethyl methacrylate particles (1.5 μm in diameter) 0.4 Sodium 1-oxy-3,5-dichloro-s-triazate 0.04 Photosensitive material prepared in this manner (Sample 101 ~ 128)
Was cut into a size of 35 mm × 120 mm, exposed to white light having an exposure intensity of 40 cms using a wedge of continuous density, and then subjected to the following color development processing.

Color development processing (temperature 38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Fixing 4 minutes 20 seconds Rinse 5 minutes Stable 1 minute The composition of the processing solution used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g sodium sulfite 4.0 g potassium carbonate 30.0 g potassium bromide 1.4 g potassium iodide 1.3 mg hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino) 2-methylaniline sulfate 4.5 g Add water 1.0 pH 10.0 Bleaching solution Ferric ammonium 1,3-diaminopropanetetraacetate 105.0 g Aqueous ammonia 3.0 ml Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water 1.0 pH 4.2 Settled solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1.0 pH 6.6 Stable Liquid Formalin (40%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization ≒ 10) 03 g The sample (101-128) that developed cyan in the 1.0 standard color development process was added to the gamma value (gradient of the sensitometric curve) and Dmax (maximum color density) using Fuji-type density type (FDS). Was measured. The results are shown in Table 1. Each value is a sample
The relative value when the measured value of 101 was 1 was expressed.

Table 1 shows that when the compound of the present invention was used, γ and the maximum color density were obtained as compared with the case where the comparative coupler was used.

Further, when those represented by the general formulas (II) and (III) were used as the leaving groups, even better results were obtained.

Example 2 A multilayer silver halide photosensitive material having a photosensitive layer having the following composition coated on an undercoated cellulose triacetate support (sample
201-218).

(Composition of photosensitive layer) The numerical value corresponding to each component indicates a coating amount expressed in g / m ² , and for silver halide, it indicates a coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver silver 0.18 gelatin 0.90 2nd layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0Z002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 0.88 Third layer (first red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 coupler (see Table 2) 6.3 × 10 ^-4 (mol / m ² ) EX-10 0.020 HBS-1 0.060 Gelatin 0.73 Fourth layer (second red Emulsion layer) Emulsion G Silver 1.0 Sensitizing dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 Coupler (see Table 2) 7.5 × 10 ^-4 (mol / m ² ) EX-3 0.020 EV-4 0.030 EX-10 0.015 HBS-1 0.060 Gelatin 1.1 Fifth layer (third red-sensitive emulsion layer) Emulsion D Silver 1.60 Sensitizing dye I 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 EX-3 0.010 E X-4 0.080 EX-2 0.097 HBS-1 0.22 HBS-U 0.10 Gelatin 1.39 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.68 7th layer (1st green sensitive emulsion layer) Emulsion A silver 0.15 Emulsion B silver 0.15 sensitizing dye V 3.0 × 10 ^-5 sensitizing dye VI 1.0 × 10 ^-5 sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-2 0.010 gelatin 0.53 8th layer (second green-sensitive emulsion layer) Emulsion C silver 0.45 sensitizing dye V 2.1 × 10 ^-5 sensitizing dye VI 7.0 × 10 ^-5 sensitizing dye VII 2.6 × 10 ^-4 EX -6 0.094 EX-8 0.018 EX-7 0.026 HBS-1 0.160 HBS-3 0.008 Gelatin 0.43 Ninth layer (third green-sensitive emulsion layer) Emulsion E Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 sensitizing dye VII 3.0 × 10 ^-4 EX-13 0.015 EX-14 0.015 EX-11 0.100 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.31 Layer 10 (yellow filter layer) Yellow colloidal silver Silver 0.05 EX-5 0.08 HBS-1 0.03 Gelatin 0 .81 11th layer (first blue-sensitive emulsion layer) Emulsion A silver 0.08 Emulsion B silver 0.07 Emulsion F silver 0.07 sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.72 EX-8 0.042 HBS-1 0.28 gelatin 0.94 twelfth Layer (second blue-sensitive emulsion layer) Emulsion G silver 0.45 Sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.154 EX-10 0.007 HBS-1 0.05 gelatin 0.66 13th layer (third blue-sensitive emulsion layer) Emulsion H silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-15 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (first protective layer) Emulsion I Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 0.85 15th layer (Second protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) 0.54 S-1 0.20 Gelatin 1.02 In addition to the above components, gelatin hardener HI and a surfactant were added to each layer.

The prepared samples (201 to 218) were cut to a width of 35 mm and processed to give a red light wedge exposure.

Next, processing was carried out using a cine-type automobile developing machine according to the following processing prescription. However, the samples for which the performance was evaluated were processed after the samples subjected to imagewise exposure were processed until the cumulative replenishment amount of the developing solution became three times the mother liquor tank capacity.

The composition of the treatment liquid is shown below.

(Fixing solution) Common for mother liquor and replenisher (g) Diammonium ethylenediaminetetraacetate 1.7 Ammonium sulfite 14.0 Aqueous ammonium thiosulfate (700 g /) 340.0 ml Add water 1.0 pH 7.0 (wash water) Common for mother liquor and replenisher Tap water Water is passed through a mixed-bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH-type strong base type anion exchange resin (Amberlite IRA-400). And magnesium ion concentration of 3 mg / or less, followed by sodium dichloroisocyanurate 20 mg / sodium sulfate 150 mg
/ Was added. The pH of this solution was in the range of 6.5-7.5.

(Stabilizing Solution) mother liquor replenisher common (units g) Formalin (37%) 1.2 ml Surfactant 0.4 _{C 10 H 21 -0CH 2 CH 2} 10 H ] was added to ethylene glycol 1.0 Water 1.0 pH 5.0-7.0 development The samples (201 to 218) that developed color by the treatment were measured for red density using a Fuji densitometer. Table 2 shows sample 20
The density of each sample at the exposure amount given a density of 1.0 in 1 is shown.

From the results in Table 2, when the compound of the present invention was used,
It can be seen that high color developability can be obtained also in the multilayer photosensitive material.

(Effects of the Invention) As is clear from the above description, when the compound of the present invention is used, a photosensitive material having high coupling reactivity and high generation density can be obtained.

Example 3 A multilayer color photographic paper having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating preparation solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) To 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7), 27.2 cc of ethyl acetate and 8.2 g of the solvent (Solv-3) were added and dissolved, and the resulting 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: 8 mixture of 0.78 μm and 0.77 μm in average grain size) (silver molar ratio), the coefficient of variation in grain size distribution was 0.08 and 0.10, and each emulsion had 0 silver bromide. .
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 , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition.

Coating solutions 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 were used as spectral sensitizing dyes in each layer.

(Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion, or 2.5 × 10 ^-4 mol for small-size emulsion, respectively) (4.0 × 10 ^-4 mole for large-size emulsion and 5.6 × 10 ⁴ mole for small-size emulsion per mole of silver halide)
^-4 mol) and (Per mol of silver halide, 7.0 × 10 ^-5 mol for large-size emulsion and 1.0 × ^10-5 mol for small-size emulsion)
^-5 mol) (Per mole of silver halide, 0.9 × 10 ^-14 mole for large size emulsion, 1.1 × 1 for small size emulsion)
0 for ^-4 mol) red-sensitive emulsion layer, and the following compound was added per mol of silver halide 2.6 × 10 ^-3 mol.

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.

Dyes were added below the emulsion layer to prevent irradiation.

(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 [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (BxY 0.82 Color image stabilizer (Cpd1) 0.19 Solvent (Solv-3) 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 a mean grain size of 0.55 µm and a 0.33 µm 1: 3 mixture (Ag mole) ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, and each emulsion contained 0.8 mol% of ArBr locally on the grain surface.) 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 absorber (UV-1) 0.47 Anti-color mixing agent (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, having an average grain size of 0.58 μm and 0.45 μm 1: 4 mixture (Ag molar ratio) with a variation coefficient of grain size distribution of 0.09 and 0.11, AgBr for each emulsion
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.24 Color image stable (Cpd-6) 0.17 Color image stable (Cpd-7) 0.40 Color image stable ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 6th layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorbing (UV-1) 0.16 Color mixture prevention (Cpd-5) 0.02 Solvent (Solv-5) 0.08 7th layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Then, the compound (I-28) (I-30) (I-32) (I-34) (I-3) of the present invention was equimolar to ExC in the fifth red-sensitive layer.
A similar photosensitive material was prepared except that 6) was used.

First, each sample was exposed imagewise through an optical wedge. The sample obtained from the exposure was processed using a paper processor.
Continuous processing (running test) was carried out until replenishment of twice the tank capacity of color development in the next processing step.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Add water 1000ml pH ( 25 ° C) 6.0 Rinse solution (same for tank solution and replenisher) Deionized water (3ppm for calcium and magnesium respectively)
After the treatment, the same operation as in Example 2 was carried out. As a result, the coupler of the present invention exhibited improved color development and Dmax in the same manner as in Example 2.

Continuation of the front page (56) References JP-A-59-139031 (JP, A) JP-A-62-275262 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, characterized by containing at least one cyan dye-forming coupler represented by the following general formula (I). Silver halide color photographic light-sensitive material. (Wherein, R ¹ represents a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group or aryl group, R ² represents a group capable of being substituted on a benzene ring, and R ³ represents a substituted or unsubstituted aryl group. , Z is a hydrogen atom or a coupling-off group, Q represents an oxygen atom or -NR ^0, R ⁰ is the same group as R ^1, represents each an integer of 0 to 4.)