JP2860417B2 - 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, whereby an oxidized aromatic primary amine developer reacts with a dye-forming coupler (hereinafter referred to as a coupler),
A color image is formed. Generally, in this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan, which have complementary colors, respectively, are formed. A phenol derivative or a naphthol derivative is often used as a coupler for forming a cyan image. In color photography, the color-forming coupler is added to a developer or incorporated in a photosensitive photographic emulsion layer or other color image-forming layer and reacts with an oxidized form of a color developer formed by development. This forms a non-diffusible dye.

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 at a long wavelength and little overlap with the absorption of the magenta dye image, and has a low coupling reactivity with the oxidized 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, the performance requirements for photographic materials in recent years are severe, and even with these couplers, higher coupling reactivity and higher dye absorption density are continuously required.

JP-A-57-204544, JP-A-57-204545, and JP-A-1-204544
No. 172951 discloses a 2-arylureido group at the 2-position,
Phenol type cyan couplers each having a 5-position m-alkoxycarbonylbenzamide group are disclosed. However, the cyan couplers described in these documents did not meet the requirements for higher coupling reactivity and higher dye absorption density.

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, the present invention provides: (1) 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): A silver halide color photographic light-sensitive material, characterized by the general formula (I) (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. And Z represents a hydrogen atom or a coupling-off group, and l represents an integer of 0 to 4.) and (2) the silver halide emulsion layer has a silver chloride content of 90 mol% or more. The silver halide color light-sensitive material according to the above (1).

Hereinafter, the cyan coupler represented by formula (I) will be described in detail. In the general formula (I), R ¹ is preferably a linear or branched alkyl group having 1 to 36 (more preferably 6 to 24) carbon atoms, and 2 to 26 carbon atoms. (More preferably 6 to 24) linear or branched alkenyl groups, 3 to 36 C atoms (more preferably 6 to 24) 3 to 12 membered cycloalkyl groups or 6 C atoms
To 36 (more preferably 6 to 24) aryl groups,
These substituents (for example, halogen atom, hydroxyl group, carboxyl 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, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamino 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, arylthio, alkylsulfonyl, arylsulfonyl, aryl, alkoxycarbonyl, epoxy, cyano or Alkyl group having a halogen atom) [for example, n-octyl, n-decyl, n-dodecyl, n
-Hexadecyl, 2-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],
An unsubstituted or substituted alkenyl group (eg, a halogen atom, an aryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group or an alkoxycarbonyl group) [eg, allyl, 10-undecenyl, oleyl, citronellyl, cinnamyl], A cycloalkyl group having a substituent or a substituent (halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group or aryloxy group) [for example, cyclopentyl, cyclohexyl, 3,5-dimethylcyclohexyl,
4-t-butylcyclohexyl] or an unsubstituted or substituted group (halogen atom, alkyl group, alkoxy group,
An aryl group having an alkoxycarbonyl 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, 3-pentadecylphenyl], particularly preferably the above-mentioned linear, branched or substituted alkyl group.

In the general formula (I), R ² is a group that can be substituted on the benzene ring, and is preferably a group selected from the above-mentioned substituent group A. When 1 is plural, even if R ² is the same, It may be different. 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), and 3 to 24 carbon atoms. (E.g., cyclopentyl, cyclohexyl), an alkoxy group having 1 to 24 carbon atoms (e.g., methoxy, butoxy, dodecyloxy, benzyloxy, 2-ethylhexyloxy, 3-dodecyloxypropoxy, 2-dodecylthioethoxy, dodecyloxy) Carbonylmethoxy), a C2-24 carbonamide group (eg, acetamido, 2-ethylhexaneamide, trifluoroacetamide) or a C1-24 sulfonamide group (eg, methanesulfonamide, dodecanesulfonamide, toluenesulfonamide) ).

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

In the general formula (I), R ³ preferably represents an aryl group having a C number of 6 to 36, more preferably 6 to 15, and is a condensed ring even if it is substituted with a substituent selected from Substituent Group A. Is also good. Here, preferred substituents include a halogen atom (F, Cl, Br, I), a cyano group, a nitro group, an acyl group (eg, acetyl, benzoyl), 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, toluenesulfonamide), carbamo Il 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-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 3-cyano-4
-Halogenophenyl, 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 , 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 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, a cycloalkyl group having 3 to 36 carbon atoms, an aryl group having 6 to 36 carbon atoms, or 2 to 36 carbon atoms.
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.

General formula (II) (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
Represents an integer of 0 to 5. Here, when m is plural, R ⁵ may be the same or different. ) General formula (III) (Wherein, W represents an oxygen atom or a sulfur atom, preferably an oxygen atom. R ⁶ and R ⁷ each represent a hydrogen atom or a monovalent group, R ₈ and R ₉ each represent 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;
Represents an integer of up 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, benzyloxy) Methoxyethoxy), a carbonamide group (eg, acetamido, 3-carboxypropanamide) or a sulfonamide group (eg, methanesulfonamide, toluenesulfonamide, p-dodecyloxybenzenesulfonamide), particularly preferably an alkyl group or an alkoxy group. Group. m is preferably an integer of 0 to 2, more preferably 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 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.

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).

Specific examples of the cyan coupler represented by the general formula (I) are shown below. However, () shows the substitution position of R ² .

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

Compound b is synthesized by reacting phthalic anhydrides with alcohols or phenols. A reaction solvent may not be used, but a solvent such as ethyl acetate, acetonitrile, toluene, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide may be used. It is preferable to use a base in this reaction, and pyridine, p-dimethylaminopyridine, DA
BCO (diazabicyclooctane), triethylamine,
N-methylmorpholine, DBU (diazabicycloundecene), DBN (diazabicyclononene) and the like are preferred. Reaction temperature is -20 ° C to 200 ° C, preferably 0 ° C to 150 ° C
It is.

The derivation of b to c is thionyl chloride, phosphorus oxychloride,
Use phosphorus pentachloride, oxalyl chloride, etc. without solvent or methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N, N-dimethylformamide, N, N
The reaction is carried out in a solvent such as dimethylacetamide. The reaction temperature is generally -20C to 150C, preferably -10C to 80C.

Compound d is disclosed in U.S. Pat.No. 4,333,999, JP-A-60-35731.
Nos. 61-2757, 61-42658 and JP-A-63-20856.
It can be synthesized by the synthesis described in the specification of No. 2.

The reaction between c and d is carried out without solvent or with acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N'-dimethylacetamide, N,
In a solvent such as N'-dimethylimidazolin-2-one,
Usually, the reaction is carried out in a temperature range of -20 ° C to 150 ° C, preferably -10 ° C to 80 ° C. At this time, pyridine, imidazole, N, N
-A weak base such as dimethylaniline may be used. The cyan coupler represented by the general formula (I) can also be synthesized by a direct dehydration condensation reaction between b and d . At this time, N, N'-dicyclohexylcarbodiimide, carbonyldiimidazole or the like is used as a condensing agent.

Synthesis Example 1 Synthesis of Exemplified Coupler 1 18.6 g of dodecanol and 7.9 g of pyridine were dissolved in 100 ml of ethyl acetate, and 14.8 g of phthalic anhydride was added at room temperature with stirring. After stirring at 50 ° C. for 3 hours, the reaction solution was transferred to a separating funnel, washed twice with dilute hydrochloric acid, and concentrated.

The concentrate was dissolved in 50 ml of methylene chloride, 0.3 ml of N, N-dimethylformamide was added, and 13 g of oxalyl chloride was added dropwise with stirring at room temperature in about 30 minutes. After stirring for about 1 hour, the mixture was concentrated to obtain an oil of 2-dodecyloxycarbonylbenzoyl chloride.

24.2 g of 5-amino-2- [3- (4-cyanophenyl) ureido] phenol synthesized according to the synthesis method described in U.S. Pat. No. 4,333,999 was dissolved in 200 ml of N, N-dimethylacetamide, and the solution was dissolved at room temperature. Under stirring, 2-dodecyloxycarbonylbenzoyl chloride was added dropwise in about 30 minutes. After the addition, the mixture was stirred for 2 hours, and the reaction solution was transferred to a separating funnel. 500 ml of ethyl acetate was added, and the mixture was washed twice with dilute hydrochloric acid and then with an aqueous sodium hydrogen carbonate solution, and then dried over sodium sulfate. The ethyl acetate solution is concentrated to about 1/2, and the precipitated crystals are filtered and dried to obtain the desired exemplified coupler 5.
37.9 g was obtained. The melting point of this compound is 118-121 ° C,
The structure was confirmed by ¹ H NMR spectrum, mass spectrum and elemental analysis.

Synthesis Example 2 Synthesis of Illustrative Coupler 7 36.9 g of the desired exemplary coupler 7 was obtained in the same manner as in Synthesis Example 1 except that 24.2 g of 2-hexyldecanol was used instead of dodecanol of Synthesis Example 1. The melting point of this compound is 1
85-189 ° C., and the structure was confirmed by ¹ H NMR spectrum, mass spectrum and elemental analysis.

In the present invention, the cyan coupler is usually used in an amount of 0.002 to 0.3 mol, preferably 0.01 to 0.2 mol, per 1 mol of the photosensitive silver halide.

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, but phthalic acid ester-based, fatty acid ester-based, and chlorinated paraffin-based high-boiling organic solvents are preferable for the cyan coupler. The relative permittivity is preferably about 6.5 or less, preferably 6.5 to 5 measured at 25 ° C. and 10 kHz.
Of these, high boiling organic solvents are preferred. A phthalic acid ester of a long-chain alkyl alcohol having a relative dielectric constant of about 5.2 is preferable because the resulting hue has a long wavelength.

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.

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, but silver chlorobromide or silver chloride containing substantially no silver iodide is preferably used. it can. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less.

The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the distribution of the halogen composition inside the silver halide emulsion grains, a so-called uniform type grain having the same composition at any part of the silver halide grains, and a core (core) inside the silver halide grains and the same. A so-called laminated type particle having a different halogen composition from the surrounding shell (single layer or plural layers) or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, Particles having a structure in which different composition portions are joined on edges, corners, or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use any one of the latter two of the particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, the boundary between different portions in the halogen composition may be a clear boundary or an unclear boundary due to the formation of 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.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used as a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%, more preferably at least 95 mol%. Silver chloride content of 90
If it is less than mol%, the color development during rapid processing is significantly reduced,
Also, the color mixture becomes remarkable.

Such high silver chloride emulsions preferably have a structure in which a silver bromide localized layer is formed in a layered or non-layered form as described above on the inside and / or on the surface of silver halide grains.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized layers can be on the inside of the particle, on the edge, on the corner or on the surface of the particle. One preferable example is a layer grown epitaxially on the corner of the particle.

Average grain size of 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 multi-layer coated in 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), 648
Page, "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chemie et Phisique Photograhiq
ue, Paul Montel, 1967), "Photoemulsion 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,
Nos. 619, 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 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, No. 4,296,200, No. 2,369,929, No. 2,801,1
No. 71, No. 2772,162, No. 2,895,826, No. 3,772,0
No. 02, No. 3,758,308, No. 4,334,011, No. 4,327,
No. 173, West German Patent Publication No. 3,329,729, European Patent No. 121,36
No. 5A, No. 249,453A, U.S. Pat.No. 3,446,622, No.
No. 4,333,999, No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212,
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, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
And 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 (OLS) 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 88/00723.

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,
In the case of a cyan coupler, the amount is 0.002 to 0.3 mol.

In the color light-sensitive material of the present invention, JP-A-63-257747 is used.
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 the coating method, see Research Disclosure, Volume 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 anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples 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 the organic anti-fading agent are described in the specifications of the following patents.

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

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and 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 is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

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

The color 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-N-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, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazites, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane ), Organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers,
Cabraze such as sodium boron hydride, 1
An auxiliary developing agent 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 representative 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-pyrazolides 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 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. 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), peracids, quinones, nitro compounds and the like are used.
Representative bleaching agents are pheiliocyanides; dichromates; organic complexes of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diamino. Aminopolycarboxylic acids such as propanetetraacetic acid and glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; and nitrobenzenes can be used. Among these, iron (III) complex salts of aminopolycarboxylic acid such as ethylenediaminetetraacetic acid (III) complex salt and persulfate are preferable 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-fixing solution 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 bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-812.
No. 95630, Research Disclosure No. 17,129 (July 1978), etc .; compounds having a mercapto group or disulfide bond; thiazolidine derivatives described in JP-A-50-140129; US Pat. No. 3,706,561 Described thiourea derivatives; iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B No. 45-8836; Can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and particularly, U.S. Patent No. 3,893,
No. 858, West German Patent No. 1,290,812 and JP-A-53-95630 are preferred. No. 4,552,834.
The compounds described in (1) are also preferred. 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 of the bleach-fixing solution, 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 propagate, 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.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 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 Application Publication No.
All of the known methods described in Nos. 57-8543, 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 also be added to this 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-based compounds described in U.S. Pat. And urethane compounds described in JP-A-53-135628.

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 JP-A-58-144547.
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 A light-sensitive material (sample) composed of two layers, an emulsion layer and a protective layer, was formed on an undercoated cellulose triacetate support.
101 to 113) were prepared with the compositions shown below. Numerical values were expressed in g / m ² except for the coupler. Emulsion layer Silver iodobromide emulsion (2 mol% of silver iodide, average grain size of 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 Color light-sensitive material thus prepared (Sample 101) ~ 1
13) Using a continuous density wedge, exposure intensity 40 cms
, And the following standard color development processing was performed.

Standard 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 process 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 l pH10.0 Bleach solution Ferric ammonium propylenediaminetetraacetic acid 105.0 g Ammonia water 3.0 ml Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water 1.0 l pH4. 2 Fixer 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 l pH6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene -P-Monononyl phenyl ether (average degree of polymerization: ≒ 10) 0.3 g Water was added to 1.0 L A sample (101-113) that developed cyan in the standard color development process was measured using a Fuji densitometer (FSD). Gamma values (gradients of sensitometric curves) and Dmax (maximum color density) were measured. The results are shown in Table 1. Each value was expressed as a relative value when the measured value of the sample 101 was set to 1.

Table 1 shows that when the compound of the present invention was used, both the G value and Dmax were higher than when the comparative compound was used.

Example 2 A multilayer silver halide light-sensitive material (Sample 201) was prepared by coating a light-sensitive material having the following composition on an undercoated cellulose triacetate support.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount is expressed 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 0.34 2nd layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 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 (Example A) 0.38 EX-10 0.020 HBS-1 0.060 gelatin 0.73 4th layer (second red-sensitive emulsion layer) Emulsion G silver 1.0 sensitization Dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 coupler (Example A) 0.45 EX-3 0.020 EX-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 EX- 4 0.080 EX-2 0.097 HBS-1 0.22 HBS-2 0.10 Gelatin 1.39 Sixth Layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 1.68 Seventh Layer (first 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 ^-4 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-3 0.010 Gelatin 0.53 8th layer 2 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) milk Agent 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 12th 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 Layer 13 (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 methacrylate particles (diameter approx. 0.54 S-1 0.20 Gelatin 1.20 In addition to the above components, gelatin hardener H-1 and a surfactant were added to each layer.

Next, Samples 202 to 213 were prepared in which the couplers added to the third and fourth layers were changed as shown in Table 2. At this time, the coupler was added so that the coating amount per 1 m ² of the light-sensitive material was equimolar.

The prepared samples (201 to 213) were cut and processed into a width of 35 mm, and were subjected to red light wedge exposure.

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

Washing is a countercurrent method from (2) to (1).

 The composition of the treatment liquid is shown below.

(Washing water) Common to mother liquor and replenisher Tap water is replaced with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IRA-400). Water was passed through the packed mixed-bed column to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, followed by sodium diisocyanurate 20 mg / l and sodium sulfate 150 mg / l.
Was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common for mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Surfactant 0.4 [C ₁₀ H ₂₁ -OCH ₂ CH ₂ O ₁₀ H] Ethylene glycol 1.0 Add water 1.0 l pH 5.0- 7.0 The red density of each of the samples (201 to 213) developed by the development processing was measured using a Fuji densitometer. Table 3 shows the density of each sample at the exposure amount given the density of 2.00 in Sample 201.

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.

Example 3 Each sample was prepared in exactly the same manner as Sample No. 208 of Example 2 except that Coupler 8, 15, or 31 was used instead of Coupler 5, and the concentration was measured in the same manner.
The darkness values were 1.32, 1.29 and 1.22, respectively.

Example 4 (Preparation of Sample 401) A sample 401 having the following layer constitution was prepared on an undercoated cellulose triacetate film base. The first layer coating solution was prepared as follows.

(Preparation of First Layer Coating Solution) 0.81 g of cyan coupler (H), 0.2 g of sodium dodecylbenzenesulfonate, and 0.5 c of dibutyl phthalate
c was completely dissolved in 10 cc of ethyl acetate. A 14% aqueous gelatin solution was added to the whole ethyl acetate solution of the coupler,
Emulsification and dispersion were performed with a homogenizer. After emulsification and dispersion, distilled water was added to make the total amount 100 g. 100 g of this emulsified dispersion and silver chlorobromide emulsion EM-1 were mixed and dissolved to prepare a first layer coating solution having the following composition. As a gelatin hardener, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

(Layer composition) Support Cellulose triacetate film First layer Chlorobromide emulsion 0.26 g / m ² gelatin in terms of silver 5.42 g / m ² Coupler 0.8 mmol / m ² Dibutyl phthalate 0.24 cc / m ² Protective layer Gelatin 1.55 g / m ² (Preparation of Samples 402 to 410) A sample was prepared in the same manner as in Sample 401 except that the coupler and the silver chlorobromide emulsion in Sample 401 were replaced as shown in Table 3. At this time, the couplers were replaced so as to be equimolar, and the emulsion was replaced so as to have the same weight in terms of silver. The halogen composition of the silver chlorobromide emulsion used is as follows.

EM-1 Cl = 80 mol%, Br = 20 mol% EM-2 Cl = 95 mol%, Br = 5 mol% (Treatment of sample and evaluation of color development) After the wedge exposure, a developing process was performed in the following process steps. Using a Fuji densitometer for the samples 401 to 410 after the development processing, the gradient of the gamma value sensitometry curve) and Dmax
(Maximum color density) was measured. The results are shown in Table 4. Note that each value was expressed as a relative value to the value of the sample 401.

Processing time Temperature Color development 30 ° C 45 seconds Bleaching and fixing 35 ° C 45 seconds Rinse 35 ° C 30 seconds Rinse 35 ° C 30 seconds Rinse 35 ° C 30 seconds Drying 80 ° C 60 seconds The composition of each processing solution is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 3.0 g Triethanolamine 8.0 g Potassium chloride 3.1 g Potassium bromide 0.015 g Potassium carbonate 25 g Hydrazinodiacetic acid 5.0 g N-ethyl-N- (Β-methanesulfonamidoethyl)-
3-methyl-4- aminoaniline sulfate 5.0 g Optical brightener (WHITEX-4 manufactured by Sumitomo Chemical) 2.0 g Add water 1000 ml pH (add potassium hydroxide) 10.05 Bleaching fixer Water 400 ml Ammonium thiosulfate solution ( 700 g / l) 100 ml ammonium sulfite 45 g iron (III) ammonium ethylenediaminetetraacetate 55 g ethylenediaminetetraacetic acid 3 g ammonium bromide 30 g nitric acid (67%) 27 g with water 1000 ml pH 5.8 rinse solution Ion exchange water (calcium and magnesium are 3 ppm each) Less than) From Table 4, it can be seen that the samples prepared according to the present invention show high color development during rapid processing.

Example 5 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied to form a layer structure shown below. Was produced. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) 27.2 cc of ethyl acetate and 4.1 g of each of the solvents (Solv-3) and (Solv-7) were added to 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7), and the mixture was dissolved. Emulsified dispersion A was prepared by emulsifying and dispersing in 185 cc of a 10% aqueous gelatin solution containing 8 cc of sodium benzenesulfonate. On the other hand, silver chlorobromide emulsion A (cubic, average grain size 0.88 μm
3: 7 of large size emulsion A and 0.70 μm small size emulsion A
Mixture (silver molar ratio). The variation coefficients of the grain size distribution were 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface in each size emulsion. In this emulsion, blue-sensitive sensitizing dyes A and B shown below were 2.0 × 10 ^-4 mol per mol of silver per mol of silver, and 2.5 × ^10-4 mol per mol of silver. 10 ^-4 mol is added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. At this time, samples 501 to 505 were prepared by changing the cyan coupler added to the fifth layer as shown in Table 4. As a gelatin hardener for each layer, 1-oxy-3,5
-Dichloro-s-triazine sodium salt was used.

The total amount of Cpd-10 and Cpd-11 in each layer was 25.0% each.
It was added to a mg / m ² and 50.0 mg / m ^2.

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

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

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

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

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

(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 emulsion layer) Silver chlorobromide emulsion A 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06 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 emulsion layer) Silver chlorobromide emulsion (cube, large size emulsion B having an average grain size of 0.55 μm) , A 1: 3 mixture (Ag molar ratio) with 0.39 μm small size emulsion B. The coefficient of variation of the grain size distribution was
0.10 and 0.08, each emulsion contains 0.8 mol% of AgBr locally in part of the grain surface) 0.12 Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer ( Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large emulsion C having an average grain size of 0.58 μm and small emulsion of 0.45 μm 1: 4 mixture (Ag mole ratio) with size emulsion C. Coefficient of variation of grain size distribution is 0.09 and 0.1.
11. In each size emulsion, 0.6 mol% of AgBr was locally contained in a part of the grain surface.) 0.23 Gelatin 1.34 Cyan coupler (see Table 4) Color image stabilizer (Cpd-2) 0.03 Color image stabilizer ( Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification)
17%) 0.17 Liquid paraffin 0.03 First, each sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The exposed samples were subjected to continuous processing (running test) using a paper processor using a solution having the following processing step and processing solution composition, until the replenishment was twice the tank capacity of color development. Process temperature Time Replenisher ^* Tank capacity Color development 35 ° C. 45 seconds 161 ml 17l blix 30-35 ° C. 45 seconds 215 ml 17l Rinse 30-35 ° C. 20 sec - 10l Rinse 30-35 ° C. 20 sec - 10l rinse 30-35 ° C. 20 sec 350 ml 10l drying 70 to 80 ° C. 60 seconds * replenishment rate is composition (3 and a tank countercurrent system. to rinse →) each processing solution per photosensitive material 1 m ² is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Add 40 g of ammonium bromide 1000ml pH (25 ℃) 6.0 Rinse solution (tank solution and replenisher are the same) Deionized water (Calcium and magnesium are 3ppm each
Next, the samples 501 to 505 were exposed to red light through a continuous-density optical wedge, and then developed with the processing solution prepared in the previous running test.

The maximum cyan density (Dmax R) and the maximum magenta density (Dmax G) were measured for the samples (501 to 505) that developed color in the development processing step. Table 5 shows the relative value of Dmax R of each sample when Dmax R of sample 501 was set to 1.00, and the value of Dmax G / Dmax R of each sample as the color mixing ratio.

From Table 5, it can be seen that the silver halide light-sensitive material according to the present invention provides an image having high maximum density and little color mixture even in a multilayer light-sensitive material.

(Effects of the Invention) From the above results, when the compound of the present invention is used, a silver halide color light-sensitive material having a high coupling reactivity and a high color-forming density can be obtained. This is remarkable when combined with an emulsion.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shuichi Sakai 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Inside Fujisha Shin Film Co., Ltd. 56) References JP-A-63-14146 (JP, A) JP-A-63-159848 (JP, A) JP-A-60-225155 (JP, A) JP-A-62-275262 (JP, A)

Claims (2)

(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. General formula (I) (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 represents a hydrogen atom or a coupling-off group, and l represents an integer of 0 to 4, respectively.) 2. A silver halide color light-sensitive material according to claim 1, wherein the silver chloride content in the silver halide emulsion layer is 90 mol% or more.