JPH0769589B2 - Image forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a reflective support such as color paper, which enables particularly rapid development processing. In addition, the present invention relates to a color photographic image forming method excellent in stability of a color image.

(Prior Art) Generally, the speed of color development differs depending on the type of the para-phenylenediamine derivative that is the color developing agent used,
In order to accelerate color development, N, N-diethyl-p-phenylenediamine sulfate or 3-methyl-4-amino-
N-alkyl substituted color developing agents such as N, N-diethylaniline hydrochloride have been used. However, although these have high developing activity and can speed up development, there is a problem in that the dark fading property of a color image after processing is poor.

Then, as a result of various studies, N-hydroxyalkyl-substituted p-phenylenediamine derivatives have been proposed as a color developing agent capable of rapid development (Japanese Patent Laid-Open No. 62-49350, 62).
-112156 and 62-49352). This developing agent is widely used in the development of color negative films and color reversal films, but in the case of color paper, which is a light-sensitive material having a reflective support, the dark fading is superior to that required for color negative films. In the present situation, development is carried out using a developing agent different from the above-mentioned developing agents because of the requirement for the properties. In other words, 4 for developing color paper
-Amino-3-methyl-N-methyl (β-methanesulfonamidoethyl) aniline sulfate is used, and although the dark fading is improved, the developing agent has a low developing activity and is generally a color accelerator. It is necessary to perform development in the coexistence of benzyl alcohol. However, the use of benzyl alcohol causes problems such as a decrease in solubility of the developing solution and an increase in stain after processing.

Therefore, at present, color paper can be processed rapidly,
Moreover, a treatment method with improved dark fading is not known.

On the other hand, as a method for improving the color image stability, a dispersion method using a coupler polymer has been developed. For example, a method of dissolving a hydrophobic substance such as an oil-soluble coupler in a water-miscible organic solvent in U.S. Pat.No. 4,203,716 and mixing the liquid with a loadable polymer latex to load the hydrophobic substance into the polymer is disclosed. It is disclosed. Further, JP-B-48-30494 does not use a high-boiling point coupler solvent, and instead, an organic solvent-soluble homopolymer of a hydrophobic monomer having a specific structure, or a hydrophilic monomer having a specific structure. Coupler dispersion using the above copolymer (the particle size of the dispersed particles is about 0.5 μ-5 μ)
A light-sensitive material containing is described. Furthermore, Japanese Patent Application Sho 61
-162813 also describes a dispersion method using a polymer in order to improve image fastness and the like. In addition, JP-A-52-
No. 102722 describes that the desilvering property is improved by a dispersion method using a polymer.

However, even for a light-sensitive material using such a polymer, color development with a color developing agent such as 4-amino-3-methyl-N-ethyl- (β-methanesulfonamidoethyl) aniline sulfate is sufficient. Not effective.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide an image forming method excellent in stability of a dye image of a silver halide color photographic light-sensitive material having a reflective support.

Further, the present invention uses a color developing agent having an excellent developing activity, has little stain after the processing even if a rapid color developing process is carried out, and a silver halide which gives a color photograph having an excellent dark fading property of a dye image. An object is to provide an image forming method for a color photographic light-sensitive material.

(Means for Solving Problems) As a result of various studies conducted by the present inventors to overcome the drawbacks of the conventional color photographic image forming method, the object of the present invention can be achieved by the following method. I found a thing.

That is, the present invention provides at least a diffusion-resistant oil-soluble coupler which forms a substantially non-diffusible dye on a reflective support by coupling with an oxidized product of an aromatic primary amine color developing agent. A silver halide color photographic light-sensitive material provided with a layer containing a dispersion of lipophilic fine particles containing one kind and at least one kind of water-insoluble and organic-solvent-soluble polymer is used as an N-hydroxyalkyl-substituted-p-phenylenediamine derivative. And a substantially no benzyl alcohol-containing color developing solution.

In the present invention, various polymers can be used as the water-insoluble organic solvent-soluble polymer contained in the lipophilic fine particles together with the specific oil-soluble coupler. this house,
It is preferable to use a water-insoluble and organic solvent-soluble polymer consisting of at least one repeating unit having no main chain or side chain acid group. A polymer having a bond is preferable from the viewpoints of the effect of improving color development and fading.

Further, in the present invention, the repeating unit having no acid group of the polymer is in its main chain or side chain. Or a repeating unit having no acid group of the polymer has a side chain (However, G ¹ and G ² each represent a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group).

The polymers used in the present invention are exemplified below.

(A) Vinyl Polymer As the monomer forming the vinyl polymer used in the present invention, acrylic acid esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl. Acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate,
Hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate , Methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate , 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxy polyethylene glycol acrylate (addition mole number n = 9)
1-Bromo-2-methoxyethyl acrylate, 1,1-
Examples thereof include dichloro-2-ethoxyethyl acrylate. In addition, the following monomers can be used.

Methacrylic acid esters; specific examples thereof include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec.
-Butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy)
Ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol mono Methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-
Propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy polyethylene glycol methacrylate ( Addition mole number n = 6), allyl methacrylate, methacrylic acid dimethylaminoethyl methyl chloride salt and the like can be mentioned.

Vinyl esters: Specific examples thereof are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate. Acrylamides: For example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide. , Diethyl acrylamide, β-cyanoethyl acrylamide, N- (2-acetoacetoxyethyl)
Acrylamide, diacetone acrylamide, etc .; Methacrylamides: for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-
Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N
-(2-acetoacetoxyethyl) methacrylamide and the like; olefins: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethyl. Butadiene, etc .; Styrenes:
For example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, etc .; Vinyl ethers: For example , Methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc .; Others: butyl crotonic acid, hexyl crotonic acid, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate , Diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone
Methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile, vinylidene chloride, methylene malon nitrile, vinylidene and the like can be mentioned.

As the monomers for forming the polymer used in the present invention (for example, the above-mentioned monomers), two or more kinds of monomers can be used as comonomers with each other according to various purposes (for example, solubility improvement). Further, in order to adjust the color developability and the solubility, a monomer having an acid group as shown below as a comonomer can be used as long as the copolymer does not become water-soluble.

Acrylic acid: Methacrylic acid: Itaconic acid: Maleic acid:
Monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc .; Monoalkyl maleate, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc .; citraconic acid; styrene sulfonic acid; vinylbenzyl sulfone Acid; vinyl sulfonic acid; acryloyloxyalkyl sulfonic acid, such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc .; methacryloyloxyalkyl sulfonic acid, such as methacryloyloxymethyl sulfonic acid, methacryloyloxyethyl Sulfonic acid, methacryloyloxypropyl sulfonic acid, etc .; acrylamidoalkyl sulfonic acid, such as 2-acrylic acid De-2-methyl-ethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2 and methyl butanoic acid; methacrylamide alkyl sulfonic acids, for example,
2-methacrylamido-2-methylethanesulfonic acid,
2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc .; these acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions.

When the hydrophilic monomers among the vinyl monomers listed above and other vinyl monomers (here, those that become water-soluble when made into a homopolymer) are used as comonomers, the copolymer is water-soluble. The ratio of the hydrophilic monomer in the copolymer is not particularly limited as long as it does not become acidic, but is usually preferably 40 mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less. is there. Further, when the hydrophilic comonomer copolymerized with the monomer for forming the polymer used in the present invention has an acid group, from the viewpoint of image storability as described above, in the copolymer of the comonomer having an acid group, Is usually 20 mol%
Hereafter, it is preferably 10% or less, and most preferably the case where such a comonomer is not contained.

The monomer forming the polymer used in the present invention is preferably a methacrylate type, an acrylamide type or a methacrylamide type. Further, it is usually preferable to copolymerize two or more kinds of monomers, and particularly preferable is a copolymer of an acrylamide monomer and another monomer of the present invention or a copolymer of a methacrylate monomer and another monomer. Is. Moreover, even if two or more kinds of polymers are used in combination,
Of course good.

(B) Polyester Resin Obtained by Condensing Polyhydric Alcohol and Polybasic Acid As the polyhydric alcohol, HO—R ₁ —OH (R ₁ is 2 to 2 carbon atoms
About 12 hydrocarbon chain, especially glycols having an aliphatic hydrocarbon chain) comprising structure or polyalkylene glycols are effective, polybasic _{acids, HOOC-R 2 -COOH (R} 2
Is a mere bond or has a hydrocarbon chain having 1 to about 12 carbon atoms).

Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol,
Isobutylene diol, 1,5-pentane diol, neopentyl glycol, 1,6-hexane diol, 1,7-heptane diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,4-diol, glycerin, diglycerin,
Examples thereof include triglycerin, 1-methylglycerin, erythritol, mannitol and sorbit.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid. Acids, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, methaconic acid, isohimmeric acid, cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc. To be

(C) Others Polyester obtained by, for example, the following ring-opening polymerization In the formula, m represents an integer of 4 to 7. The —CH ₂ — chain may be branched.

Suitable monomers that can be used to make this polyester include β-propiolactone, ε-caprolactone, dimethylpropiolactone, and the like.

In the present invention, these polymers are dissolved in an organic solvent together with at least one diffusion-resistant oil-soluble coupler, and mixed as a fine particle dispersion in the coating liquid. In this case, the procedure for dissolving the polymer in the organic solvent is not particularly limited, as long as the polymer and the coupler are contained in the fine particle dispersion.

In the present invention, as the organic solvent used for dissolving the polymer, a conventional high boiling point coupler solvent and an auxiliary solvent are appropriately used.

Examples of the auxiliary solvent include ethyl acetate, butyl acetate and methyl ethyl ketone.

The molecular weight and the degree of polymerization of the polymer used in the present invention have substantially no significant influence on the effect of the present invention, but as the molecular weight becomes higher, the problem that it takes time to dissolve in an auxiliary solvent, or the like,
Since the solution viscosity is high, it becomes difficult to emulsify and disperse, and coarse particles are generated, and as a result, problems such as a decrease in color developability and a cause of poor coatability are likely to occur. If a large amount of auxiliary solvent is used to reduce the viscosity of the solution as a countermeasure, a new process problem will occur. From the above viewpoint, the viscosity of the polymer is the polymer 3 per 100cc of the auxiliary agent used.
The viscosity when 0 g is dissolved is preferably 5000 cps or less, and more preferably 2000 cps or less. The molecular weight of the polymer usable in the present invention is preferably 150,000 or less, more preferably 80,000 or less, still more preferably 30,000 or less.

The ratio of the polymer used in the present invention to the co-solvent varies depending on the type of the polymer used, and varies over a wide range depending on the solubility in the co-solvent, the polymerization degree, the solubility of the coupler and the like. Usually, the amount required to have a sufficiently low viscosity so that a solution prepared by dissolving at least a coupler, a high-boiling coupler solvent and a polymer in an auxiliary solvent can be easily dispersed in water or a hydrophilic colloid aqueous solution. Co-solvent is used. Since the higher the degree of polymerization of the polymer, the higher the viscosity of the solution, it is difficult to uniformly determine the ratio of the polymer to the co-solvent regardless of the polymer species, but usually about 1: 1 to 1:50 ( The range of (weight ratio) is preferable.

Some specific examples of the polymer used in the present invention are shown below, but the present invention is not limited thereto.

Specific Example P-1 Polyvinyl acetate P-2 Polyvinyl propionate P-3 Polymethyl methacrylate P-4 Polyethyl methacrylate P-5 Polyethyl acrylate P-6 Vinyl acetate-vinyl alcohol copolymer (95:
5) P-7 poly n-butyl acrylate P-8 poly n-butyl methacrylate P-9 polyisobutyl methacrylate P-10 polyisopropyl methacrylate P-11 polyoctyl acrylate P-12 n-butyl acrylate-acrylamide copolymer (95 : 5) P-13 stearyl methacrylate-acrylic acid copolymer (90:10) P-14 1,4-butanediol-adipic acid polyester P-15 ethylene glycol-sebacic acid polyester P-16 polycaprolactone P-17 polypropyi Olactone P-18 polydimethylpropiolactone P-19 n-butyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) P-20 methyl methacrylate-vinyl chloride copolymer (7
0:30) P-21 methyl methacrylate-styrene copolymer (90:
10) P-22 methyl methacrylate-ethyl acrylate copolymer (50:50) P-23 n-butyl methacrylate-methyl methacrylate-styrene copolymer (50:30:20) P-24 vinyl acetate-acrylamide copolymer (85:15) P-25 vinyl chloride-vinyl acetate copolymer (65:35) P-26 methyl methacrylate-acrylonitrile copolymer (65:35) P-27 diacetone acrylamide-methyl methacrylate copolymer ( 50:50) P-28 methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) P-29 ethyl methacrylate-n-butyl acrylate copolymer (70:30) P-30 diacetone acrylamide-n-butyl acrylate Copolymer (60:40) P-31 Methyl Methacrylate-Styrene Methyl Methacrylate-Diacetone Acrylamide Copolymer (40:40:
20) P-32 n-butyl acrylate-styrene methacrylate-diacetone acrylamide copolymer (70:20:10) P-33 stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) P-34 Methyl methacrylate-styrene-vinyl sulfonamide copolymer (70:20:10) P-35 Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) P-36 n-butyl acrylate-methyl methacrylate-n-butyl methacrylate Rate copolymer (35:35:30) P-37 n-butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38: 38: 2
4) P-38 methyl methacrylate-n-butyl methacrylate-isobutyl methacrylate-acrylic acid copolymer (37: 29: 25: 9) P-39 n-butyl methacrylate-acrylic acid (95: 5) P-40 methyl methacrylate -Acrylic acid copolymer (9
5: 5) P-41 benzyl methacrylate-acrylic acid copolymer (90:10) P-42 n-butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (3
5: 35: 25: 5) P-43 n-butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (35:30:30) P-44 polypentyl acrylate P-45 cyclohexyl methacrylate-methyl methacrylate-n-propyl methacrylate Copolymer (37: 2
9:34) P-46 Polypentyl methacrylate P-47 Methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-48 Vinyl acetate-vinyl propionate copolymer (75:25) P-49 n -Butylmethacrylate-3-acryloxybutane-1-sodium sulfonate copolymer (97: 3) P-50 n-Butylmethacrylate-methylmethacrylate-acrylamide copolymer (35:35:30) P-51 n- Butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) P-52 n-butyl methacrylate-styrene copolymer (90:10) P-53 methyl methacrylate-N-vinyl-2-pyrrolidone copolymer Combined (90:10) P-54 n-Butyl Methacrylate-Vinyl Chloride Copolymer (90:10) P-55 n-Butyl Methacrylate-Styrene Copolymer (70:30) P 56 Poly (N-sec-butyl acrylamide) P-57 Poly (N-tert-butyl acrylamide) P-58 Diacetone acrylamide-methyl methacrylate copolymer (62:38) P-59 Polycyclohexyl methacrylate P-60 N- tert-butylacrylamide-methylmethacrylate copolymer (40:70) P-61 poly (N, N-dimethylacrylamide) P-62 poly (tert-butylmethacrylate) P-63 tert-butylmethacrylate-methylmethacrylate copolymer (70:30) P-64 poly (N-tert-butylmethacrylamide) P-65 N-tert-butylacrylamide-methylphenylmethacrylate copolymer (60:40) P-66 methylmethacrylate-acrylonitrile copolymer (70:30) P-67 methyl methacrylate-methyl vinyl ketone copolymer (38:72) P-68 methyl Methacrylate - styrene copolymer (75:
25) P-69 Methyl Methacrylate-Hexyl Methacrylate Copolymer (70:30) In the present invention, the above-mentioned water-insoluble and organic solvent-soluble polymer undergoes a coupling reaction with an oxidant of an aromatic primary amine developing agent. A diffusion-resistant oil-soluble coupler capable of forming a substantially non-diffusible dye is contained in the lipophilic fine particles. Examples of color couplers used here include naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (1
December 978) VII-D and the patent cited in 18717 (November 1979).

The coupler used in the present invention is preferably a coupler having a ballast group or polymerized to make it diffusion resistant. A two-equivalent color coupler in which a coupling active position is substituted with a leaving group is preferable to a four-equivalent color coupler having a hydrogen atom because the amount of coated silver can be reduced. Further, a DIR coupler which releases a development inhibitor or a coupler which releases a development accelerator upon coupling reaction can also be used.

Examples of the magenta coupler that can be used in the present invention include oil-protected type isazozolone type or cyanoacetyl type couplers, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole-based coupler, US Pat.
Pyrazolobenzimidazoles described in 9,879, preferably pyrazolo [5,1] described in U.S. Patent No. 3,725,067.
-C] [1,2,4] triazoles, pyrazolotetrazoles described in Research Declosure 24220 (June 1984) and Research Disclosure 24230 (1
Pyrazolopyrazoles described in Jun. 984). The imidazo compound described in European Patent 119,741 [1,2-
b] Pyrazoles are preferred, and the pyrazolo [1,5-b] [1,2,4] triazoles described in EP 119,860 are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers which are fast against temperature and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or higher at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan coupler, U.S. Pat.
No. 3,758,308, No. 4,126,396, No. 4,334,011, No.
4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Application Sho
2,5-diacylamino-substituted phenolic couplers described in 58-42671 and U.S. Pat.No. 3,446,622,
No. 4,333, 999, No. 4,451,559 and No. 4,427,7
Phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, such as those described in No. 67.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No. 2,1.
Specific examples of magenta couplers are described in 25,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a polymer of a duplex or more. Typical examples of polymerized dye formation are U.S. Pat.
4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the arrow coupler, 0.003 to 0.3 mol for the magenta coupler, and cyan coupler. Is 0.002 to 0.3 mol.

The couplers preferably used in the present invention are 2-equivalent couplers, the cyan couplers are represented by the general formulas (I) and (II), the magenta couplers are represented by (III) and (IV), and the yellow couplers are represented by (V).

In the general formulas (I) to (V), Y ⁷¹ , Y ⁷² , Y ⁷³ , Y ⁷⁴ or Y ⁷⁵ is a coupling leaving group (hereinafter referred to as a leaving group).
Wherein the leaving group is a coupling activated carbon with an oxygen, nitrogen, sulfur or carbon atom, and an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic / aromatic or heterocyclic sulfonyl group, an aliphatic group. A group that binds to an aromatic or heterocyclic carbonyl group, a nitrogen-containing heterocyclic group that connects to the coupling position with a nitrogen atom, a halogen atom, an aromatic azo group, etc., and an aliphatic group included in these leaving groups. , The aromatic or heterocyclic group may be substituted with a substituent permissible in R ⁷¹ (described later), and when two or more of these substituents are present, they may be the same or different. The group may further have a substituent that R ⁷¹ can accept.

In the general formulas (I) and (II), R ⁷¹ , R ⁷⁴ and R ⁷⁵ are each preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms (for example, Phenyl group, naphthyl group, etc.), heterocyclic group (eg, 3-pyridyl group, 2-furyl group, etc.), or aromatic or heterocyclic amino group (eg, anilino group, naphthylamino group, 2-benzothiazolylamino) Group, 2-pyridylamino group, etc.), and these groups further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyl group, an astel group,
Amide group, sulfamide group, imide group, ureido group, aliphatic or aromatic sulfonyl group, aliphatic or aromatic thio group, hydroxy group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. It may be substituted with a group.

In the present specification, the “aliphatic group” means a linear, branched or cyclic aliphatic hydrocarbon group, and is meant to include saturated and unsaturated groups such as alkyl, alkenyl and alkynyl groups.

In the general formula (I), R ⁷² preferably represents an aliphatic group having 1 to 20 carbon atoms, and may be substituted with a substituent that is allowed by R ⁷¹ .

R ⁷³ and R ^{76 in the} general formula (I) and the general formula (II)
Are each a hydrogen atom, a halogen atom, preferably an aliphatic group having 1 to 20 carbon atoms, preferably an aliphatic oxy group having 1 to 20 carbon atoms, or an acylamino group having 1 to 20 carbon atoms (for example, acetamide group, benzamide). Group, tetradecanamide group, etc.), these aliphatic groups, aliphatic oxy groups, and acylamino groups may be substituted with a substituent acceptable to R ⁷¹ .

In the general formula (I), R ⁷² and R ⁷³ may together form a 5- to 7-membered ring.

In the general formula (II), R ⁷⁵ and R ⁷⁶ may together form a 5- to 7-membered ring.

Independently by any one group of R ⁷¹ , R ⁷² , R ⁷³ or Y ^{71 in} the general formula (I) and any one group of R ⁷⁴ , R ⁷⁵ , R ⁷⁶ or Y ^{72 in} the general formula (II). Or, they may together form a multi- or multimer coupler. In the case of a dimer, those groups are used as a mere bond or a divalent linking group (for example, a divalent group such as an alkylene group, an arylene group, an ether group, an ester group, an amide group, or a divalent group combining these groups). When forming an oligomer or polymer, these groups are preferably the polymer backbone or are attached to the polymer backbone through divalent groups such as those mentioned for dimers. When forming a polymer, even if it is a homopolymer of a coupler derivative, other non-chromogenic ethylene-like monomer (for example, acrylic acid,
Methacrylic acid, methyl acrylate n-butyl acrylamide, β-hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone, etc.), one or more of which may form a copolymer. .

Preferred R ^{71 in the} general formula (I) and the general formula (I) N
Preferable R ^{75 in} I is a substituted or unsubstituted alkyl group or aryl group, and the substituent of the alkyl group is preferably an optionally substituted phenoxy group or a halogen atom, and at least one aryl group is preferable. Particularly preferred is a phenyl group substituted with a halogen atom, an alkyl group, a sulfonamide group, a sulfamoyl group, a carboxy group or an acylamino group.

R ⁷⁴ in the general formula (II) is preferably a substituted alkyl group or a substituted or unsubstituted aryl group, a halogen atom is particularly preferable as the substituent of the alkyl group, and the aryl group is a phenyl group or a halogen atom, a sulfonamide group, Particularly preferred is a phenyl group substituted with at least one sulfamoyl group.

In formula (II), preferred R ⁷² is an optionally substituted alkyl group having 1 to 20 carbon atoms. The substituent of R ⁷² is preferably an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imide group, a ureido group, an alkyl or arylsulfonyl group.

In the general formula (I), R ⁷³ is preferably a hydrogen atom, a halogen atom (particularly a fluorine atom or a chlorine atom) or an acylamino group, and particularly preferably a halogen atom.

In formula (II), R ⁷⁶ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkenyl group, and particularly preferably a hydrogen atom.

In the general formula (II), it is preferable that R ⁷⁵ and R ⁷⁶ form a 5- to 6-membered nitrogen-containing heterocycle.

In formula (I), R ⁷² is more preferably an alkyl group having 2 to 4 carbon atoms.

In formulas (I) and (II), each of Y ⁷¹ and Y ⁷² is preferably a halogen atom, and more preferably a chlorine atom.

The couplers represented by the general formulas (I) and (II) can be used alone or as a mixture of a plurality of couplers.

It is known in the art that the magenta coupler represented by the general formula (III) has the following keto-enol tautomerism when R ⁷⁸ is a hydrogen atom.

In the general formula (III), the permissible substituents for R ⁷⁹ and R ⁷⁷ are the same as the permissible substituents for the aromatic group for R ⁷¹ , and when two or more substituents are present, they are the same. But it can be different.

Preferred R ⁷⁸ in formula (III) is a hydrogen atom, an aliphatic acyl group or an aliphatic sulfonyl group, and a particularly preferred R ⁷⁸ is a hydrogen atom. Preferred Y ⁷³ is of the type that leaves at either a sulfur, oxygen or nitrogen atom,
Sulfur atom leaving groups are particularly preferred.

The compound represented by the general formula (IV) is a 5-membered-5-membered condensed nitrogen hetero coupler (hereinafter referred to as a 5,5N heterocyclic coupler), and its color-developing nucleus has an isoelectronic aromaticity with naphthalene. It has a chemical structure commonly referred to as azapentalene. Among the couplers represented by the general formula (IV), preferred compounds are 1H-imidazo [1,2-b] pyrazoles, 1H-pyrazolo [5,1-c] [1,2,4] triazoles, 1H -Pyrazolo [1,5-b] [1,2,4] triazoles and 1H-pyrazolo [1,5-d] tetrazoles.

In the general formula (V), an N-phenylcarbamoyl group Q
The substituents of the femil group of can be arbitrarily selected from the group of substituents which are permissible when R ⁷¹ is an aromatic group, and when there are two or more substituents, they may be the same or different. Good.

Preferred leaving group Y ⁷⁵ includes groups represented by the following general formulas (VI) to (XII).

R ⁹⁰ represents an optionally substituted aryl group or heterocyclic group.

R ⁹¹ and R ⁹² are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfonamide group, an arylsulfonamide group, a sulfamoyl group, an alkylsulfinyl group. Represents a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group or a heterocyclic group, and these groups may be the same or different.

W ₁ in the formula Represents a non-metal atom required to form a 4-membered ring, 5-membered ring or 6-membered ring.

Of the general formula (IX), preferred are (X) to (XII).

In the formula, R ⁹³ and R ⁹⁴ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a sulfonamide group, a sulfamoyl group, a carboxy group, an aryloxy group or a hydroxy group, and R ⁹⁵ , R ⁹⁶ and R ⁹⁷ each represent It represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group, and W ₂ represents an oxygen or sulfur atom.

References that describe other exemplary compounds or synthetic methods of the couplers represented by the general formulas (I) to (V) are given.

The cyan couplers represented by the general formulas (I) and (II) can be synthesized by a known method. For example, the general formula (I)
The cyan coupler represented by U.S. Pat. No. 2,423,730
No. 3,772,002 and the like.
The cyan coupler represented by the general formula (II) is described in US Pat.
2,895,826, 4,333,999, 4,327,173 and the like.

Magenta couplers represented by the general formula (III) are disclosed in JP-A-49-74027, JP-A-49-74028, JP-B-48-27930,
It is synthesized by the method described in U.S. Pat. No. 53-33846 and U.S. Pat. No. 3,519,429. The magenta couplers represented by formulas (IV-1) to (IV-4) are described in JP-A-59-16, respectively.
2548, US Pat. No. 3,725,067, JP-A-59-171956, JP-A-60-33552 and the like.

The yellow coupler represented by the general formula (V) is disclosed in JP-A-54.
-48541, JP-B-58-10739, U.S. Pat.No. 4,326,024
And Research Disclosure No. 18053, and the like.

Preferred specific examples of the coupler are shown below.

In the present invention, the water-insoluble polymer soluble in an organic solvent and the specific oil-soluble coupler are dissolved in a high-boiling organic solvent to be introduced into the light-sensitive material in the form of lipophilic fine particles.
Here, as the high-boiling point organic solvent, those described in US Pat. No. 2,322,027 and the like can be used, and specifically, phthalic acid alkyl ester (dibutyl phthalate,
Dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate,
Tricresyl phosphate, dioctyl butyl phosphate, monophenyl-pt-butylphenyl phosphate), citric acid ester (eg tributyl acetylcitrate), benzoic acid ester (eg octyl benzoate), alkylamide (eg diethyl lauryl) Amides, dibutyllaurylamide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate), compounds containing an epoxy ring (eg compounds described in US Pat. No. 4,540,657) ), Phenols (eg Examples thereof include ethers (for example, phenoxyethanol and diethylene glycol monophenyl ether).

The size of the fine particles to be formed is not particularly limited, but is usually
0.05-2.0μ, preferably 0.05-1.0μ, more preferably
It is 0.1 to 0.20μ. The polymer / coupler ratio (weight ratio) in the fine particles is preferably 1/20 to 20/1, and more preferably 1/10 to 10/1.

Furthermore, the total amount of polymer and coupler is 20 to 10 in the fine particles.
It is good to set it to 0%, preferably 30 to 100%.
As described above, an auxiliary solvent for dissolving the polymer may be added to the fine particles.

The fine grain dispersion is introduced into an emulsion layer and coated on a reflective support by a known method to form a silver halide light-sensitive material which is the object of the present invention. here,
Various known materials are used to form the emulsion layers. That is, the silver halide emulsion may be of any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride. For example, when performing rapid processing or low replenishment processing, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and a silver chloride content of 80 mol% or more is preferable.
The case of up to 100 mol% is particularly preferable. Further, when high sensitivity is required and fog during production, storage, and / or processing is required to be suppressed to a particularly low level, a silver chlorobromide emulsion containing 50 mol% or more of silver bromide (3 mol % Or less of silver iodide may be contained), and more preferably 70 mol% or more. Silver iodobromide and silver chloroiodobromide are preferred for the color light-sensitive material for photographing, and the silver iodide content is 3 to 15 mol%.
Is preferred.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size distribution of the silver halide grains used in the present invention may be narrow or wide, but the standard deviation value in the grain size distribution curve of the silver halide emulsion is the value divided by the average grain size (variation). Rate) is within 20%, particularly preferably 15%
The so-called monodisperse silver halide emulsions within are preferably used in the present invention. Further, 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 the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be used as a mixture or a multilayer.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a rhodohedron, and a tetradecahedron, or may have a coexisting form thereof. It may have an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, an emulsion in which tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more account for 50% or more of the total projected area of grains may be used. An emulsion composed of a mixture of these various crystal forms may be used.

These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is Research Disclosure.
It can be prepared using the method described in vol.170Item No.17643 (I, II, III) (1978.12).

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol. 187, No. 187.
18716 (November, 1979), the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Desert Dix Rogers, and the locations described in the table below are shown.

The reflective support coated with the above-mentioned emulsion layer enhances the reflectivity to make the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide on the support. , Those coated with a hydrophobic resin containing a light-reflecting substance such as zinc oxide, calcium carbonate, and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light-reflecting substance dispersed therein as a support.

In the present invention, the above silver halide color photographic light-sensitive material is
Processing is carried out, for example, by the following method using a color developer containing an N-hydroxyalkyl-substituted p-phenylenediamine derivative and containing substantially no benzyl alcohol.

A. Color development-rinse-bleach-fix-wash-dry-B. Color development-rinse-bleach-fix-wash-dry C. Black-white development-rinse-reflection exposure-color development-rinse-
Bleach-fix-wash-dry Here, instead of washing, (i) stabilization or (ii) washing-stabilization can be performed, and rinsing can be omitted.

Next, each processing step and processing solution will be described.

Development Processing In the present invention, a developing agent and N-hydroxyalkyl-substituted-p are used.
-A development processing solution containing phenylenediamine is used. Preferred developing agents can be represented by the following general formula.

In the formula, R ₁₁ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and R ₁₂ is a hydrogen atom or 1 to 4 carbons. An alkyl group having an atom, R ₁₃ is an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, A has at least one hydroxyl group, and has a branch. Is also an alkyl group, more preferably, Is. Here, R ₁₄ , R ₁₅ and R ₁₆ each represent a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group, and R ₁₄ , R ₁₅ and R ₁₆ At least one is an alkyl group having a hydroxyl group.
n ₁ , n ₂ and n ₃ are 0, ₁ , 2 or 3, respectively, and HX is hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, nitric acid or phosphoric acid.

It is unstable with the free amines of such p-phenylenediamine color developing agents and is commonly used as a salt (most commonly identified by the above formula). A typical example is 4-amino-3-methyl-N
Examples include -ethyl-N- (β-hydroxyethyl) -aniline salt and 4-amino-N-ethyl-N- (β-hydroxyethyl) -aniline salt.

Preferably, in the present invention, 4-amino-3-methyl-
N-Ethyl-N- (β-hydroxyethyl) -aniline sulphate hydrate [This is commercially available under the name CD-4 and is used in most color photographic systems (eg Eastman Kodak C41 system or , Which is used for developing a color negative film such as Konishi Photo Industry Co., Ltd. CNK-4 system), has been found to be particularly effective.

The preferred N-hydroxyalkyl-substituted-p-phenylenediamine derivatives used in the present invention include the following, but are not limited to these exemplified compounds.

Among these exemplified compounds, those represented by the symbols, a, b, f, g and h are preferable, and those represented by a, b and f are particularly preferable. More preferably, it is represented by a.

The amount of these compounds used is preferably in the range of 1 g to 100 g, more preferably 3 g to 30 g, per treatment liquid.

These N-hydroxyalkyl-substituted-p-phenylenediamine derivatives of the present invention can be easily synthesized by the method described in Journal of American Chemical Society, Vol. 73, page 3100 (1951).

The developer of the present invention is further characterized by containing substantially no benzyl alcohol. Here, the term "substantially free" means that the amount is not more than 3 g, preferably not more than 1 g, more preferably not contained at all per one developer.

In addition, the color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to contain agents or antifoggants. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids,
Triethylenediamine (1,4-diazabicyclo [2,2,2]
Various preservatives such as octane, ethylene glycol,
Organic solvents such as diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, amine salts, dye forming couplers, competing couplers, fogging agents such as sodium boron hydride, 1-phenyl-3-pyrazolidone Auxiliary developing agents, 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'-tetramethylene Phosphonic acid, ethylenediamine-di ( - hydroxyphenylacetic acid) and salts thereof can be increased as a representative example.

The pH of these color developing solutions is generally 9-12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally per square meter of light-sensitive material.
It is 3 liters or less and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

Bleaching and / or fixing treatment (desilvering treatment) Usually, bleaching treatment is carried out after color development. The bleaching process may be performed simultaneously with the fixing process. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used (bleach-fixing processing), or it may be carried out at a location. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. Examples of bleaching agents include iron (III), cobalt (III), chromium (V
Compounds of polyvalent metals such as I) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, or citric acid,
Complex salts of tartaric acid, malic acid, etc .; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III)
Aminopolycarboxylic acid iron (III) complex salts such as complex salts and persulfates 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 both the bleaching solution and the 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 a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. As a useful bleaching accelerator, specifically, U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, JP-A-53-95,630, Research
Compounds having a mercapto group or a disulfide bond described in Disclosure No. 17,129 (July 1978), etc .; Thiazolidine derivatives described in JP-A No. 50-140,129; Thiourea derivatives described in US Pat. No. 3,706,561;
Iodide salts described in JP-A-58-16,235; West German Patent No. 2,74
Polyoxyethylene compounds described in No. 8,430; Japanese Patent Publication No. 4
Examples thereof include polyamine compounds described in 5-8836; bromide ions and the like. Of these, compounds having a mercapto group or a disulfide group are preferred because of their large accelerating effect,
Especially U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
The compounds described in JP-A-53-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 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 light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

Washing and / or Stabilization Treatment After the above desilvering treatment, a washing and / or stabilization step is generally performed. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers (Volume 64, P.248-253 (1955
May issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The washing water used has a pH of 4-9, preferably 5-
8 The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, it is 20 seconds at 15-45 ° C.
A range of 10 minutes, preferably 30-40 seconds at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, JP-A-57-8543, 58-14,834
All known methods described in No. 60-220, 345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and as an example, it is used as a final bath of a color light-sensitive material for photographing. Mention may be made of a stabilizing bath containing formalin and a surfactant. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the 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 accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff's base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, metals described in U.S. Pat.No. 3,719,492. Salt complex, JP-A-5
The urethane compound described in 3-135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339, JP-A-57-144547, and JP-A-58-11.
It is described in No. 5,438.

The various treatment solutions described above are used at 10 ° C to 50 ° C. Normally 33 ° C
A temperature of ˜38 ° C. is standard, but a higher temperature can be used to accelerate the processing to shorten the processing time, and conversely, a lower temperature can be used to improve the image quality and improve the stability of the processing liquid. In addition, West German Patent No. 2,226,770 for silver saving of light-sensitive materials
Alternatively, treatment with cobalt intensification or hydrogen peroxide intensification as described in US Pat. No. 3,674,499 may be performed.

〔The invention's effect〕

According to the present invention, when a color developing agent such as 4-amino-3-methyl-N-ethyl- (β-methanesulfonamidoethyl) aniline sulfate, which was conventionally said to have relatively good color image stability, is used. It is possible to achieve further color image stability (especially excellent in dark fading) and rapid processing as compared with those of (1).

Furthermore, according to the present invention, since the color negative film can be developed and processed with the same developer, a great advantage over the conventional processing method in which the negative film and the paper are treated with different developers. Is obtained.

(Example) The present invention will be described in more detail based on an example.

Example 1 Each layer was coated on a paper support laminated on both sides with polyethylene to have the layer constitution shown in Table A, and the coupler and the polymer were multilayer color printing papers S11 to S14 as shown in Table 1.
Were produced respectively. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer: 23.8 mmol of a yellow coupler (a) and 4.4 g of a color image stabilizer (b), 27.2 cc of ethyl acetate and 7.7 cc of a solvent (c).
Was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. The polymer (n) is dissolved in the above ethyl acetate (dissolved at a ratio of 7.7 g per 10 cc of ethyl acetate). On the other hand, silver chlorobromide emulsions (EM1, EM2) were prepared by adding the following blue-sensitive sensitizing dyes at 5.0 × 10 ⁻⁴ mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution for the first layer having the composition shown in Table A.
Thus, the fine particles containing the yellow coupler (a) and the polymer (n) dispersed in the coating solution had a particle size of about 0.15μ.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. In this case, the method for preparing the polymer solution and the particle size of the polymer-containing fine particles were the same as those for the first layer.
As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizing dye for each 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.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, per mol of silver halide.
5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.6 × 10 ^-4 mol were added.

Further, 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 1.2 × 10 ^-2 mol and 1.1 × 10 mol, respectively, per mol of silver halide. ^-2 mol was added.

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

(Note) The compounds and the like used for the multilayer color photographic paper are as follows.

(A) Yellow coupler: shown in Table 1.

(E) Magenta coupler: shown in Table 1.

(K) the solvent _{O = PO-C 9 H 19} (iso)) 3 (l) Cyan Coupler: shown in Table 1.

(N) Polymer Table 1 shows the polymers used. However, the number average molecular weight of each polymer in this example and each of the following examples is as follows.

P-3 30,000 P-56 70,000 P-57 60,000 P-58 50,000 P-59 30,000 P-60 60,000 P-64 70,000 Then, a light-sensitive material R11 was prepared in the same manner as described above except that the yellow, magenta and cyan couplers were changed to the following 4-equivalent couplers YA, MA and CA.

The treatment process and treatment liquid formulation are as follows.

Processing temperature Time Color development 38 ℃ 1 minute 00 seconds Bleaching and fixing 34 ℃ 1 minute 00 seconds Washing with water 34 ℃ 20 seconds Washing with water 34 ℃ 20 seconds Washing with water 34 ℃ 20 seconds Drying with 80 ℃ 50 seconds (Washing → 3 A countercurrent flow system was used.) The composition of each processing solution is as follows.

Color developer Water 800 ml Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 2.0 g Nitrilotriacetic acid 2.0 g Potassium bromide 0.5 g Potassium carbonate 30 g Diethylhydroxyamine 4.0 g Triethylenediamine (1, 4-Diazabicyclo [2,2,2] octane 5.0g Sodium sulfite 2.0g Color developing agent See Table 1 Fluorescent brightener (UVITEX-CK manufactured by Ciba-Geigy) 1.5g Water added 1000ml pH (25 ℃) 10.25 Bleach Fixer Water 400 ml Ammonium thiosulfate (70%) 200 ml Sodium sulfite 20 g Ammonium iron (III) acetate (III) ethylenediaminetetraacetate 5 g Disodium ethylenediaminetetraacetate 5 g Water was added to 1000 ml pH (25 ° C) 6.70 Rinse water (calcium and magnesium are (3ppm or less for each) Tungsten light source was applied to the photosensitive materials S11 to S14 and R11 prepared as described above with a filter to obtain a color temperature of 4800. 20 CMS adjusted to K
After applying the wedge exposure, the color development processing was performed in the above processing step. Here, the color development rate of the maximum density of the yellow dye obtained by the above-mentioned processing with respect to the maximum density of the yellow dye when the color development time was 2 minutes was calculated as a percentage (D
_max %).

Each sample treated in the above treatment step was stored at 70 ° C. and 80% for 2 weeks, and yellow, magenta, and
The decrease in the density of each cyan dye after storage with respect to the density before storage of 2.0 (ΔD _2.0 ) was examined.

The results are shown in Table 1. As is clear from Table 1, in the case of the color developing agent used in Comparative Examples, the improvement of ΔD _2.0 from the addition of no polymer to the use of the polymer is not remarkable (No. 1, 2).
On the other hand, according to the present invention, the combination of the polymer, the specific coupler and the specific color developing agent significantly improves the ΔD _2.0 (No. 3, 4 vs. No. 7, 8).

At this time, it is also understood that D _max is sufficient according to the present invention. Furthermore, it can be seen that even better results are obtained when using a 2-equivalent coupler (No. 7, 8 vs. No. 12 to 3).
Four).

In Table 1, the color developing agent was used at a concentration of 12 mmol / l,
D-1 to D-3 have the following structures (hereinafter the same).

Further, the cyan coupler C-1 / C-4 was used together in a molar ratio of 1/1 (the same applies hereinafter).

Example 2 Each layer was coated on a paper support laminated on both sides with polyethylene to have the layer constitution shown in Table B, and the coupler and the polymer were each multilayer color printing paper S21 to S24 as shown in Table 2. It was made. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer: 23.8 mmol of a yellow coupler (a) and 4.4 g of a color image stabilizer (b), 27.2 cc of ethyl acetate and 7.7 cc of a solvent (c).
Was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a blue sensitizing dye shown below was added to silver chlorobromide emulsions (EM7, EM8) in an amount of 5.0 × 10 ⁻⁴ mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution for the first layer having the composition shown in Table B. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer,
1-oxy-3,5-dichloro-s-triazine sodium salt was used.

In this case, the method for preparing the polymer solution and the particle size of the obtained polymer-containing fine particles were the same as in Example 1.

The following were used as the spectral sensitizing dye for each layer.

And 5-3 of Example 1 (7.
0 × 10 ⁻⁵ mol) Red-sensitive emulsion layer: the same compound 5-4 as in Example 1 was used.

To the red-sensitive emulsion layer, the same compound as in Example 1 was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

Further, 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 mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 7.5 × 10 ^-4 mol were added.

The same dye as in Example 1 was added to the emulsion layer to prevent irradiation.

(Note) The compounds and the like used for the multilayer color photographic paper are as follows.

(A) yellow coupler, (e) magenta coupler,
Table 1 shows (1) cyan coupler and (n) polymer. (B), (f) and (m) color image stabilizer, (c),
The solvent (d) and (j) color mixing inhibitor (k) and (o) and the ultraviolet absorber (i) are the same as those used in Example 1.

Next, a light-sensitive material R21 was prepared in the same manner as described above except that the yellow, magenta and cyan couplers of the light-sensitive material were changed to YA, MA and CA similar to those in Example 1.

After imagewise exposure of the light-sensitive material shown in Experiment No. 10 of Table 2,
Using a paper processor, continuous processing (running test) was performed in the following processing steps until the tank capacity for color development was doubled.

The composition of each treatment liquid is as follows.

Bleach-fixing solution (common to tank solution and replenisher) Water Ethylenediaminetetraacetic acid Ferric acid 60.0g Ammonium dihydrate Ethylenediaminetetraacetic acid 5.0g Disodium salt Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution 260.0ml (1.23mol) (70%) Acetic acid (98%) 5.0 ml Water added 1000 ml pH (25 ° C) 6.0 Washing solution (common to tank solution and replenisher) Deionized water ^* 1000 ml Sodium diisocyanurate 0.02 g Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 g * Deionized water was obtained by passing tap water through a mixed bed column in which a strongly basic anion exchange resin and a strongly acidic cation exchange resin were mixed.

The conductivity was 1.0 μs / cm (25 ° C).

After continuous processing, each photosensitive material was treated with 20 CMJ as in Example 1.
After the exposure, the development rate of the yellow dye at the development time of 1 minute and 30 seconds was determined, and the color development rate of the maximum density of the yellow dye by the above treatment was determined, and the yellow stain immediately after the treatment was measured. Furthermore, the fading of each dye at the position of density 2.0 immediately after the treatment was evaluated in the same manner. The results are shown in Table 2.

As is apparent from Table 2, according to the present invention, it is possible to obtain a sufficient color development rate and a good dark heat fading property.

Example 3 As shown in Table C, the first layer (lowermost layer) to the seventh layer (uppermost layer) were sequentially applied and formed on a double-sided polyethylene laminated paper that had been subjected to corona discharge processing to prepare a printing paper sample S31. The preparation of the coating liquid for each layer is as follows. The details of the structural formulas of the coupler, color image stabilizer and the like used in the coating liquid will be described later.

The coating liquid for the first layer was prepared as follows. That is, a mixture of 263.6 g of a yellow coupler, 93.3 g of an anti-fading agent, 10 g of a high boiling point solvent (p) and 5 g of a solvent (q), and 600 ml of ethyl acetate as an auxiliary solvent was dissolved by heating at 60 ° C.,
It was mixed with 3300 ml of a 5% aqueous gelatin solution containing 330 ml of a 5% aqueous solution of alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by DuPont). Next, this solution was emulsified using a colloid mill to prepare a coupler dispersion. From this dispersion, ethyl acetate was distilled off under reduced pressure, and a sensitizing dye for blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole were added to 1400 g of emulsion (Ag
As 96.7g. (Including 170g of gelatin), 1 more
A coating solution was prepared by adding 2600 g of 0% gelatin aqueous solution. The coating solutions for the second layer to the seventh layer were prepared according to the composition of Table C according to the first layer.

In this case, the method of preparing the polymer solution and the particle size of the obtained polymer-containing fine particles were the same as in Example 1.

(Note) The compounds used for the above photographic paper are as follows.

n 2- (2-Hydroxy-3,5-di-tert-amylphenyl) benzotriazole o 2- (2-Hydroxy-3,5-di-tert-butylphenyl) benzotriazole p Di (2-ethylhexyl) phthalate q dibutyl phthalate r 2,5-di-tert-amylphenyl-3,5-di-tert
-Butyl hydroxybenzoate s 2,5-di-tert-octylhydroquinone t 1,4-di-tert-aluminum-2,5-dioctyloxybenzene u 2,2'-methylenebis (4-methyl-6-tert-
Butylphenol) The following substances were used as sensitizing dyes in each emulsion layer.

Blue-sensitive emulsion layer; Anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide Green-sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3'- Disulfoethyloxacarbocyanine hydroxide Red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9-,
9 '-(2,2-Dimethyl 1,3-propano) thiadicarbocyanine iodide Also, 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole was added as a stabilizer for each emulsion layer. Using.

The following dyes were used as the anti-irradiation dye.

4- (3-carboxy-5-hydroxy-4- (3-
(3-carboxy-5-oxo-1- (4-sulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) 1-pyrazolyl) benzenesulfonate-di-potassium salt N, N '-( 4,8-Dihydroxy-9,10-dioxo-3,7-disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt 1,2-bis (vinyl) as a hardener Sulfonyl) ethane was used.

The couplers used are as follows.

Yellow coupler Next, the yellow, magenta, and cyan couplers of the above-mentioned light-sensitive material were used as YA and M-, respectively, used in Example 1.
A color photographic printing paper R31 was produced in the same manner as above except that the color printing paper R31 was changed to A or CA.

As described above, a running process (continuous process) test was performed after imagewise exposure of the produced color photographic paper S31 until each of the color developing solutions was replenished in an amount three times the tank capacity in the following process steps.

The composition of each treatment liquid used is as follows.

Bleach-fixing solution Water 400ml Ammonium thiosulfate (70%) 100ml Ammonium sulfite (40%) 27.5ml Ethylenediaminetetraacetic acid iron (III) ammonium 60g Ethylenediaminetetraacetic acid disodium 3g Add water 1000ml pH (25 ℃) 7.10 Stabilizer 1- Hydroxyethylidene 1,1-diphosphonic acid (60
%) 1.6 ml Bismuth chloride 0.3 g Polyvinylpyrrolidone 0.3 g Ammonia water (26%) 2.5 ml Nitrilotriacetic acid 1.0 g 5-Chloro-2-methyl-4-isothiazoline-3-
On 0.05g 2-octyl-4-isothiazolin-3-one 0.05g Fluorescent brightener (4,4'-diaminostilbene type 1.0g Water added 100ml pH 7.5 After continuous processing 7.5 S31 and R31 were exposed to a wedge and evaluated in the same manner as in Example 2. The results are shown in Table 3.

It can be seen from Table 3 that, according to the present invention, as in the case of Example 2, good color development and fading can be obtained.

Example 4 A color photographic light-sensitive material was prepared by coating the following first to eleventh layers on a paper support laminated on both sides with polyethylene. Titanium white was contained as a white pigment, and a slight amount of ultramarine was contained as a bluish dye on the side coated with the first layer of polyethylene.

(Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below.

For silver halide, the coating amount in terms of silver is shown.

1st layer (anti-halation layer) Black colloidal silver 1.00 Gelatin 2.00 2nd layer (low-sensitivity red-sensitive layer) Silver iodobromide (silver iodide 3.5 silver spectrally sensitized with red sensitizing dye (ExS-1,2) Mol%, average particle size 0.5μ) 0.15 Gelatin 1.00 Polymer (p-57) 0.40 Cyan coupler (ExC-1) 0.30 Antifade agent (Cpd-1,2,3) 0.15 Coupler solvent (Solv-1,2) 0.06 Third layer (high-sensitivity red-sensitive layer) Silver iodobromide spectrally sensitized with a red sensitizing dye (ExS-1,2) (8.0 mol% silver iodide, average particle size 0.7μ) 0.11 gelatin 0.50 polymer ( p-57) 0.40 Cyan coupler (ExC-1) 0.10 Anti-fading agent (Cpd-1,2,3) 0.50 Coupler solvent (Solv1,2) 0.04 Fourth layer (intermediate layer) Yellow colloidal silver 0.02 Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.08 Anti-color mixing agent Solvent (Solv-3,4) 0.16 Polymer latex (Cpd-5) 0.10 Fifth layer (low sensitivity green sensitive layer) Green Silver iodobromide spectrally sensitized with a sensitizing dye (ExS-3) (2.5 mol% silver iodide, average particle size 0.4μ) 0.20 gelatin 0.70 polymer (p-57) 0.40 magenta coupler (ExM-1) 0.40 Anti-fading agent (Cpd-6) 0.05 Anti-fading agent (Cpd-7) 0.05 Anti-fading agent (Cpd-8) 0.02 Coupler solvent (Solv3,5) 0.15 6th layer (high sensitivity green sensitive layer) Green sensitizing dye ( ExS-3) spectrally sensitized silver iodobromide (3.5 mol% silver iodide, average particle size 0.9μ) 0.20 gelatin 0.70 polymer (p-57) 0.40 magenta coupler (ExM-1) 0.04 anti-fading agent ( Cpd-6) 0.05 Anti-fading agent (Cpd-7) 0.05 Anti-fading agent (Cpd-8) 0.02 Coupler solvent (Solv3,5) 0.15 7th layer (yellow filter layer) Yellow colloidal silver 0.20 Gelatin 1.00 Anti-fading agent (Cpd) -4) 0.06 Anti-fading solvent (Solv3,5) 0.15 Polymer latex (Cpd-5) 0.10 8th (Low-sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (ExS-4) (silver iodide 2.5 mol%, average grain size 0.5 µ) 0.15 gelatin 0.50 polymer (p-57) 0.40 Yellow coupler (ExY-1) 0.20 Anti-staining agent (Cpd-8) 0.001 Coupler solvent (Solv-2) 0.05 9th layer (high sensitivity blue sensitive layer) Spectral sensitized with blue sensitizing dye (ExS-4) Silver iodobromide (2.5 mol% silver iodide, average grain size 1.4μ) 0.20 Gelatin 0.50 Polymer (p-57) 0.40 Yellow coupler (ExY-1) 0.20 Anti-staining agent (Cpd-8) 0.001 Coupler solvent (Solv- 2) 0.05 10th layer (UV absorbing layer) Gelatin 1.50 UV absorbing agent (Cpd-9,1,3) 1.00 Color mixing inhibitor (Cpd-10) 0.08 UV absorbing agent (Solv-2) 0.30 Anti-irradiation dye (Cpd) -11) 0.04 Irradiation prevention dye (Cpd-12) 0.04 11th layer (protective layer) Fine particle chlorobromide (Silver 97 mol% chloride, the average size 0.2.mu.)
0.07 Gelatin 1.00 Gelatin hardening agent (H-1) 1.17 (Note) The compounds and the like used in the above color photographic light-sensitive material are as follows.

Cpd-4: same as (j) of Example 1.

Cpd-5 Polyethylene acrylate (P-4: average molecular weight 100,000) Cpd-6; the same as (f) of Example 1.

Cpd-10: same as (d) of Example 1.

The light-sensitive material prepared as described above was processed in the processing steps shown below.

[Treatment process]

First phenomenon (black and white phenomenon) 38 ℃ 1'15 "Rinse 38 ℃ 2'15" Reverse exposure at least 100 Lux for 1 second or longer Color phenomenon 38 ℃ 1'00 "Rinse 38 ℃ 45" Bleach-fix 38 ℃ 2'00 "Water Washing 38 ℃ 2'15 ″ [Treatment liquid composition] First phenomenon liquid Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 0.6g Diethylenetriamine pentaacetic acid pentasodium salt 4.0g Potassium sulfite 30.0g Potassium thiocyanate 1.2g Potassium carbonate 35.0g Hydroquinone monosulfonate / potassium salt 25.0g Diethylene glycol 15.0ml 1-Phenyl-4-hydromethyl-4-methyl-3-pyrazolidone 2.0g Potassium bromide 0.5g Potassium iodide 5.0mg Add water 1 ( pH9.70) Color developer 3,6-dithia-1,8-octanediol 0.2g Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 0.5g Diethylenetri Min pentaacetate, pentasodium salt 2.0 g 2-methyl-1,4-diazabicyclo [2,2,2] octane 5.
0g Potassium carbonate 25.0g Diethylhydroxylamine 3.0g Color developing agent (D-1 or compound a) 12mmol Potassium bromide 0.5g Potassium iodide 1.0mg Add water 1 (pH 10.40) Bleach-fixing solution 2-Mercapto-1 1,3,4-Triazole 1.0g Ethylenediaminetetraacetic acid / sodium dihydrate / 5.0g Ethylenediaminetetraacetic acid / Fe (III) / ammonium monohydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (70% solution) 160.0ml Ice Acetic acid 5.0 ml Water was added 1 (pH6.50) Rinse solution and wash water Ion-exchanged water Calcium, magnesium 3 ppm or less Dmax% and ΔD _2.0 were evaluated after treatment with each color phenomenon liquid as in Example 1, and color development It was found that when the compound a was used as the developing agent, D-1 was used, the coloring property and the dark fading property were improved.

Example 5 Multi-layer color photographic paper 31 and R3 similar to those in Example 3 except that each layer is coated on a paper support laminated on both sides with polyethylene.
1 was created for each.

Next, a color negative film for photographing was prepared by coating each layer of the composition shown below on a subbed cellulose triacetate support.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) 1st layer; antihalation layer Black colloidal silver ..... Silver 0.18 gelatin ........ 0.40 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 ・ ・ ・ ・ 1.04 Third layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (6 mol% of silver iodide, average grain size of 0.
Coefficient of variation for 6μ particle size 0.15) ・ ・ ・ ・ Silver 0.55 Sensitizing dye I ・ ・ ・ 6.9 × 10 ^-5 Sensitizing dye II ・ ・ ・ 1.8 × 10 ^-5 Sensitizing dye III ・・ ・ ・ ・ 3.1 × 10 ^-4 Sensitizing dye IV ・ ・ ・ ・ ・ 4.0 × 10 ^-5 EX-2 ・ ・ ・ ・ ・ ・ 0.350 HBS-1 ・ ・ ・ ・ ・ ・ ・ 0.005 EX-10 ・ ・・ ・ ・ 0.020 Gelatin ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.20 4th layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion (10 mol% silver iodide, average grain size of 0.
7μ, average aspect ratio 5.5, average thickness 0.2μ)
・ ・ ・ Silver 1.0 Sensitizing dye I ・ ・ ・ ・ ・ 5.1 × 10 ^-5 Sensitizing dye II ・ ・ ・ 1.4 × 10 ^-5 Sensitizing dye III ・ ・ ・ ・ ・ 2.3 × 10 ^-4 Sensitizing dye IV ・ ・ ・ ・ ・ 3.0 × 10 ^-5 EX-2 ・ ・ ・ ・ ・ ・ ・ 0.400 EX-3 ・ ・ ・ ・ ・ ・ ・ 0.050 EX-10 ・ ・ ・ ・ ・ ・ ・ 0.015 Gelatin ・ ・ ・ ・ ・..1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (16 mol% silver iodide, average grain size 1.1 μ)
............ silver 1.60 Sensitizing dye IX ····· 5.4 × 10 ^-5 Sensitizing dye II ····· 1.4 × 10 ^-5 Sensitizing dye III ····· 2.4 × 10 ^{- 4} Sensitizing dye IV ・ ・ ・ ・ ・ 3.1 × 10 ^-5 EX-3 ・ ・ ・ ・ ・ 0.240 EX-4 ・ ・ ・ ・ ・ 0.120 HBS-1 ・ ・ ・ ・ ・ 0.22 HBS- 2 ・ ・ ・ ・ ・ ・ ・ 0.10 gelatin ・ ・ ・ ・ ・ ・ ・ 1.63 6th layer (intermediate layer) EX-5 ・ ・ ・ ・ ・ ・ ・ 0.040 HBS-1 ・ ・ ・ ・ ・ ・ ・ 0.020 EX-12・ ・ ・ ・ ・ ・ ・ ・ ・ 0.004 Gelatin ・ ・ ・ ・ ・ ・ ・ 0.80 7th layer (1st green emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.
6μ, average aspect ratio 6.0, average thickness 0.15μ) ...
・ ・ ・ Silver 0.40 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-4 ・ ・ ・ ・ ・ ・ 0.010 Gelatin ・ ・ ・ ・ 0.75 Eighth layer (second green emulsion layer) Monodisperse silver iodobromide emulsion (9 mol% silver iodide, average grain) Diameter 0.
Coefficient of variation for 7μ grain size 0.18) ・ ・ ・ ・ ・ ・ ・ Silver 0.80 Sensitizing dye V ・ ・ ・ ・ ・ 2.1 × 10 ^-5 Sensitizing dye VI ・ ・ ・ ・ ・ 7.0 × 10 ^-5 Sensitizing dye VII ・・ ・ ・ ・ 2.6 × 10 ^-4 EX-6 ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.180 EX-8 ・ ・ ・ ・ ・ ・ 0.010 EX-1 ・ ・ ・ ・ 0.008 EX-7 ・ ・ ・ ・ ・・ ・ 0.012 HBS-1 ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.160 HBS-4 ・ ・ ・ ・ ・ ・ ・ 0.008 Gelatin ・ ・ ・ ・ 1.10 9th layer (3rd green emulsion layer) Silver iodobromide emulsion (Silver iodide 12 mol%, average particle size 1.0μ)
…… 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-6 ・・ ・ ・ ・ ・ ・ 0.065 EX-11 ・ ・ ・ ・ ・ ・ ・ 0.030 EX-1 ・ ・ ・ ・ ・ ・ 0.025 HBS-1 ・ ・ ・ ・ ・ ・ 0.25 HBS-2 ・ ・ ・ ・ ・ ・ ・0.10 Gelatin ・ ・ ・ ・ ・ 1.74 10th layer (yellow filter layer) Yellow colloidal silver ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Silver 0.05 EX-5 ・ ・ ・ ・ ・ ・ 0.08 HBS-3 ・ ・ ・ ・ ・ ・・ 0.03 Gelatin ・ ・ ・ ・ ・ ・ ・ 0.95 11th layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (6 mol% of silver iodide, average grain size of 0.
6μ, average aspect ratio 5.7, average thickness 0.15μ) …… Silver 0.
24 Sensitizing dye VIII ・ ・ ・ ・ ・ ・ ・ 3.5 × 10 ^-4 EX-9 ・ ・ ・ ・ ・ 0.85 EX-8 ・ ・ ・ ・ ・ ・ 0.12 HBS-1 ・ ・ ・ ・ ・ ・ ・ 0.28 Gelatin ・・ ・ ・ ・ ・ 1.28 Layer 12 (second blue emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.
Coefficient of variation for 8μ particle size 0.16) ・ ・ ・ ・ Silver 0.45 Sensitizing dye VIII ・ ・ ・ 2.1 × 10 ^-4 EX-9 ・ ・ ・ ・ ・ ・ ・ 0.20 EX-10 ..0.015 HBS-1 ........ 0.03 Gelatin ........ 0.46 13th layer (third blue sensitive emulsion layer) Silver iodobromide emulsion (14 mol% silver iodide, average grain size) 1.3μ)
・ ・ ・ ・ ・ ・ ・ Silver 0.77 Sensitizing dye VIII ・ ・ ・ ・ ・ 2.2 × 10 ^-4 EX-9 ・ ・ ・ ・ ・ ・ 0.20 HBS-1 ・ ・ ・ ・ 0.07 Gelatin ・ ・ ・ ・... 0.69 14th layer (first protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average grain size 0.07μ)
・ ・ ・ ・ ・ ・ ・ Silver 0.5 U-4 ・ ・ ・ ・ ・ ・ ・ 0.11 U-5 ・ ・ ・ ・ ・ 0.17 HBS-1 ・ ・ ・ ・ ・ ・ ・ 0.90 Gelatin ・ ・ ・ ・ ・ ・ ・1.00 Fifteenth layer (second protective layer) Polymethyl acrylate particles (diameter about 1.5μ)
・ ・ ・ 0.54 S-1 ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.15 S-2 ・ ・ ・ ・ ・ ・ ・ 0.05 Gelatin ・ ・ ・ ・ 0.72 In addition to the above components, each layer contains gelatin hardener H- 1 and a surfactant were added.

HBS-1 Tricresyl Phosphate HBS-2 Dibutylphthalate HBS-3 Bis (2-ethylexyl) phthalate The color negative film produced as described above was cut into a width of 35 mm, and the color photographic paper was cut into a width of 82.5 mm.These color negative films and the color photographic paper were respectively imagewise exposed.
Processing was performed while supplementing at the rate shown in Table 4 with an automatic processor (FIG. 1) prepared so as to be processed with a common processing solution.

The details of the processing are described below.

The composition of each treatment liquid is the same as that shown in Example 2.

After filling the processing solution in the automatic processor, the following processing was performed.

First treatment: The color negative film sample 101 was photographed and then continuously treated for 30 m.

Second treatment: The color photographic paper was exposed by an automatic printer and then continuously treated for 90 m.

Third treatment: The same treatment as the first treatment was carried out.

After the above continuous processing, the color photographic paper was evaluated in the same manner as in Example 2. The results are shown in Table 5. It can be seen from Table 5 that, according to the constitution of the present invention, good color development and fading can be obtained.

[Brief description of drawings]

FIG. 1 shows a tank arrangement (plan view) of an automatic processor for mixing processing. In the figure 1 …… color development tank (10l) 2 …… bleach-fixing tank (10l) 3 …… water washing tank (5l) 4 …… water washing tank (5l) 5 …… water washing tank (5l) 6 …… drying section 7 …… Color negative film insertion part 8 …… Color photographic paper insertion part 9 …… Color negative film collection part 10 …… Color photographic paper collection part The hatched (A) part shows the transport part of the color negative film, and the hatched (B) part Indicates a portion for carrying color photographic paper.

Claims (2)

[Claims] 1. At least a diffusion-resistant oil-soluble coupler which forms a substantially non-diffusible dye on a reflective support upon coupling with an oxidant of an aromatic primary amine color developing agent. A silver halide color photographic light-sensitive material provided with a layer containing a dispersion of lipophilic fine particles containing one kind and at least one kind of water-insoluble and organic solvent-soluble polymer,
An image forming method comprising: a color developing solution containing a hydroxyalkyl-substituted-p-phenylenediamine derivative and containing substantially no benzyl alcohol. 2. At least one of the oil-soluble couplers,
The image forming method according to claim 1, wherein the image forming method is a 2-equivalent coupler.