JPH01134452A - Image forming method - Google Patents

Abstract

PURPOSE:To improve the stability of a color image by developing a silver halide color photographic sensitive material provided with a layer contg. the dispersion of a lipophilic fine particle, with a color developer which contains N-hydroxy alkyl substd.-p-phenylene diamine derivative and does not substantially contain benzyl alcohol. CONSTITUTION:The silver halide color photosensitive material provides with the layer contg. the dispersion of the lipophilic fine particle which contains at least one kind of an oil soluble coupler capable of forming a non-dispersible color matter and having been subjected to an anti-dispersive treatment is developed with the color developer which contains N-hydroxy alkyl substd.-p- phenylene diamine derivative, and does not substantially contain benzyl alcohol. As the water insoluble and oil solvent soluble polymer to be incorporated in the lipophilic fine particle in combination with the specified oil soluble coupler, the water insoluble and org. solvent soluble polymer consisting of at least one kind of recurrent unit having no acid group in a main or side chain is used. Thus, the stability of a color image and the rapid processing of the photosensitive material superior to the conventional method can be accomplished.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a reflective support such as a color paper, and particularly enables rapid development processing. The invention also relates to a color photographic image forming method with excellent color image stability.

(Prior Art) Generally, the speed of color development varies depending on the type of paraphenylenediamine derivative used as the color developing agent.
N,N-diethyl-p-
N-alkyl-substituted color developing agents such as phenylenediamine sulfate and 3-methyl-p-amino-N,N-diethylaniline hydrochloride are used. However, these have high development activity and can speed up development;
The problem is that the color image after processing tends to darken and fade.

As a result of various studies, N-hydroxyalkyl-substituted p-phenylenediamine derivatives have been proposed as color developing agents capable of rapid development (Japanese Patent Laid-Open No. 62-4935).
0.62-1)2156 and 62-49352). This developing agent is widely used (1) for developing color negative films and color reversal films; Since dark fading properties are required, development is currently carried out using a developing agent different from the above-mentioned developing agents. In other words, 4-amino-3-methyl-N-methyl (β-methanesulfonamidoethyl) aniline sulfate is used to develop color paper, and although the problem of dark fading has been improved, this developing agent has low development activity. Since the color development is low, it is generally necessary to perform development in the coexistence of benzyl alcohol, which is a color development accelerator. However, the use of benzyl alcohol causes problems such as a decrease in the solubility of the developer and an increase in staining after processing.

Therefore, at present, color paper can be processed quickly.
Moreover, there is no known processing method that improves dark fading.

On the other hand, as a method for improving color image stability, a dispersion method using a coupler polymer has been developed. For example, in U.S. Pat. No. 4,203,716, a hydrophobic substance such as an oil-soluble coupler is dissolved in a water-miscible organic solvent, and this solution is mixed with a loader pull polymer latex to impregnate the polymer with the hydrophobic substance. ) is disclosed. Moreover, in Japanese Patent Publication No. 48-30494, a high-boiling point coupler solvent is not used, and instead, a homopolymer of a hydrophobic monomer with a specific structure or a hydrophilic monomer with a specific structure that is soluble in an organic solvent is used. A photosensitive material containing a coupler dispersion (the particle size of the dispersed particles is approximately 0.5 to 5 microns) using a copolymer is described. Further, Japanese Patent Application No. 162813/1983 also describes a dispersion method using a polymer in order to improve image fastness and the like. Further, JP-A-52-102722 describes that desilvering properties are improved by a dispersion method using a polymer.

However, even for photosensitive materials using such polymers, color development using a color developing agent such as 4-amino-3-methyl-N-ethyl-(β-methanesulfonamidoethyl) aniline sulfate is not sufficient. No effect has been obtained.

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

Furthermore, the present invention uses a color developing agent with excellent development activity, and even when rapid color development processing is performed, there is little staining after processing, and the silver halide silver halide provides color photographs with excellent dark fading resistance of dye images. An object of the present invention is to provide an image forming method for color photographic materials.

(Means for Solving the Problems) The present inventors have made various studies to overcome the drawbacks of the above-mentioned conventional color photographic image forming methods, and as a result, the objects of the present invention have been achieved by the following method. I discovered that.

That is, the present invention provides at least one diffusion-resistant oil-soluble coupler that couples with an oxidized aromatic primary amine color developing agent to form a substantially non-diffusible dye on a reflective support. A silver halide color photographic material provided with a layer containing a dispersion of lipophilic characteristic particles containing one kind of polymer and at least one kind of water-insoluble and organic solvent-soluble polymer is prepared by adding N-hydroxyalkyl-substituted p-phenylenediamine. This was achieved by an image forming method characterized by processing with a color developer containing M1 body and substantially not containing benzyl alcohol.

In the present invention, various polymers can be used as water-insoluble and organic solvent-soluble polymers to be contained in the lipophilic fine particles together with the specific oil-soluble coupler. this house,
It is better to use a water-insoluble and organic solvent-soluble polymer consisting of at least one repeating unit that does not have an acid group in the main chain or side chain, but a polymer having -C- bonds as a repeating unit is preferable. , is preferable from the viewpoint of color development and fading improvement effect.

Furthermore, in the present invention, the repeating unit having no acid group of the polymer has a 10-0- group in its main chain or side chain, or the repeating unit having no acid group of the polymer has a 10-0- group on its main chain or side chain. Preference is given to polymers having a substituent (representing an alkyl or aryl group, substituted or unsubstituted) in the chain.

Examples of polymers used in the present invention are shown below.

(A) Vinyl polymer Monomers forming the vinyl polymer used in the present invention include acrylic esters, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and isobutyl acrylate. Acrylate, 5ec-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, tetrahydro Furfuryl 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-methoxypolyethylene glycol acrylate (number of moles added = 9) 1-bromo -2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like. In addition, the following monomers can be used. .

Methacrylic acid esters: Specific examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5e
c-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, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-
Hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 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- Examples include methoxypolyethylene glycol methacrylate (additional mole number n=6), allyl methacrylate, and methacrylic acid dimethylaminoethyl methyl chloride salt.

Vinyl esters: Specific examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, salicylic acid. Vinyl, etc.; Acrylamides: For example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, Dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetone acrylamide, etc.; Methacrylamides: For example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide amide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N- (2-'acetoacetoxyethyl) methacrylamide, etc.; Olefins: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2.3- Dimethylbutadiene, etc.; Styrenes:
For example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene,
Acetoxystyrene, chlorstyrene, dichlorostyrene, bromustyrene, vinylbenzoic 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 include butyl crotonate , hexyl crotonate, 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,
Examples include glycidyl methacrylate, N-vinyloxazolidone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, vinylidene chloride, methylenemalonitrile, and vinylidene.

Two or more monomers for forming the polymer used in the present invention (e.g., the above monomers) can be used as comonomers depending on various purposes (e.g., improving solubility). Furthermore, in order to control color development and solubility, monomers having acid groups such as those listed below can also be used as comonomers, provided that 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; acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid,
Acryloyloxypropylsulfonic acid, etc.; Methacryloyloxyalkylsulfonic acid, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.; Acrylamidoalkylsulfonic acid, such as 2-acrylamido-2-methylethanesulfone acid,
2-acrylamido-2-methylpropanesulfonic acid,
2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, e.g. 2-
methacrylamide-2-methylethanesulfonic acid, 2-
methacrylamide-2-methylpropanesulfonic acid, 2
- methacrylamide-2-methylbutanesulfonic acid, etc.; these acids are alkali metals (e.g. Na5K etc.)
Alternatively, it may be a salt of ammonium ion.

When using hydrophilic monomers (here, those that become water-soluble when made into a homopolymer) among the vinyl monomers and other vinyl monomers mentioned above as comonomers, the copolymer is water-soluble. There is no particular restriction on the proportion of the wood-philic monomer in the copolymer as long as it does not affect the properties, but it is usually preferably at most 40 mol%, more preferably at most 20 mol%, even more preferably at most 10 mol%. It is. In addition, 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 storage stability as described above,
The proportion of comonomers having acid groups in the copolymer is usually 2
It is 0 mol% or less, preferably 10% or less, and most preferably does not contain such a comonomer.

The monomers forming the polymer used in the present invention are preferably methacrylate-based, acrylamide-based, and methacrylamide-based. In addition, it is usually preferable to copolymerize two or more types of monomers, and particularly preferable are copolymers of acrylamide monomers and other monomers of the present invention, and copolymers of methacrylate monomers and other monomers. It is. Moreover, even if two or more types of polymers are used together,
Of course it's good.

(B) Polyester resin obtained by condensing a polyhydric alcohol and a polybasic acid The polyhydric alcohol is HO-R1-OH (R1 is a hydrocarbon chain having 2 to about 12 carbon atoms, especially an aliphatic hydrocarbon chain) )
Glycols or polyalkylene glycols having the structure are effective, and as polybasic acids, HOOC
-Rt -COOH- (R, represents a simple bond,
Alternatively, those having a hydrocarbon chain having 1 to about 12 carbon atoms are effective.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, ■
, 2-propylene glycol, 1.3-propylene glycol, trimethylolpropane, 1.4-butanediol, isobutylene diol, 1,5-bentanediol, neopentyl glycol, 1.6-hexanediol, 1.7-to Butanediol, 1.8-octanediol, 1.9-nonanediol, 1.10-decanediol, 1.1)-undecanediol, 1.12-dodecanediol, 1.13-)lysocanediol, 1. 4
-diol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol, sorbitol, and the like.

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, and fumaric acid. acids, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, methaconic acid, isohimelic acid, cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc. can give.

(C) Other polyesters obtained by ring-opening polymerization, such as those shown below. In the formula, m represents an integer of 4 to 7. The -〇H2- 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 into the coating liquid as a fine particle dispersion. In this case, there is no particular restriction on the procedure for dissolving the polymer in the organic solvent 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 this polymer, in addition to conventional high-boiling coupler solvents, appropriate auxiliary solvents are used.

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

The molecular weight and degree of polymerization of the polymer used in the present invention do not substantially affect the effects of the present invention, but as the molecular weight increases, problems such as the time it takes to dissolve in an auxiliary solvent, etc.
The high solution viscosity makes it difficult to emulsify and disperse, producing coarse particles.As a result, problems such as decreased color development and poor coating properties tend to occur. To counter this problem, using a large amount of auxiliary solvent to lower the viscosity of the solution will cause new process problems.From the above point of view, the viscosity of the polymer is 30g for every 100cc of auxiliary used. The viscosity when dissolved is preferably 5,000 cps or less, more preferably 2,000 cps or less.The molecular weight of the polymer that can be used in the present invention is preferably 150,000 or less, more preferably 80,000 or less, and still more preferably 30,000 or less. It is as follows.

The ratio of the polymer used in the present invention to the auxiliary solvent varies depending on the type of polymer used, and varies over a wide range depending on the solubility in the auxiliary solvent, the degree of polymerization, or the solubility of the coupler.

Usually, at least the amount of coupler, high-boiling coupler solvent, and polymer king dissolved in a cosolvent will be sufficient to provide a sufficiently low viscosity for the solution to be easily dispersed in water or in an aqueous hydrophilic colloid solution. 0 where co-solvent is used
The higher the degree of polymerization, the higher the viscosity of the solution.
Although it is difficult to uniformly determine the ratio of polymer to co-solvent regardless of the type of polymer, it is usually about 1=1 to 1:50 (
weight ratio) is preferred.

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

Specific examples 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-1) 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 polypropyl Lactone P-18 polydimethylpropiolactone P-19 n-butyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90: P-20 methyl methacrylate-vinyl chloride copolymer (
70:30) P-21 methyl methacrylate-styrene copolymer (9
0:10) 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 Union (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-36n-butyl acrylate- Methyl methacrylate-n-butyl methacrylate copolymer (35:35:30) P-37n-butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38:38:24)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 <
95: 5) P-41 benzyl methacrylate-acrylic acid copolymer (90:10) P-42n-butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35:35:25:5) 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 (3
, 7:29: P-46 polypentyl methacrylate P-47 methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-48 vinyl acetate-vinyl propionate copolymer (75:25) P-49n-butyl methacrylate-3-acryloxybutane-1-sodium sulfonate copolymer (97:3) P-50n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) P-51n -Butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) P-52n-butyl methacrylate-styrene copolymer (90:10) P-53 methyl methacrylate-N-vinyl-2-pyrrolidone copolymer Combined (90:10) P-54n-butyl methacrylate-vinyl chloride copolymer (90:10) P-55n-butyl methacrylate-styrene copolymer (70:30) P-56 poly(N-see-butylacrylamide ) P-57 poly(N-tert-butylacrylamide) P-58 diacetone acrylamide-methyl methacrylate copolymer (62:38) P-59 polycyclohexyl methacrylate P-60N
-tert-butylacrylamide-methyl methacrylate copolymer (40 near 0) P-61 poly (N,N-dimethyl acrylamide) P-62 poly (tert-butyl methacrylate) P
-63 tert-butyl methacrylate-methyl methacrylate copolymer (70:30) P-64 poly (N
-tert-butyl methacrylate) P-65N-tert-butylacrylamide-methylphenyl methacrylate copolymer (60:40) P-66 methyl methacrylate-acrylonitrile copolymer (70:30) P-67 methyl methacrylate-methylvinyl Ketone copolymer (3B Near 2) P-68 methyl methacrylate-styrene copolymer (7
5:25) P-69 methyl methacrylate-hexyl methacrylate copolymer (70:30) In the present invention, along with the water-insoluble and organic solvent-soluble polymer described above, an oxidized product of an aromatic primary amine developer and a camp A diffusion-resistant oil-soluble coupler capable of producing a substantially non-diffusible dye through a ring reaction is contained in the lipophilic fine particles. Color couplers used here include naphthol or phenolic 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 is Research Disclosure (RD) 176
43 (December 1978) ■-D Section and 1B71
7 (January 1979)).

The couplers used in the present invention are preferably those that have a ballast group or are polymerized to have diffusion resistance.The coupling active position is substituted with a leaving group rather than a hydrogen atom equivalent color coupler. A two-equivalent color coupler is preferable because the amount of coated silver can be reduced. DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

Examples of magenta couplers that can be used in the present invention include oil-protected isodasilon-based or cyanoacetyl-based couplers, preferably pyrazoloazole-based couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone 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 coloring dye, and a typical example thereof is as described in US Pat. No. 2.31). No. 082, No. 2.3
No. 43.703, No. 2.600.788, No. 2.
No. 908.573, No. 3.062.653, No. 3
．． No. 152.896 and No. 3.936.015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat. No. 4,351
, No. 897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, US Patent No. 3.
369.879, preferably pyrazolo(5,1-C] (1,,2,-4) triazoles, as described in U.S. Pat. 24220
(June 1984) and Research Disclosure 24230 (1)
The imidazo[1,2- b) Pyrazoles are preferred, as described in European Patent No. 1
) pyrazolo(1,5-b)(1,
2,4)) Riazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474.293, preferably U.S. Pat. No. 4.052.
, No. 212, No. 4,146.396, No. 4.22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8.233 and No. 4.296.200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369.929 and U.S. Pat.
No. 01,171, No. 2.772.162, No. 2.
895.826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3,772.
．． Phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus described in US Pat. No. 2,772.162 and US Pat. No. 3.75
8.308, 4,126.396, 4.33
No. 4.01), No. 4.327,173, West German Patent Publication No. 3.329.729 and Patent Application No. 1983-4267
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 3,446,622.
No. 4.333.999, No. 4.451.55
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 9 and No. 4,427.76.7.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusing couplers are magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570; .234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and specialty couplers described above may form dual or more polymeric polymers; typical examples of polymerized dye-forming are U.S. Pat. .21). Specific examples of polymerized magenta couplers are given in British Patent No. 2.1.
No. 02.173 and US Pat. No. 4.367.282.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mole, 0 for magenta coupler, OO3 to 0.
3 mol, and for cyan couplers 0.002 to 0.
It is 3 moles.

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

- Formula (1) General formula (") H Y7 - Formula (III) General formula (IV) General formula (V) CHl General formula (I) ~ (V) Ite, Y"% Y"%Y
", Y" or Y7s is a coupling-off group (hereinafter referred to as a leaving group), and the leaving group is a coupling-off group via an oxygen, nitrogen, sulfur or carbon atom to a coupling active carbon, an aliphatic group, an aromatic group. , a heterocyclic group, an aliphatic/aromatic or heterocyclic sulfonyl group, a group that binds an aliphatic/aromatic or heterocyclic carbonyl group, a nitrogen-containing heterocyclic group that connects with a nitrogen atom at the coupling position, These are halogen atoms, aromatic azo groups, etc., and the aliphatic, aromatic, or heterocyclic groups contained in these leaving groups may be substituted with substituents permissible under R71 (described below), and these substituents When there are two or more groups, they may be the same or different, and if these substituents are further R? l may have permissible substituents.

- In the formula (ri and - formula (n), R'FI, R?
4 and R? Each S preferably has 1 to 36 carbon atoms.
an aliphatic group, preferably an aromatic group having 6 to 36 carbon atoms (e.g., phenyl group, naphthyl group, etc.), a heterocyclic group (e.g., 3-pyridyl group, 2-furyl group, etc.), or an aromatic or heterocyclic group. represents an amino group (e.g., anilino group, naphthylamino group, 2-benzothiazolyl amino group, 2-pyridylamino group, etc.), and these groups further include:
Alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkenyloxy group, acyl group, ester group, amide group, sulfamide group, imide group, ureido group, aliphatic or aromatic sulfonyl group, aliphatic or It may be substituted with a group selected from an aromatic thio group, a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom, and the like.

As used herein, the term "aliphatic group" refers to a linear, branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl and alkynyl groups.

-31 In formula (I), R”lt preferably has 1 carbon number
-20 aliphatic groups, which may be substituted with the permissible substituents for R'1).

In the general formula CI) and formula (If), R7'' and R?& are each a hydrogen atom, a halogen atom, preferably an aliphatic group having 1 to 20 carbon atoms, and preferably 1 carbon atom.
~20 aliphatic oxy groups or acylamino groups having 1 to 20 carbon atoms (e.g., acetamido, penzamide, tetradecaneamide, etc.), and these aliphatic groups, aliphatic oxy groups, and acylamino groups contain R? I may be substituted with a permissible substituent.

In general formula (I), R''lt and R71 may jointly form a 5- to 7-membered ring.

-i In formula (II), R7S and R? - may jointly form a 5- to 7-membered ring.

-R in formula (1)? ISR? ft.R? ! Or Y
? +, or - in formula (II), R''
, R"% R" or Y" may independently or jointly form a dimer or more multimeric coupler. When a dimer, those groups are It can be used as a simple bond or as a divalent linking group (e.g., divalent groups such as alkylene groups, arylene groups, ether groups, ester groups, amide groups, and divalent groups combining these groups), and can be used as an oligomer or When forming polymers, these groups are preferably attached to the polymer backbone through divalent groups such as those described for dimers. Even if it is a homopolymer, other non-chromogenic ethylene-like monomers (e.g. acrylic acid, methacrylic acid, methyl acrylate n-butylacrylamide, β-hydroxy methacrylate, vinyl acetate, acrylonitrile, styrene, croton V, = water (maleic acid, N-vinylpyrrolidone, etc.) may form a copolymer with one or more types.

In general formula (I), preferable R'' and - formula (II
) is the preferred R? % is a substituted or unsubstituted alkyl group or aryl group, and as a substituent for the alkyl group, an optionally substituted phenoxy group or a halogen atom is particularly preferable, and the aryl group has at least one halogen atom, alkyl group, etc. Particularly preferred are phenyl groups substituted with groups, sulfonamido groups, sulfamoyl groups, carboxy groups or acylamino groups.

In the general formula (I[), R'' is preferably a substituted alkyl group or a substituted or unsubstituted aryl group, and the alkyl group or substituent is particularly preferably a halogen atom, and the aryl group is a phenyl group, a halogen atom, or a sulfonamide group. , a phenyl group substituted with at least one sulfamoyl group is particularly preferred.

In general formula (I[), R12 is preferably an optionally substituted alkyl group having 1 to 20 carbon atoms.

The substituent for R72 is preferably an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imido group, a ureido group, or an alkyl or arylsulfonyl group.

- In formula (I), R? 3 is preferably a hydrogen atom, a halogen atom (particularly preferably a fluorine atom or a chlorine atom), or an acylamino group, and particularly preferably a halogen atom.

In the general formula (n), R'' is a hydrogen atom and has 1 to 20 carbon atoms.
An alkyl group or an alkenyl group is preferred, and a hydrogen atom is particularly preferred.

In general formula (If), R? It is preferred that S and R'' form a 5- to 6-membered nitrogen-containing heterocycle.

In general formula (I), R? More preferably, 2 is an alkyl group having 2 to 4 carbon atoms.

-i In formulas (I) and (II), Y'' and Y'' are each preferably a halogen atom, more preferably a chlorine atom.

Couplers represented by general formulas (1) and (II) are:
Each coupler can be used alone or a plurality of couplers can be used in combination.

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

In general formula (III), R? 9 and R? ? The substituents allowed for are the same as the substituents allowed for the aromatic group in R71, and when there are two or more substituents, they may be the same or different.

-i Preferred R in formula (III)? I is a hydrogen atom,
R7s is an aliphatic acyl group or an aliphatic sulfonyl group, and particularly preferred R7s is a hydrogen atom. Preferable? 2
is a type that leaves with either a sulfur, oxygen or nitrogen atom, and a sulfur atom leaving group is particularly preferred.

The compound represented by the general formula (IV) is a 5-5 membered fused nitrogen heterocyclic coupler (hereinafter referred to as 5.5N heterocyclic coupler), and its color-forming nucleus is isoelectronic aromatic with naphthalene. It has a chemical structure that is generally referred to as azapentalene. - Among couplers represented by formula (rV), preferred compounds are IH-imidazo (1,2
-b) Pyrazole, IH-pyrazolo(5,1-c) (
1゜2.4)) Riazoles, IH-pyrazolo [1゜5
-b)(1,2,4)) riazoles and IH-pyrazolo(1,5-d)tetrazoles.

-fQ In formula (V), the substituent of the phenyl group of the N-phenylcarbamoyl group Q can be arbitrarily selected from the group of permissible substituents when R'' is an aromatic group, When there are two or more substituents, they may be the same or different.

Preferred leaving groups Y'' include groups represented by the following general formulas (Vl) to (XIr).

OR''° (VI) R91) represents an optionally substituted aryl group or heterocyclic group.

(■) (■) R91SRI2 each represents 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 alkylsulfonamide group, and a sulfamoyl group. represents a group, an alkylsulfinyl group, 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.

Represents a nonmetallic atom required to form a ring or a six-membered ring.

Among general formula (IX), preferably (X) to (XI[)
can be mentioned.

In the formula, R93 and RS4 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 R9s SRs s and Rs i
each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group, and W2 represents an oxygen or sulfur atom.

References describing other exemplary compounds or synthetic methods of couplers represented by the formulas (1) to (V) are listed below.

-ffi The cyan coupler represented by formula (1) and -formula (If) can be synthesized by a known method.
23.730, 3.772.002, etc. - The cyan coupler represented by formula (II) is disclosed in U.S. Pat.
．． 333.999, 4.327.173, etc.

Magenta couplers represented by the -i formula (III) are disclosed in JP-A-49-74027, JP-A-49-74028, JP-A-4B-27930, JP-A-53-33846, and U.S. Patent No. 3,519,429. It is synthesized by the method described in . - Magenta couplers represented by formulas (IV-1) to (IV-4) are disclosed in Japanese Patent Application Laid-Open No. 59-1625, respectively.
No. 48, U.S. Patent No. 3,725.067, JP-A-59
-171956 and JP-A-60-33552.

The yellow coupler represented by the general formula (V) was published in Japanese Unexamined Patent Publication No. 5
It can be synthesized by the methods described in Japanese Patent Publication No. 4-48541, Japanese Patent Publication No. 58-10739, US Patent No. 4.326.024, Research Disclosure No. 18053, and the like.

Preferred specific examples of couplers are shown below.

II II I CI! I ■ M-2 Shig Yes 1 C.I. υ1・n+7 M-17 CI(.

In the present invention, the water-insoluble, organic solvent-soluble polymer and the specific oil-soluble coupler are dissolved in a high-boiling organic solvent to form lipophilic fine particles. into the photosensitive material. Here, the high boiling point organic solvent is US Pat. No. 2.322.02
7, etc., and specifically, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phthalate, etc.), phosphate, tricresyl phosphate, dioctyl butyl phosphate, monophenyl-pt-7'tylphenyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate) , alkylamides (e.g. diethyl laurylamide, dibutyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesates (e.g. tributyl trimesate), compounds containing epoxy rings (e.g. U.S. Pat. No. 4,540,657),
Phenol M (e.g. ethers (e.g. phenoxylene glycol monophenyl ether)).

The size of the fine particles to be formed is not particularly limited, but is usually 0.05 to 2.0μ, preferably 0.05 to 1.0μ,
More preferably, it is 0.1 to 0.20μ.

In addition, the ratio of polymer/coupler in fine particles (weight ratio)
is preferably from 1/20 to 20/1, more preferably from 1/10 to 10/1.

Furthermore, the total amount of polymer and coupler in the fine particles is 20~
It is preferable to set it to ioo%, preferably ao-too%. As mentioned above, a co-solvent for dissolving the polymer may be added to the fine particles.

The silver halide light-sensitive material that is the object of the present invention is formed by introducing the above-mentioned fine particle dispersion into an emulsion layer and coating it on a reflective support by a known method. here,
A variety of known materials are used to form emulsion layers. That is, the silver halide emulsion contains silver iodobromide, silver bromide,
Any halogen composition such as silver chlorobromide or silver chloride can be used. 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 more preferably a silver chloride content of 80 mol% or more.
It is particularly preferable to use silver bromide in an amount of 5 to 100 mol%, and when high sensitivity is required and fog during production, storage, and/or processing needs to be particularly low.
Silver chlorobromide emulsions containing 0 mol% or more (may contain 3 mol% or less silver iodide) are preferred, and more preferably 70 mol%.
The above is preferable. Silver iodobromide and silver chloroiodobromide are preferable for color light-sensitive materials for photography, where the silver iodide content is 3 to 1.
5 mol% is preferred.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain, or may have different phases. 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 value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size ratio) is within 20%, particularly preferably 1
It is preferable to use a so-called monodispersed silver halide emulsion of 5% or less in the present invention, and in order to satisfy the target gradation of the light-sensitive material, grains in the emulsion layer having substantially the same color sensitivity are preferably used. Two or more types of monodisperse silver halide emulsions having different sizes (preferably those having the above-mentioned fluctuation rate as monodispersity) can be mixed in the same layer or coated in separate layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or a multilayer.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical
It may have a crystalline form (ular) (or it may have a composite form of these crystal forms).

Tabular grains may also be used, especially when the length/thickness ratio is 5.
~8 or more tabular grains account for 5 of the total projected area of the grains
An emulsion containing 0% or more may also be used. An emulsion consisting of a mixture of these various crystal forms may also be used.

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

The photographic emulsion used in the present invention is Re5earChDi
closure vol, l 7 Q Item N
o, 17643 (L n, ■) (1978, 12).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are described in Research Disclosure Vol. 176, No. 17643 (197
August, December) and volume 187, Nα18716
(January, 1979)), and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the locations are shown in the table below.

1 Chemical sensitizer page 23 page 648 right column 2
Sensitivity enhancer Same as above 4 Brightener
24 page 6 Coupler 25 page 7 Organic solvent 25 page 9 Stain inhibitor Page 25 right column 650 page left to right column l
O dye image stabilizer page 25 1) Hardener page 26 page 651 left column 12 Binder page 26 Same as above 13
Plasticizer, lubricant Page 27 Page 650 Right column 15
Static inhibitor Page 27 Same as above The reflective support on which the above emulsion layer is coated increases the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. , titanium oxide on support,
Examples include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing dispersed light-reflecting substances as a support.

In the present invention, the above-mentioned silver halide color photographic light-sensitive material is
A color developer containing an N-hydroxyalkyl-substituted p-phenylenediamine derivative and substantially free of benzyl alcohol is used for processing, for example, by the following method.

A. Color development - rinsing - bleach fixing - washing - drying B. Color development - rinsing - bleach fixing - washing - drying C0 black and white development - rinse - reflective exposure - color development - rinse - bleach fixing - washing - drying Here, Instead of washing with water (i) stabilization or (ii) washing with water -
Stabilization can be performed and rinsing can be omitted.

Next, each treatment step and treatment liquid will be explained.

1. Floating Process The present invention is characterized by using a developing solution containing N-hydroxyalkyl-substituted p-phenylenediamine as a developing agent. Preferred developing agents can be represented by the following formula.

In the formula, R□ 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+z is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. RI3 is an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and A is an alkyl group having at least one hydroxyl group and which may have a branch. A group, more preferably I4+CHzHc)tr(COboxTRI&■s), where RI4 and RIjsR1& are each a hydrogen atom, a hydroxyl group, or 1 to 3 which may have a hydroxyl group.
represents an alkyl group having R1 carbon atoms;
At least one of SSRI & is an alkyl group having a hydroxyl group * nl S”12, ns are 0 and 1, respectively
．． 2 or 3, and HX is hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, nitric acid or phosphoric acid.

A typical example of such p-phenylenediamine color developing agents is that they are unstable in their free amine form and are commonly used as salts (most commonly those specified by the formula above). 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 sulfate hydrate [This is commercially available under the name CD-4 and is used in most color photographic systems (e.g. Eastman Kodak C41 system, , Konishi Photo Industry Co., Ltd. CN
(used for developing color negative films such as the K-4 system) has been found to be particularly effective.

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

(Exemplary compounds) Hz N.H.

N.H.

Hz NH2 NH1 g　　HsC(C mountain 0R 1N NH2 N.H.

Among these exemplified compounds, the symbols a, bSf.

Those represented by g and h are preferred, those represented by a, b and f are particularly preferred, and those represented by a are more preferred.

The amount of these compounds used is 1g to 10g per 12 of the processing solution.
It is preferably used within the range of 0g, more preferably 3g.
~30g is used.

These N-hydroxyalkyl-substituted p-phenylenediamine derivatives of the present invention are described in Journal of the American Chemical Society, Vol. 73, p. 3100 (19
It can be easily synthesized by the method described in 1995).

The developer of the present invention is further characterized in that it substantially does not contain benzyl alcohol. Here, "substantially not containing" means 3g or less, preferably 1g per developing solution 1).
Below, it is more preferable not to contain it at all.

The color developing solution may also contain pH buffering agents such as alkali metal carbonates, borates, or phosphates, and development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles, or mercapto compounds. It is common to include an agent or an antifoggant. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo(2
, 2, 2) octane), organic solvents such as ethylene glycol, diethylene glycol, polyethylene glycol, development accelerators such as quaternary ammonium salts, amine salts, dye-forming couplers, competitive couplers, sodium caprase agents such as boron hydride,
Auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetra Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, ethylene glycol (〇-hydroxyphenylacetic acid) and their salts. This can be cited as a representative example.

The PTT of these color developing solutions is generally 9 to 12, and the replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 31 or less per square meter of light-sensitive material. By reducing the bromide ion concentration in the replenisher, the bromide ion concentration can be reduced to 500++1 or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, bleaching is usually applied. The bleaching treatment may be carried out simultaneously with the fixing treatment, or may be carried out separately (bleaching and fixing), or in order to speed up the processing, a bleaching and fixing treatment may be carried out after the bleaching. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■), cobalt (■), chromium (Vl),
Compounds of polyvalent metals such as copper (n), peracids, quinones,
Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (I), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediamine. Aminopolycarboxylic acids such as tetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or citric acid,
Complex salts such as tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron(III) complex salts and persulfates, including iron(m) complex salt of ethylenediaminetetraacetate, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (II) complexes is usually 5.5 to 8, but in order to speed up the processing, it can be processed at an even lower pH. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Useful bleach accelerators include those specifically described in U.S. Pat.
No. 893.858, West German Patent No. 1,290.812,
Compounds having a mercapto group or disulfide bond as described in JP-A-53-95,630, Research Disclosure + No. 17+ 129 (July 1978), etc.; as described in JP-A-50-140,129; thiazolidine derivatives; thiourea derivatives as described in U.S. Pat. No. 3,706,561; iodide salts as described in JP-A-58-16,235; Oxyethylene compounds; Japanese Patent Publication No. 45-883
Examples include the polyamine compound described in No. 6; bromide ion, etc. Among these, compounds having a mercapto group or a disulfide group are preferred because they have a large promoting effect, and are particularly preferred, such as U.S. Pat. No. 3,893,858 and West German Patent No. 1,290.
．． Compounds described in No. 812 and JP-A No. 53-95.630 are preferred. Furthermore, compounds described in US Pat. No. 4,552,834 are also preferred; these bleach accelerators may be added to the sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the above desilvering treatment, a washing and/or stabilization process is generally carried out. can be set over a wide range depending on the washing water temperature, the number of washing tanks (number of stages), replenishment methods such as countercurrent or forward flow, and various other conditions.

Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the 5ociet.
y of Motion Picture and Te
1evision Engineers Volume 64,
P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" written by Hiroshi Horiguchi, "Microbial It is also possible to use the disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by Japan Antibacterial and Antifungal Science Kinsen.

The pH of the washing water used is 4-9, preferably 5.
-8. Washing water temperature and washing time also vary depending on the characteristics of the photosensitive material.
Although various settings can be made depending on the application, -m is 20 seconds to 10 minutes at 15-45°C, preferably 30 seconds to 5 minutes at 25-40°C.
A range of minutes is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8.543 and 58-14
．． All known methods described in No. 834, 60-220.345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed, and as an example, the bath is used as a final bath for color photographic materials. Mention may be made of stabilizing baths containing formalin and surfactants.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

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 processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342.59
Indoaniline compound described in No. 7, No. 3.342,
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35.628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64.339, JP-A-57-144547, and JP-A-58-1) 5.438.

The above-mentioned various processing liquids are used at 10°C to 50°C.

Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. In addition, West German Patent No. 2.226.770 or U.S. Patent No. 3.674,
A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 499 may be performed.

〔Effect of the invention〕

According to the present invention, when a color developing agent such as 4-amino-3-methyl-N-ethyl-(βmethanesulfonamidoethyl)aniline sulfate, which is conventionally said to have relatively excellent color image stability, is used. It is possible to achieve better color image stability (particularly excellent dark fading resistance) and rapid processing compared to the conventional method.

Furthermore, according to the present invention, color negative film can be processed with the same developer after processing, which is a great advantage compared to conventional processing methods in which negative film and paper are processed using separate developers. is obtained.

(Example) The present invention will be explained in more detail based on examples.

Example 1 Each layer was coated on a paper support laminated on both sides with polyethylene to have the layer structure shown in Table A, and the coupler and polymer were as shown in Table 1.
314 were produced respectively. The coating solution was prepared as follows.

Preparation of coating solution for the -th layer Add and dissolve 27.2 cc of ethyl acetate and 7.7 cc of solvent (c) to 23.8+on+ol of yellow coupler (a) and 4.4 g of color image stabilizer (b), and dissolve this solution in 1
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 0% sodium dodecylbenzenesulfonate.

The polymer (fl) was dissolved in the above ethyl acetate (dissolved at a rate of 7.7 g per 10 cc of ethyl acetate), while the silver chlorobromide emulsion (EMI, EM2) was added with the following blue-sensitized sensitizer. A dye was prepared by adding 1) s, oxio-' moles per mole of dye. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown in Table A. The fine particles containing yellow coupler (a) and polymer (fl) dispersed in the coating liquid had a particle size of about 0.15 μm.

Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. In this case, the method for preparing the polymer solution and the particle size of the polymer-containing fine particles were also the same as in the case of the first layer.

The gelatin hardening agent for each layer is 1-oxy-3,5-
Dichloro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

5.0 x 10-' mol per 1 mol of blue-sensitive emulsion layer (halogenated 1))
Green-sensitive emulsion layer SO+N(CzHs)z (halo, 4.0×10-' mole per mole of Sl genide) and SOsHN(CJs)a (per mole of silver halide?, 0x1O-' mole) red-sensitive emulsion layer (0.9xlO-' mole per mole of silver halide) For the red-sensitive emulsion layer, the following compounds were added to 1 mole of silver halide.
Added 2.6X10-3 moles per mole.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)=5-mercaptotetrazole was added per mole of silver halide, respectively.
5 X 10'' moles, ?, 7 X 10-' moles, 2.
5XIO-' moles were added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, and 7-titrazaindene were each added at 1.2 x 1 per mole of halogenated i.
o-" mole, 1.1 x 10-" mole L/added.

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

(Note) The compounds used in the above multilayer color photographic paper are as follows.

(a) Yellow coupler: Shown in Table 1.

(b) Color image stabilizer (6) Color mixing prevention agent H (e) Magenta coupler: Shown in Table 1.

(f) Color image stabilizer (Xuan color image stabilizer H (h) Solvent 2:1 mixture (volume ratio) (1) Ultraviolet absorber CHtCllzCOOCJtl, 2:9:8 mixture (weight ratio) of (Jl Color mixing prevention agent H H (kl solvent o=p÷OCJ+q(iso))+ (1) Cyan coupler: Shown in Table 1.

(e) Color image stabilizer H CHzCHzCOOCsLt, (n) Polymer The polymers used are shown in Table 1. However, the number average molecular weight of each polymer in this example and each example below is as follows.

P-330,000 P-5.67 million P-5.76 million P-5.85 million P-5.93 million P-6.06 million P-6.47 million (0) Solvent Emulsion used *Represents particle distribution.

Next, photosensitive material R1) was prepared in the same manner as above except that the yellow, magenta, and cyan couplers were changed to the following 4-equivalent couplers Y-A, M-A, and C-A.

-A M-A -A OI( The treatment steps and treatment liquid formulation are as follows.

-Sara-Ikko-ri l-degree-Satsu-Ichi-Sara-Ichiriki-U-
Development 38℃ 1 minute 00 seconds Bleach fixing 34℃
Wash with water for 1 minute 00 seconds ■ Wash with water for 20 seconds at 34℃ ■ Wash with water for 20 seconds at 34℃ ■ Dry for 20 seconds at 34℃ 80℃ 50
Second (Water wash ■ → ■ 3-tank countercurrent force type.) The composition of each treatment solution is as follows.

Meng]: Old Shunli Water 800m
1 diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid (602) 2.0 g nitrilotriacetic acid 2.0 g potassium bromide 0.5 g potassium carbonate,
30g diethylhydroxyamine 4.0g 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 Geigi) 1.
Add 5g water to 1000ml/lp
H (25℃) 10.251 engineering 1 storm water 4 Q 0
mff1 ammonium thiosulfate (70χ) 200III
I! Sodium sulfite 20g Ethylenediaminetetraacetate Iron(II) Ammonium 60g Ethylenediaminetetraacetic acid disodium 5g Add water 1000+j! pH (25℃")
6.70 water-mass water ion-exchanged water (calcium, magnesium each 3 ppm or less) Photosensitive materials prepared as described above (5ll-314 and R1)
After adjusting the color temperature of a tungsten light source to 4800K with a filter and applying wedge exposure of 20 CMS, color development processing was performed in the above processing step. Here, the color development rate of the maximum density of the yellow dye obtained in the above 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□8%).

In addition, each sample treated in the above treatment step was heated to 70°C and 80%
The sample was stored for two weeks under the following conditions, and the decrease (ΔD!, .) in the density of each of the yellow, magenta, and cyan dyes before and after storage relative to the density of 2.0 before and after storage 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 the comparative example, the change in ΔD2 from no polymer addition to polymer use. . Although the improvement was not remarkable (patient 1
．． N1) 5.6) for 2), according to the invention the polymer,
Certain coupler and certain color developing agent combinations significantly reduce ΔD2. . is improved (llh3.4 vs. N1)
L7.8).

Also, at this time, it can be seen that according to the present invention, D + asx is also sufficient. Furthermore, it can be seen that even better results are obtained using a 2-equivalent coupler (llh7.8
vs. 1) h12-34).

In Table 1, the color developing agent is 12 m+noj! 7
D-1 to D-3 have the following structures (the same applies hereinafter).

In addition, the cyan coupler C-1/C-4 has a molar ratio of 1/1.
They were used together so that (the same applies below).

Example 2 Multilayer color photographic paper S21-3 having the layer structure shown in Table B by coating each layer on a paper support laminated on both sides with polyethylene, and having couplers and polymers as shown in Table 2.
24 were produced respectively. The coating solution was prepared as follows.

Preparation of coating solution for the first layer: 23.8 mmol of yellow coupler (a) and 4.4 g of color image stabilizer (b), and 27.2 c of ethyl acetate.
c and solvent (C) 7,7 cc were added and dissolved, and this solution was added with 8 cc of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing cc. -Force field silver bromide emulsions (EM7, EM8) were prepared by adding the following blue-sensitive sensitizing dyes in 5.0×10 −' mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown in Table B. Coating solutions for the second to seventh layers were also prepared in the same manner as the first N coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-di5chloro-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 exactly the same as in Example 1.

The following spectral sensitizing dyes were used in each layer.

Front window emulsion layer (5.0xlO-' mol per mol of silver halide) Green-sensitive emulsion layer (4.0x10-' mol per mol of halide f1)
and 5-3 of Example 1 (silver halide, per mole?, OX 10-'-1-l) Red-sensitive emulsion layer; the same compound 5-4 as in Example-1 was used.

For the red-sensitive emulsion layer, the same compound as in Example 1 was added at 2.6 x 10-' moles per mole of halogenated GM.

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the pre-malignant emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer at a concentration of 8% per mole of silver halide, respectively.
．． 5X10-' mol, 7.7x10-4 mol, 7.5X
10-'mol was added.

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

(Note) The compounds used in the above multilayer color photographic paper are as follows.

(a) Yellow coupler, (e) Magenta coupler, (
1) Cyan coupler and (n) polymer are shown in Table 2.

伽), (f) and (-color image stabilizer, (C), □□□)
and (0), solvent (d) and color mixing inhibitor of U) and (il
The ultraviolet absorber is the same as that used in Example 1.

(gl color image stabilizer (h) Solvent 1:1 mixture (volume ratio) Emulsion used *Same as Example 1.

Next, the yellow, magenta, and cyan couplers of the above photosensitive material were Y-ASM-A as in Example 1.

Photosensitive material R21 was prepared in the same manner as above except that C-A was changed.
I made it.

After imagewise exposure of the photosensitive material shown in Experiment Nα10 in Table 2, continuous processing (running test) was performed using a paper processing machine until twice the tank capacity for color development was replenished in the following processing steps. .

Color development 35℃ 30 seconds 161m j!
17 j! Bleach fixing 30-36℃ 45 seconds 161
m 1 171Water ■ 30-37℃ 20 seconds
-101 Water wash ■ 30~37℃ 20 seconds -10f
lWash ■ 30~37℃ 20 seconds -IN water wash■
30-37℃ 30 seconds 248m R101 dry
Drying: 70 to 80° C. for 60 seconds (3 tanks with countercurrent blade type washing from ■ to ■). The composition of each treatment solution is as follows.

Color developer tank liquid replenisher water
800m 1 80
0m 1 ethylenediamine-N,N.

N',N'-tetramethylenephosphonic acid 1.5g 1.5gdiethylhydroxylamine 4.2g 5.9g2
-Methyl-1,4-diazabicyclo[2,2,23 Octane 6.0g 6.0g Sodium chloride 1.4g -Potassium carbonate 25g 25g Color developing agent See Table 2 12 mmol 17 mm
ol Fluorescent brightener (4,4'-diaminomethylben-based) 2.0g 2.5
g Add water to 1000ml1) 0100O! Water Ferric ethylenediaminetetraacetic acid 60°Og Ammonium dihydrate Ethylenediaminetetraacetic acid 5.0g Disonasodium salt Sodium sulfate 12.0g Ammonium thiosulfate aqueous solution 260.0-(1.23 mol)
(70%) Acetic acid (98%) Add 5.0ml water to 10100O! pH(
25℃) 6.0 Washing liquid (tank liquid and replenisher liquid common) Deionized water 10001IIl Sodium isocyanurate dichloride 0.02g Polyoxyethylene-p-monononylphenyl nityl (average degree of polymerization 10) 0.2g *Deionized water was obtained by passing tap water through a hotbed column containing a mixture of a strongly basic anion exchange resin and a strongly acidic cation exchange resin.

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

After the continuous processing, each photosensitive material was heated to 20C in the same manner as in Example 1.
The color development rate of the highest density of yellow dye by the above treatment was determined with respect to the highest concentration of yellow dye at a development time of 1 minute and 30 seconds after MJ exposure, and the yellow stain immediately after the treatment was measured. Further, discoloration of each dye at a density of 2.0 immediately after treatment was evaluated in the same manner. The results are shown in Table 2.

As is clear from Table 2, according to the present invention, sufficient color development speed and good implicit color fading properties can be obtained.

Example 3 The first layer (bottom layer) to the seventh layer (
The photographic paper sample S31 was prepared by sequentially applying and forming the uppermost layer). The coating solution for each layer was prepared as follows. The details of the structural formulas of the couplers, color image stabilizers, etc. used in the coating solution will be described later.

The coating liquid for the first layer was prepared as follows. That is, 263.6 g of yellow coupler and 93.6 g of anti-fading agent.
3 g, high boiling point solvent (p) 10 g and solvent (q) 5 g,
600 mj of ethyl acetate as a co-solvent! After heating and dissolving the mixture to 60°C, 330 mI of a 5% aqueous solution of Alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by Denipon) was added. 3300ml of 5% gelatin aqueous solution containing
j! mixed with. This liquid was then emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the sensitizing dye for the blue-sensitive emulsion layer and 1
-methyl-2-mercapto-5-acetylamino-1,
Added to 1400 g of emulsion (containing 96.7 g as Ag and 170 g of gelatin) containing 3,4-triazole,
Further, 2,600 g of a 10% aqueous gelatin solution was added to prepare a coating solution.

The coating liquids for the second layer to the 71i were prepared in accordance with the composition of Table C.
It was made according to.

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

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

n2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole o2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole p di(2-ethylhexyl) phthalate q dibutyl phthalate r 2,5-diter t-amylphenyl-3゜5
-di-tert-butylhydroxybenzoate s 2,5-di-tert-octylhydroquinone t 1,4-di-tert-amyl-2,5-dioctyloxybenzene u2,2'-methylenebis(4-methyl-6-tert
-butylphenol) The following were used as sensitizing dyes for each emulsion layer.

Blue-sensitive emulsion layer; anhydro-5-methoxy-5'-methyl-3,3'-disulfoprobyl selenacyanine hydroxide; green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3' -Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer i3.3'-diethyl-5-methoxy-9
,9'-(2,2-dimethyl-1,3-propano)thiadicarbocyanine iodide and 1-methyl-2-mercapto-5-acetylamino-1,3,4- as a stabilizer for each emulsion layer. Triazole was used.

The following dyes were used as anti-irradiation dyes.

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-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt and 1,2-bis(vinylsulfonyl) as a hardening agent. ) using ethane.

The couplers used are as follows.

Yellow coupler Magenta coupler Cyan coupler Next, the yellow, magenta and cyan couplers of the above light-sensitive material were respectively used in Y-ASM-A used in Example 1.
Color photographic paper R31 was produced in the same manner as above except that the paper was changed to , CA.

As described above, after the produced color photographic paper 331 is exposed in a wedge pattern, various color developing solutions are applied in the following processing steps.
Running process until replenishing 3 times the tank capacity (
Continuous processing) tests were conducted.

Processing process Temperature Time Replenishment amount Color development 35℃ 30 seconds 160 ml/m”
Bleach fixing 35℃ 45 seconds 100ml/m
'Stabilization■ Stabilization at 30℃ for 20 seconds■ Stabilization at 30℃ for 20 seconds■ 30℃, 20 seconds 200m1/rr
r Drying 60-70°C for 30 seconds Stabilization 3-tank countercurrent force method from ① to ② The composition of each treatment solution used is as follows.

Difference: JILL LIL fit Filter length melon Diethylhydroxylamine 4.2g 6.0g Fluorescent brightener (4,4'-diaminomethylben type) 3.0g 4.0
g Ethylenediaminetetraacetic acid 1.0 g 1.5 g Potassium carbonate 30.0 g 30.0 g
Sodium chloride 1.4g 0.1g Color developing agent 12mn+ol 17m+m
ol (see Table 3) Triethylenediamine (1,4-diazabicyclo(2,2,2) octane 1,2-dihydroxyben 3,4°6-Doris 7L, fonic acid 300n+g 300
Add mg water 1000m 12 10
00ml pH10,1010,50 1 liquid water from counterfeit 40
0m j! Ammonium thiosulfate (70%) 100m
l! Ammonium sulfite (40%) 27.5mf
Ethylenediaminetetraacetic acid Acetate I[) Ammonium 60g Ethylenediaminetetraacetic acid disodium 3g Add water 1000m j! pH (25
7.10% 1-hydroxyethylidene 1,1 monodiphosphonic acid (60%) 1.6ml Bismuth chloride 0.3g Polyvinylpyrrolidone 0.3g Aqueous ammonia (26%
) 2.5mj! Nitrilotriacetic acid
1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.05 g 2-octyl-4-isothiazolin-3-one 0.05 g Fluorescent brightener (4,4'-diaminomethylben-based 1. Add 0g water to 1000ae j!pH (2
5°C) 7.5 After continuous processing, the above photosensitive materials S31 and R31 were prepared in Example 2.
Wedge exposure was performed in the same manner as above and evaluation was made. The results are shown in Table 3.

From Table 3, it can be seen that according to the present invention, similar to Example 2, good color development and fading properties can be obtained.

Example 4 A color photographic material was prepared by coating the following layers 1 to 1) on a paper support laminated on both sides with polyethylene. The side of the polyethylene coated with the first layer contained titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive N composition) The components and coating amounts in g/rd are shown below.

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

1st layer (antihalation multilayer) Black colloidal silver 1.00 Gelatin 2.00 2nd layer (low sensitivity red sensitive layer) Silver iodobromide spectrally sensitized with red sensitizing dye (ExS-1, 2) Silver iodide 3.5 mol%, average grain size 0.5μ)
0.15 gelatin
1.00 polymer (p-57)
0.40 cyan coupler (ExC-1)
0.30 Anti-fading agent (Cpd-1,2,3) ()
,,15 coupler solvent (Solv-1,2) 0.0
6 Third layer (high sensitivity red sensitivity N) Silver iodobromide spectrally sensitized with red sensitizing dye (ExS-1, 2) (silver iodide 8.0 mol%, average grain size 0.7μ)
') 0.1) 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 (Solv-1,2) 0.0
4 4th layer (middle layer) Yellow colloidal silver 0.02 Gelatin 1. OO color mixing inhibitor (Cp
d-4) 0.08 color mixing inhibitor solvent (S o
1 v-3,' 4) 0.16 Polymer latex (Cpd-5) 0.10 5th layer (low sensitivity green sensitive layer) Iodobromide spectrally sensitized with green sensitizing dye (ExS-3) Silver (silver iodide 2.5 mol%, average grain size 0.4μ)
0.20 gelatin
0.70 polymer (p-57)
0.40 magenta coupler (ExM-1) 0.
40 Anti-fade agent (Cpd-6) 0.05 Anti-fade agent (Cpd-7) 0.05 Anti-fade agent (Cpd-8) 0.02 Coupler solvent (
Solv-3,5) 0.15゛6th N (high sensitivity green sensitive layer) Silver iodobromide spectrally sensitized with green sensitizing dye (ExS-3) (silver iodide 3.5 mol%, average grain size 0.9μ)
0.20 gelatin
0.70 polymer (p-57>
0.40 magenta coupler (ExM-1>0.
40 Anti-fade agent (Cpd-6) 0.05 Anti-fade agent (Cpd-7) 0.05 Anti-fade agent (Cpd-8) 0.02 Coupler solvent (
Solv-3,5) 0.15 7th layer (yellow filter layer) Yellow colloid! 0.20 Gelatin 1.00 Antifading agent (Cp
d-4) 0.06 anti-fade solvent (So
1 v-3,5) 0.15 Polymer Latex (Cp
d-5) 0.10 8th layer (low sensitivity blue sensitive layer) Silver iodobromide spectrally sensitized with blue sensitizing dye (ExS-4) (silver iodide 2.5 mol, %, average grain size 0.5μ)
0.15 gelatin
0.50 polymer (p-57)
0.40 yellow coupler (ExY-1)
0.20 Stain inhibitor (Cpd-8) 0.0
01 Coupler solvent (SOIV-2) 0.05 9th layer (high sensitivity blue sensitive layer) Silver iodobromide spectrally sensitized with blue sensitizing dye (ExS-4) (silver iodide 2.5 mol%, Average particle size 1.4μ)
0.20 gelatin
0.50 polymer (p-57)
0.40 yellow coupler (ExY-1)
0.20 Stain inhibitor (Cpd-8) 0.00
1 coupler solvent (Solv-2) 0.05 1st
0 layer (UV absorbing layer) Gelatin 1.50 UV absorber (Cpd-9,1,3) 1.00 Color mixing prevention agent (Cp
d-10) 0.08 ultraviolet absorber (Sol
v-2) 0.30 anti-irradiation dye (
Cpd-1)) 0.04 Anti-irradiation dye (Cpd-12) 0.04 1st) N (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.2
μ > 0.07 gelatin
1.00 gelatin hardener (H-1
) 1.17 (Note) The compounds used in the above color photographic material are as follows.

xS-I X5-2 X5-3 XS-4 Cpd-4: Same as 0) of Example 1.

Cpd-5 Polyethylene acrylate CP-47 average molecular weight 100,000) Cpd-6; Same as (fl) in Example 1.

Cpd-7 Cpd-8 Cpd-10: Same as Example 1 (d).

Cpd-1) Cpd-12 XC-I EXI'l-1 XY-1 The photosensitive material prepared as above was processed in the processing steps shown below.

[Processing process]

First development (black and white development) 38℃ 1'15'' Rinse 38℃ 2'15' Reversal exposure At least 100 Lux or more Color development for 1 second or more
38℃ 1'OO' rinse
38℃ 45# bleach fixing 38℃
2'00' water wash 38℃
2'15" [Treatment liquid composition] Nitrilo-N, N, N-)rimethylenephosphonic acid, pentasodium salt 0.6 g Diethylenetriaminepentaacetic acid, pentasodium salt 4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1.2g Potassium carbonate
35.0 g hydroquinone monosulfonate potassium salt 25.0 g diethylene glycol 15.0 mJ1-phenyl-4-hydromethyl-4-methyl-3-pyrazolidone 2.0 g potassium bromide 0.5 g potassium iodide 5.0 mg water In addition
IIt (pH 9,70) 3.6-cythia 1.8-octanediol 0.2g Nitrilo-N,N,N-trimethylenephosphonic acid, pentasodium salt 0.5g, diethylenetriaminepentaacetic acid. Pentasodium salt 2.0 g 2-Methyl-1,4-diadibicyclo(2,2,2)octane 5.0 g Potassium carbonate 25.0 g Diethylhydroxylamine 3.0 g Color developing agent (D
-1 or compound a) 12 mmol potassium bromide
0.5g potassium iodide
t, add omg water
1) (ptl 10.40) Bleach-fix solution 2-mercapto-1,3,4-triazole 1. Og ethylenediaminetetraacetic acid, disodium, di-salt 5. Og ethylenediaminetetraacetic acid/Fe'(III)/ammonium hydrate 80.
Og Sodium Sulfite 15.0
g Sodium thiosulfate (70% liquid) 160
．． 0mj2 glacial acetic acid 5.
Add Qml water and 1f!
(pH 6,50) Rinse solution and washing water ion exchange water Calcium, magnesium 3 ppm or less Dmax% and ΔD2. as in Example 1. . When evaluated after processing with each color developer, D-
It was found that when Compound A was used, color development and dark fading properties were better than those using Compound 1.

Example 5 Multilayer color photographic papers 331 and R31 similar to Example 3 were each prepared by coating each layer on a paper support laminated on both sides with polyethylene.

Next, a color negative film for photography was prepared by coating each layer having the composition shown below on an undercoated cellulose triacetate support.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/- units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, halogenated l in the same layer
1) The coating amount is expressed in moles.

(Sample 101) 1st N: Antihalation layer black colloidal silver ..... Silver 0.18 Gelatin ..... 0.40 2nd layer; Intermediate layer 2.5-di-t-penta Decylhydroquinone ・・・・・・ 0.18EX-1
......0.07 EX-3...0.02 EX-12...0. OO2U-1...
・・・ 0.06 U-2・・・・・・ 0.08 U-3・・・・・・ 0.10 HBS-1・ ・ ・ ・ ・ ・ ・ 0.10H
BS-2・ ・ ・ ・ ・ ・ 0.02 Gelatin ・・・・・・・ 1.04 3rd layer (1st layer
Red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． Coefficient of variation regarding 6μ particle size 0.15)
Silver 0.55 Sensitizing dye I...6.9X10-' Sensitizing dye■...1.8X10''''5 Sensitizing dye■...3. lX10-'sensitizing dye■
...4.0X10-'EX-2--
----0,350 HBS-1...0.005 EX-10...0.020 Gelatin...1.20 4th layer (
2nd red-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.7μ, average aspect ratio 5.5, average thickness 0.2μ
) ......Silver 1.0 sensitizing dye I
...5. lX10-' range-enhancing dye■...
...1.4X10-'sensitizing dye■ ...
・2.3X10-' sensitizing dye ■・・・・・・3
．． 0X10-5EX-2...0.400 EX-3...0.050 EX-10-----0,015 Gelatin...1 .30 5th layer (
Third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 16 mol%, average grain size 1.1
μ) ・・・・・・Silver 1.60 sensitizing dye■
...5.4X10-'sensitizing dye■
...1.4X10''''5 sensitizing dye■
...2.4X10-'sensitizing dye■...
...3.1X10-5EX-3-----0,2
40 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-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, average aspect ratio 6.0, average thickness 0.15)
・・・・・・Silver 0.40 multiplying dye■
...3.0X10-' sensitizing dye■ ・
...1.0xlO-'sensitizing dye■ ...
・・a=axto-'EX-6・・・・・・0.26
0 EX-1...0.021 EX-7...0.030 EX-8...0.025 HBS-1... 0.100 HBS-4...0.010 Gelatin...0.75 8th layer (
Second green emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0)
．． Coefficient of variation regarding 7μ particle size 0.18)
0.80 Sensitizing dye ■ 2. 1X10-' Sensitizing dye ■...7.0X10-' Sensitizing dye■...2.6X10-'EX-6...
...0.180 EX-8...0.010 EX-1...O,OO8 EX-7...'0.012 HBS- 1...0.160 HBS-4...0.008 Gelatin...1.10 9th layer (
Third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 12 mol%, average grain size 1.θ
μ) ・・・・・・Silver 1.2 multiplying dye V
,...3.5X10-'sensitizing dye■
・・・・・・8. '0X10-' Multiplying dye ■ □
・・・・・・3.0X10-'EX-6・ ・ ・ ・
・ ・ ・ 0.065EX-1)・ ・ ・ ・
・ ・ ・0.030EX-1・ ・ ・ ・ ・ ・
・0.025HBS-1・ ・ ・ ・ ・ ・ ・
0.25HBS-2・ ・ ・ ・ ・ ・ 0.
10 Gelatin ・・・・・・1.74 1st
0 layer (yellow filter N) Yellow colloidal silver ......Silver 0.0SEX-
5...0.08 HBS-3...0.03 Gelatin...0.95 1st) layer (1st blue-sensitive emulsion layer) Tabular layer Silver bromide emulsion (silver iodide 6 mol%, average grain size 0
．． 6μ, average aspect ratio 5.7, average thickness 0.15)
・・・・・・Silver 0.24 concentrating dye■
...3.5X10-'EX-9...
...0.85 EX-8 ...0.12 HBS-1 ...0.28 Gelatin ...1.28 12th layer (2nd blue Emulsion N) Monodisperse silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.8μ grain size coefficient of variation 0.16)...
・Silver 0.45 Sensitizing dye■ ・・・・・・2. lX10-'EX
-9...0.20 EX-10...0.015 HBS-1...0.03 Gelatin...0.46th 13 layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (tff1 iodide) 4 mol%, average grain size 1.3μ) ...... Silver 0.77 sensitizing dye ■ ...・2.2X10-'EX-9・
...0.20 HBS-1 ...0.07 Gelatin ...0.69 14th layer (first protective layer) Silver iodobromide emulsion (iodide Silver 1 mol%, average particle size 0.07
μ) ......iIO, 5U-4...
・・・・・・0.1) U-5・ ・ ・ ・ ・ ・ ・0.17HBS-1
・ ・ ・ ・ ・ ・ 0.90 gelatin
......1.00 15th layer (second protective layer) Polymethyl acrylate particles (approximately 1.5 μm in diameter) ...0.54S-
1...0.15 S-2...0.05 Gelatin...0.72 In addition to the above ingredients, each layer contains a gelatin hardening agent H- 1 and a surfactant were added.

U-5 EX-2 EX-3 )υ3Na EX-4 EX-5 mouth, mouth EX
-9 X-10 tI3 4. Aggravating dye ■ C2H% zHs ■ (CL)4SO3-(+,:H2<'SU3) The color negative film prepared above was cut to a width of 35 mm, and the color photographic paper was cut to a width of 82.5 mm. After each imagewise exposure, these color negative films and color photographic papers were refilled in the proportions listed in Table 4 in an automatic processor (Figure 1) that was constructed so that they were all processed with a common processing solution. I processed it while doing so.

Details of the processing are described below.

The composition of each treatment liquid was the same as that shown in Example 2. After filling the automatic processor with a processing solution, the following processing was performed.

First processing: After the color negative film sample 101 was photographed, it was continuously processed for 30 m.

Second Processing After exposing the two-column photographic paper to light using an automatic printer, it was continuously processed for 90 m.

Third treatment: It was carried out in the same manner as the first treatment.

The same evaluation as in Example 2 was performed on the color photographic paper after the above continuous processing. The results are shown in Table 5. From Table 5, it can be seen that if the structure of the present invention is followed, good coloring properties and fading properties can be obtained.

[Brief explanation of the drawing]

FIG. 1 shows the tank arrangement (plan view) of an automatic processor for mixing processing. In the figure, 1... Color developing tank (101) > 2... Bleach-fixing I'ff (101) 3... Washing tank ■ (51) 4... Washing tank ■ (51) 5... Washing Tank (5I) 6...Drying section 7...Color negative film insertion section 8...Color photographic paper insertion section 9...Color negative film collection section 10...Color photographic paper collection section Hatching (A) The part shown in FIG. 1 shows the transport part of the color negative film, and the hatched part (B) shows the transport part of the color photographic paper. , Relationship to the case of the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 4,
Agent 5, Date of amendment order Initiator 6, Subject of amendment Detailed description of the invention in the specification field f≧ (1) Change “3-methyl-p-amine” in line 13 of page 2 of the specification to “3-methyl-p-amine” 3-methyl-4-amine". (2) The structural formula on page 93, S-2 of the same book is amended as "". (3) "After wedge-shaped exposure" in the 8th line from the bottom of page 132 of the same book is corrected to "after image-wise exposure." (4) “Octane 1.2-di” on page 132, line 1 of the same book
is corrected to “Octane 6.0 g 6.0 g J. (5) “Hydroxyben 3゜4” in the second line of page 132 of the same book.
, "rl, 2-dihydroxybenzene 3°4," is corrected.

Claims (2)

[Claims] (1) At least one diffusion-resistant oil-soluble coupler that couples with an oxidized form of an aromatic primary amine color developing agent to form a substantially non-diffusible dye on a reflective support. A silver halide color photographic light-sensitive material is provided with a layer containing a dispersion of lipophilic fine particles containing at least one kind of water-insoluble and organic solvent-soluble polymer. An image forming method characterized by processing with a color developer which does not contain benzyl alcohol and substantially does not contain benzyl alcohol. (2) At least one kind of the oil-soluble coupler is a two-equivalent coupler.
).