JPH0215256A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease the sensitization and desensitization by the pressure during development processing by incorporating an oil soluble coupler which forms a dye by coupling with the oxidant of an arom. primary amine color developing agent and is imparted with diffusion resistance and monodisperse silver halide particles into a photosensitive emulsion layer at the time of providing said emulsion layer on a base. CONSTITUTION:The polymer of an acrylamide system or methacrylamide system, polyester consisting of polyhydric alcohol and polybasic acid, and polyamide consisting of diamine and dibasic acid and W-amino-W'-carboxylic acid, etc., are incorporated into the photosensitive emulsion layer at the time of coating the base consisting of polyethylene laminated paper with the above-mentioned emulsion layer. The oil soluble coupler which is insoluble in water and is soluble in org. acid is incorporated into the emulsion layer in such a manner and further, the monodisperse silver halide particles are incorporated therein.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material that exhibits little increase or decrease in sensitivity due to pressure applied during development processing.

(Prior art) In order to form a color photographic image, three types of photographic couplers that develop yellow, magenta, and cyan colors are contained in a light-sensitive silver halide emulsion layer suitable for each color, and after exposure, the color changes. The general method is to process with a color developing solution containing a developing agent, and then remove the developed silver generated during the formation of the dye image and the silver halide remaining undeveloped through bleaching and fixing treatments, respectively. It is.

Conventional photosensitive materials have a problem in that during these treatments, the photosensitive material is subjected to pressure and a portion of the photosensitive material becomes sensitized. Although it has been found that the degree of pressure sensitization described above can be improved by monodispersing the silver halide grains contained in the emulsion layer, this effect was not fully satisfactory.

Japanese Patent Publication No. 48-30,194 contains an emulsified dispersion of a coupler using an organic solvent-soluble homopolymer formed from a hydrophobic monomer having a specific structure or a copolymer with a hydrophilic monomer having a specific structure. For photosensitive materials, there is a description that the film quality is hard to a desired degree and resistant to loss caused by pressure.

However, there is no description in this document regarding the effect of improving sensitization when pressure is applied during processing, and in fact, the effect was insufficient.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material that exhibits less sensitivity increase or decrease due to pressure applied before or during development processing.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photosensitive material that is less sensitized due to pressure applied during development processing, and has at least one photosensitive emulsion layer on a support. In a photographic material, at least one diffusion-resistant oil-soluble coupler that forms a dye by coupling with an oxidized product of an aromatic primary amine color developing agent in the light-sensitive emulsion layer is water-insoluble and organic. This is achieved by a silver halide color photographic light-sensitive material characterized by containing monodisperse silver halide grains that are dispersed in coexistence with at least one type of solvent-soluble single or copolymer. .

The polymer according to the present invention will be explained below using specific examples, but the present invention is not limited thereto.

(8) Vinyl polymer Monomers forming the vinyl polymer of the present invention include acrylic esters, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and isobutyl 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, hensyl acrylate, methoxyhensyl 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-
Examples include (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 meccrylate, 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-
4so-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-metho-)-thyl
-xy)ethyl methacrylate, 2-(2-ethoxyel l-=Fn)ethyl methacrylate, 2-(2-butoxyethoxo)ethyl methacrylate-1-1ω methoxypolyethylene glycol methacrylate + 1 ("j added moles n-
6), allyl methacrylate, meccrylic acid dimethylaminoethyl methyl chloride salt, and the like.

Vinyl esters: Specific examples include vinyl acetate, vinyl propione-1, vinyl butyrate, vinyl isobutyrate, vinyl caprony-1, vinyl chloroacetate, vinylmethoxyacetate-1, vinylphenylacetate-1, Acrylamides 1, such as acrylamide, methylacrylamide I, ethylacrylamide, propylacrylamide, butylacrylamide F, tert-butylacrylamide, cyclohexylacrylamide, hensylacrylamide, hydroxymethylacrylamide' , methoxoethyl acrylamide, dinotylaminoethyl acrylamide, phenylacrylamide, dimethylacrylamide, dimethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetone acrylamide,
tert-octylacrylamide, etc.; methacrylamides: for example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohegycylmethacrylamide, hensylmethacrylamide, hydroxy Methylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N-(2-
acetoacetoxyethyl) methacrylamide, etc.; Olefins: for example, dicyclopentadiene, ethyl
/n, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chlorine cobrene,
Butadiene, 2,3-dimethylbutadiene, etc.; Styrene neck: For example, styrene, methylstyrene, dimethylstyrene, trinotylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methkinstyrene, acetogystyrene, chlorostyrene, dimethylstyrene, Chlorstyrene, bromustyrene, vinylbenzoic acid methyl ester, etc.; Vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, nodoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.; Others include butyl crotonate, hexyl crotonate, itacon dinotyl acid, dibutyl itaconate, diethyl maleate, dimethyl maleate, diethyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methylvinylketone, fu,)-nylvinylgetone, methoxyethylvinylketone, glycozyl lac Examples include Relay I, glycidyl methacrylate, ++-vinyloxyriduridone, one-arm vinylpyrrolidone, acrylonitrile, methacrylonitrile, methylenemalonitrile, and vinylidene.

The monomers used in the polymer of the present invention (for example, the above-mentioned monomers) may be used in combination of two or more monomers as comonomers depending on various purposes (for example, improving solubility). Furthermore, in order to control color development and solubility, monomers having an acid group such as those listed below may 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.; monoargyl maleate, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.; citraconic acid; styrene sulfonic acid; vinylhensyl sulfone Pickled 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-methylethanesulfonic acid ,2
-acrylamido-2-methylpropanesulfonic acid, 2
-acrylamido-2-methylbutanesulfonic acid, etc.;
Methacrylamide alkylsulfonic acids, such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-
Methacrylamide-2-methylbutanesulfonic acid, etc.; these acids contain alkali metals (e.g. Na, K, etc.)
Alternatively, it may be a salt of ammonium ion.

Among the vinyl monomers listed above and other vinyl monomers used in the present invention, hydrophilic monomers (
Here, it refers to a polymer that has a water volume of 1 volume when made into a homopolymer. ) as a comonomer, there is no particular restriction on the proportion of the hydrophilic monomer in the copolymer as long as the copolymer does not become water-soluble, but it is usually preferably 40 mol% or less, more preferably 20 mol%. % or less, more preferably 10 mol% or less. Furthermore, when the hydrophilic comonomer to be copolymerized with the present invention has an acid group, the proportion of the comonomer having an acid group in the copolymer is usually adjusted from the viewpoint of image storage stability as described above. It is not more than 20 mol %, preferably not more than 10 mol %, and most preferably does not contain such a comonomer.

The monomers of the invention in the polymer are preferably methacrylate, acrylamide and methacrylamide. Particularly preferred are acrylamide and methacrylamide.

(B) Polymers by condensation polymerization and polyaddition reactions Polymers by condensation polymerization include polyesters of polyhydric alcohols and polybasic acids, diamines, dibasic acids, and ω-
Polyamides made from amino-ω'-carboxylic acids and the like are generally known, and polyurethanes made from dicyanate and dihydric alcohol are known as polymers made by a heavy ionic addition reaction.

As polyhydric alcohols, glycols or polyalkylene glycols having the structure tIO-R, -OH (R is a hydrocarbon chain having 2 to about 12 carbon atoms, especially an aliphatic hydrocarbon chain) are effective. , as a polybasic acid, HOO
Those having C-R2-COOII (R2 represents a simple bond or 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, 1.3-7'ropylene glycol, trimethylolpropane, 1.4-butanediol, isobutylene diol, 15-bentanediol, neopentyl glycol, 16-hexanediol, 1,7-hebutanediol , 18-octanediol, 1,9-nonanediol, 110-decanediol,
1.11-undecanediol, 1.12-dodecanediol, Li2-)lysocanediol, glycerin,
Examples include 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.

Examples of diamines include hydrazine, methylene diamine, ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, dodecylmethylene diamine, 1,4-diaminocyclohexane, 1,4-
Diaminomethylcyclohexane, O-aminoaniline,
Examples include p-aminoaniline, 1,4-diaminomethylhensen, and (4-aminophenyl)ether.

Examples of ω-amino-ω-carboxylic acids include glycine, β-alanine, 3-aminopropanoic acid, 4-aminobutanoic acid,
5-aminopencunic acid, II-amino[decanoic acid, 4-
Examples include aminobenzoic acid, 4-(2-aminoethyl)benzoic acid, and 4-(4-aminophenyl)butanoic acid.

Ethylene diisocyanate-1 as diisocyanate-1-
・, methylene diisocyanate I, m-phenylene diisocyanate, p-phenylene diisocyanate,
Examples include p-xylene diisocyanate and 1,5-naphthyl diisocyanate.

(C) Others For example, polyesters and polyamides obtained by ring-opening polymerization In the formula, X represents -0--NH-, and m represents an integer of 4 to 7. -CIl□- may be branched.

Such monomers include β-propiolactone,
ε-caprolactone, dimethylpropiolactone, α-
Examples include pyrrolidone, α-piperitone, ε-caprolactam, and α-methyl-ε-caprolactum.

Two or more types of the above-described polymers of the present invention may be used in combination.

The molecular weight and degree of polymerization of the polymer of the present invention do not have a substantial effect on 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 and the problem of solution viscosity. Because of the high viscosity, it becomes difficult to emulsify and disperse, producing coarse particles.As a result, problems such as decreased color development and poor coating properties are likely to occur. To counter this problem, using a large amount of auxiliary solvent to lower the viscosity of the solution causes new process problems. From the above point of view, the viscosity of the polymer is preferably 5000 cps or less, more preferably 2000 cps or less when dissolved in 100% of the adjuvant used. The molecular weight of the polymer used in the present invention is preferably 150,000 or less, more preferably 100,000 or less.

In the present invention, a water-insoluble polymer has a solubility of the polymer in 100 g of distilled water of 3 g or less, preferably 1 g.
A polymer that is:

The ratio of the polymer of the present invention to the co-solvent varies depending on the type of polymer used, and the solubility in the co-solvent,
It varies over a wide range depending on the degree of polymerization, solubility of the coupler, etc. Typically, a solution consisting of at least a coupler, a high-boiling coupler solvent, and a polymer dissolved in an auxiliary solvent has a sufficiently low viscosity to be easily dispersed in water (water or hydrophilic colloid water). The required amount of co-solvent is used. The higher the degree of polymerization of the polymer, ? 8
Since the viscosity of the liquid increases, it is difficult to uniformly determine the ratio of polymer to cosolvent regardless of the type of polymer, but the ratio is usually in the range of about 1:1 to 1:50 (polymerization ratio). preferable. The ratio (weight ratio) of the polymer of the present invention to the coupler is preferably 1:2 to 20:I, more preferably 1:1 to 10:1.

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

Specific examples Polymer type 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 Combine (
95: 5) Poly n-butyl acrylate P-7) P-8) P-9) P-10) P-11) P-12) P-13) P-14) P-15) P-16) P- 17) P-18) P-19) P-20) Poly n-butyl methacrylate polypentyl methacrylate polyisopropyl methacrylate polydecyl methacrylate n-butyl acrylate-acrylamide copolymer (9
5: 5-polymethylchloroacrylate 14-butanediol-adipic acid polyester ethylene glycol-sebacic acid polyester polycaprolactone poly(2-tert-butylphenyl acrylate) poly(4-tert-butylphenyl acrylate) n-butyl methacrylate-N -vinyl-2-pyrrolidone copolymer (90:10) methyl methacrylate-vinyl chloride copolymer (70:
30) P-21') P-22) P-23) P-24) P-25) P-26) P-27) P-28) P-29) P-30) Methyl methacrylate-styrene copolymer (90:10
) Methyl methacrylate-ethyl acrylate copolymer (
50: 50) n-butyl methacrylate-methyl methacrylate-styrene copolymer (50: 30: vinyl acetate-acrylamide copolymer (85: 15) vinyl chloride-vinyl acetate copolymer (65: 35) methyl methacrylate-acrylic Nitrile copolymer (6
5: 35) Diacetone acrylamide-methyl methacrylate copolymer (50: 50) Vinyl methyl ketone-isobutyl methacrylate copolymer (55: 45) Ethyl methacrylate-n-butyl acrylate copolymer (70: 30) Diacetone acrylamide -n-Butyl urea P-31) P-32) P-33) P-34) P-35) p-36) P-37) P-38) Acrylate copolymer (50: 40) To methyl methacrylate-cyclo xyl methacrylate copolymer (50: 50) n-butyl acrylate styrene methallyrecuto diacetone acrylamide copolymer (70: 20: 10) N-tert-butyl methacrylamide-methyl methacrylate acrylic acid copolymer (60: 30: 10) Methyl methacrylate-1-styrene-vinyl sulfonamide copolymer (70: 20: 10) Methyl methacrylate-phenyl vinyl keto) copolymer (70: 3)
0) n-butyl acrylate-methyl methacrylate-n-
Butyl methacrylate copolymer (35: 35:
30) n-butyl methacrylate (pentyl methacrylate)-
N-vinyl-2-pyrrolidone copolymer <38: 3g
: 24) Methyl methacrylate n-butyl mekuku P-39) P-40) P-41) P-42) P-43) P-44) P-45) P-46) P-47) Lylate isobutyl methacrylate acrylic acid co Polymer (37: 29: 25: 9
) n-butyl methacrylate-acrylic acid (95: 5
) Methyl methacrylate-acrylic acid copolymer (95:
5) Benzyl methacrylate-acrylic acid copolymer (90:
10) n-butyl methacrylate-methyl methacrylate-henzyl methacrylate-acrylic acid copolymer (35:
35:25:5) n-butyl methacrylate-
Methyl methacrylate-benzyl methacrylate copolymer (35: 35: 30) Poly-3-pentyl acrylate cyclohexyl methacrylate-methyl methacrylate-n-propyl methacrylate copolymer (37: 29
: 34) Polypentyl methacrylate methyl methacrylate-n-butyl methacrylate P-, 18) P-, 19) P-50) P-51) P-52) p-53) P-54) P-55) Lylate copolymer (65・35) Vinyl acetate-1/-vinylpropionic copolymer (
75: 25) Kanophthyl methacrylate = 1-3-acryloxobutane-1-sulfonic acid s[-lium copolymer (97: 3) n-butyl methacrylate-notylnotacrylate-acrylamyl copolymer (35 : 35 : 30) n-butyl methacrylate-methyl methacrylate I・-
Vinyl chloride copolymer (37.36:27) n-butyl methacrylate styrene copolymer (90:
10) Methyl methacrylate-1-N-vinyl-2-pyrroline copolymer (90:10) n-methyl methacrylate vinyl chloride copolymer (90:10)
10) n-methyl methacrylate-1 to styrene copolymer (70
・30) P-56) P-57) P-58) p-59) P-60) P-61) P-62) p-63) p-64) P-65) p-66) p-67 ) Poly(N-sec-butylacrylamide) Poly(N-
tert-butylacrylamide) diacetone acrylamide-methyl methacrylate copolymer (62: 38
) Polycyclohexyl methacrylate-1-methyl methacrylate 1-note copolymer (60: 40) N-tert-butylacrylamide-methyl methacrylate copolymer (4
0: 60) Poly(N-n-butylacrylamide) poly(tert-methyl methacrylate-1-)-Nter
t-Butylacrylamide copolymer (50:50) tert-butyl methacrylate-methyl methacrylate
1. Copolymer (70: 30) poly(lLtert-butyl methacrylamide) N-tert-butylacrylamide methyl methacrylate-1. Copolymer (60: 4)
0) Methyl methacrylate-acrylonitrile copolymer (70: 30) Methyl methacrylate-1-vinyl methylke P-68) p-69) P-70) P-71,) P-72) P-73) P- 74) +1-75) P-76) p-77) P-78) P-79) P-80) P-81,) Ton copolymer (38: 62) Methyl methacrylate-styrene copolymer (75: 2
5) Methyl tuacrylate-hexyl methacrylate copolymer (70+30) Poly(hensyl acrylate) Poly(4-biphenylacrylate) Poly(4-butoxycarbonylphenyl acrylate-1)
) Poly(sec-butyl acrylate) Poly(Ler-butyl acrylate-1.) Poly 3-chloro-2,2-bis(chloromethyl)propyl acrylate Poly(2-chlorophenylacrylate) Poly(4-chlorophenylacrylate) Poly(pentachlorophenyl) Acrylate +1 Poly(4-cyanohenyl acrylate) Poly(cyanoethyl acrylate) Poly(4-cyanophenyl acrylate-1.) P-82) P-83) P-84) P-85) P-86) P-87) P-88) P-89) P-90) P-91) P-92) P-93) P-94) P-95) P-96) Poly(4-cyano-3-thiabutyl) acrylate) Poly(cyclohexyl acrylate-1.) Poly(2-ethoxycarbonylphenyl acrylate) Poly(3-ethoxycarbonylphenyl acrylate) Poly(4-ethoxycarbonylphenyl acrylate) Poly(2-ethoxyethyl acrylate) Poly(3-ethoxycarbonylphenyl acrylate) -Product l-xypropyl acrylate) poly(LH, 111,
51+-octafluoropentyl acrylate) Poly(heptyl acrylate-1.) Poly(hexadecyl acrylate-1.) Poly(hexyl acrylate-1~) Poly(isobutyl acrylate) Poly(isopropyl acrylate-1-) Poly (3-Methoxybutyl acrylate) poly(2-methoxyluponylphenyl urea P-97) P-98) P-99) p-100) P-101) P-102) P-103) P-104) p -105) P-106) p-107) P-108) p-109) P-110) P-111) Acrylate) Poly(3-methoxycarbonylphenyl acrylate) Poly(4-methoxycarbonylphenyl acrylate) Poly(2 -methoxyethyl acrylate) poly(4-methoxyphenylacrylate) poly(3-methoxypropyl acrylate) poly(3,5-dimethyladamantyl acrylate) poly(3-dimethylaminophenyl acrylate) polyvinyl-tert-butyrate poly(2-methylbutyl) acrylate) poly(3-methylbutyl acrylate) poly(1,3-dimethylbutyl acrylate) poly(2-methylpentyl acrylate) poly(2-naphthyl acrylate) poly(phenyl methacrylate) poly(propyl acrylate) P-112) P -113) P-114) P-115) P-116) P-117) P-118) P-119) P-120) P-121) P-122) P-123) P-124) P-125 ) P-126) P-127) P-128) Poly(m-tolyl acrylate) Poly(o-tolyl acrylate) Poly(p-tolyl acrylate) Poly(N,N-dibutylacrylamide) Poly(isohexyl acrylamide) Poly (isooctylacrylamide) Poly(N-methyl-N-phenylacrylamide) Poly(adamantyl methacrylate) Poly(benzyl methacrylate) Poly(2-bromoethyl methacrylate) Poly(2-N
-tert-butylaminoethyl methacrylate) poly(sec-butyl methacrylate) poly(tert-butylaminoethyl methacrylate)
-butyl methacrylate) poly(2-chloroethyl methacrylate) poly(2-cyanoethyl methacrylate)
Poly (2-cyanomethylphenyl methacrylate) Poly (4-cyanophenyl methacrylate-1.) p-12
9) P-130) P-131) P-132) P-133) P-134) P-135) P-136) P-137) P-138) p-139) P-140) Poly(cyclohexyl methacrylate) ) Poly(dodecyl methacrylate) Poly(diethylaminoethyl methacrylate) Poly(2-ethylsulfinylethyl methacrylate) Poly(hexadecyl methacrylate) Poly(hexyl methacrylate) Poly(2-hydroxypropyl methacrylate) Poly(4-methoxycarbonylphenyl methacrylate) Poly(3,5-dimethyladamantyl methacrylate) Poly(dimethylamine ethyl methacrylate) Poly(3,3-dimethylbutyl methacrylate) Poly(3,3-dimethyl-2-butyl methacrylate) P-141) P-142) P- 143) P-144) P-145) P-146) P-147) P-148) P-149) P-150) P-151) P-152) P-153) Poly(3,5,5- ) dimethylhexyl methacrylate) Poly(octadecyl methacrylate) Poly(tetradecyl methacrylate) Poly(4-butoxycarbonylphenyl methacrylamide) Poly(4-carboxyphenyl methacrylamide) Poly(4-ethoxycarbonylphenyl methacrylamide) Poly(4- Poly(butylbutoxycarbonylmethacrylate) Poly(butylchloroacrylate) Poly(butylcyanoacrylate) Poly(cyclohexylchloroacrylate) Poly(ethylchloroacrylate) Poly(ethyl ethoxylponylmethacrylate) P-1,54) Poly(ethylephacrylate) P-
1,55) Poly(edylfluoromethacrylate-1-)
) P-156) Poly(hexylhexyloxycarbonyl methacrylate) P-157) Poly(isoprolchloroacrylate) P-1,58) Poly(isopropylchloroacryle-1.) P-1,59) l-li Methylene diamine-glutaric acid polyamide P-160) Hexalemethine diamine-adivic acid polyamide P-1,61) Poly(α-pyrrolidone) P-162
) Poly(ε-caprolactum) P-163) Hexamethylene diisocyanate un-1-1,1 ditanediol Polyurethane P-164) p-phenylene diisocyanate ethylene glycol Polyurethane synthesis example (1) Methyl polymer P- Person 3: Methyl methacrylate 50.0g, sodium polyacrylate 0.5g,
Distilled water 200mJ! The mixture was placed in a Mitsuro flask and heated to 80°C under stirring in a nitrogen stream. Polymerization was initiated by adding 500 mg of dimedyl azobisisobutyrate as a polymerization initiator.

After polymerizing for 2 hours, the polymerization solution was cooled, and the bead-shaped polymer was filtered and washed with water to obtain 7 g of P-348.

Synthesis example (2) Human precepts of t-butylaculamide mer P-57.

t-butylacrylamide 50. Og, toluene 2
50 ml of the mixture was placed in a 500 rd Mitsuro flask and heated to 80°C under stirring in a nitrogen stream.

Abbisisobutyronitrile 500m as a polymerization initiator
10 m of 1 to 1 solution containing ρ! was added to start polymerization.

After polymerization for 3 hours, the polymerization solution was cooled, poured into hexane LP, and the precipitated solid was filtered out, washed with hexane, and then dried under reduced pressure under heat to obtain 9 g of P-5747.

A dispersion of lipophilic fine particles containing a polymer is prepared eight times as follows.

The polymer of the present invention, which is a non-crosslinked, so-called linear polymer synthesized by solution polymerization, emulsion polymerization, turbidity polymerization, etc., the high-boiling coupler solvent, and the coupler are completely dissolved in an auxiliary organic solvent. This solution is then dissolved in water, preferably in an aqueous hydrophilic colloid solution, more preferably in gelatin water. With the help of a dispersant, the particles are dispersed into fine particles using ultrasonic waves, a colloid mill, etc., and incorporated into a silver halide emulsion. Alternatively, water or an aqueous hydrophilic colloid solution such as an aqueous gelatin solution is added to a dispersion aid such as a surfactant, the polymer of the present invention, a high-boiling coupler solvent, and an auxiliary organic solvent containing the coupler, and the oil-in-water droplets are formed with phase inversion. It may also be used as a dispersion. The auxiliary organic solvent may be removed from the prepared dispersion by a method such as distillation, noodle washing or ultrafiltration, and then mixed with the photographic emulsion. The auxiliary organic solvent referred to herein is an organic solvent that is present during emulsification and dispersion, and is ultimately removed from the photosensitive material by the drying process during coating or the method described in "-". It refers to an organic solvent with a low boiling point, or a solvent that has a certain degree of solubility in water and can be removed by washing with water. Examples of the auxiliary organic solvent include lower alcohols such as ethyl acetate and butyl acetate, acetate, ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone,
Examples include β-ethylacetate, methyl cellosolve acetate, and cyclohexanone.

Furthermore, if necessary, organic solvents that are completely miscible with water, such as methyl alcohol, ethyl alcohol, acetone, and tetrahydrofuran, can also be used in part.

Moreover, these organic solvents can be used in combination of two or more types.

The average particle diameter of the lipophilic fine particles obtained in this way is 0.
．． 04μ to 2μ is preferable, more preferably 0.0μ
It is from 6μ to 0.4μ. The particle diameter of the lipophilic fine particles can be measured, for example, using a measuring device such as Nanosizer manufactured by Coulter Co., Ltd. in the UK.

In the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as the silver halide.

In particular, when the purpose is rapid processing, silver chlorobromide containing 90 mol % or more (preferably 98 mol % or more) of silver chloride is preferred. This silver chlorobromide may contain a small amount of silver iodide, but it is preferable that it contains no silver iodide.

The average grain size of the silver halide grains in the photographic emulsion (in the case of spherical or approximately spherical grains, the grain size is taken as the grain diameter; in the case of cubic grains, the principal grain size is taken as the grain size, and expressed as an average based on the projected area) is not particularly limited. However, the thickness is preferably 2 μm or less, and particularly preferably 0.2 to 1.5 μm.

The silver halide grains in the photographic emulsion layer may have regular crystal structures such as cubes, tetradecahedrons, and hexahedrons (normal crystal emulsions), or may have irregular crystal structures such as spherical or plate shapes. It may have a crystalline form or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms.

Among these, it is preferable to use the normal crystal emulsion described above.

2. An emulsion may be used in which tabular silver halide grains having a diameter of five times or more the grain thickness occupy at least 50% of the total projected area.

The silver halide emulsion contained in at least one of the photosensitive layers has a coefficient of variation (the value obtained by dividing the statistical standard deviation by the average grain size expressed as a percentage) of 15% or less (more preferably 10%). % or less) is a monodispersed emulsion.

Such a monodispersed emulsion may be an emulsion having the above coefficient of variation alone, but in particular, two emulsions having different average grain sizes may be used.
The emulsion may be a mixture of separately prepared monodisperse emulsions having a variation coefficient of 15% or less (preferably 10% or less). Although the grain size difference or the mixing ratio can be arbitrarily selected, it is preferable to use an emulsion in which the average grain size difference is within the range of 0.2 μm or more and 1.0 μm or less.

Regarding the definition and measurement method of the above-mentioned coefficient of variation, see T.

H. James rThe Theory
The Theory of the Photographic Process, The Macmillan Company
hePhotographic Process+
The Macmillan Company 3rd edition (
(1966), page 39.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles. The latter grains are particularly useful as direct positive emulsions.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, a lead salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Silver halide emulsions are usually chemically sensitized. Conventional methods can be applied to the chemical sensitization method, details of which can be found in JP-A-62-21.
It is described in the specification of No. 5272, page 12, lower left column, line 18 to page 12, lower right column, line 16.

Additionally, silver halide emulsions are usually spectrally sensitized. For spectral sensitization, ordinary methine dyes can be used, and details thereof can be found in JP-A No. 62-215272, page 22, line 3 from the bottom of the upper right column to page 38, and March 16, 1988. It is stated in Appendix ■ of the procedural amendment.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzolidoazoles, nitrohencitriazoles, mercapdratrazoles (especially 1-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds such as oxadorinthion; Azaindenes, such as triazaindenes, tetraazaindenes ('l, 4-hydroxy substituted at S (1,3,3a7)
Many compounds known as antifoggants or stabilizers can be added, such as henzenesulfonic acid, henzenesulfinic acid, henzenesulfonic acid amide, etc. .

In color light-sensitive materials, yellow couplers, magenta couplers, and cyan couplers, which form yellow-magenta and cyan colors, respectively, by campling with the oxidized product of an aromatic amine-based color developing agent are commonly used.

Among the yellow couplers that can be used in the present invention, acylacetamide derivatives such as hendyl acetanilide and pivaloylacetanilide are preferred.

Among them, the general formula [Y-
1] and (Y-2) are preferred.

Y-13 [Y-2) (In the formula, χ represents a hydrogen atom or a coupling-off group. R21 represents a diffusion-resistant group having a total of 8 to 32 carbon atoms, and R
2□ is a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, or a total carbon number of 8 to 3
represents the diffusion-resistant group of 2.

+111 represents a hydrogen atom or a substituent. When there are two or more R23's, they may be the same or different. ) For details on the pivaloylacetanilide type yellow coupler, see U.S. Pat. - It is described in column 19, line 41.

3 For details on the sohendiylace I anilide type yellow coupler, see U.S. Pat. Nos. 3,408,194 and 3,9
33.501, 4,046.575, 4,1.
It is described in No. 33.958, No. 4.401752, etc.

Specific examples of bihaloylacetanili F-type yellow couplers include compound examples (Y-1) to (Y-
39), among which (Y-1), (
Y-4), (Y-6) (Y-7), (Y-15
), (Y-21), (Y-22) (Y-23)
, (Y-26) , (Y-35) , (
Y-36L (Y-37), (Y-38),
(Y-39) etc. are preferred.

Also, No. 1 of the above-mentioned U.S. Pat. No. 4,623.616
Compound examples (Y-1) to (Y-33) in columns 9 to 24 can be listed, among which (Y-2) (Y-7), (
'1-8), (Y-12), ('I''-20)
(Y--21), (Y-,23), (Y-
29) etc. are preferred.

Other preferred examples include U.S. Patent No. 3408.1
Typical specific example (34) described in column 6 of specification No. 94,
Compound examples 0ω and 09) described in column 8 of specification No. 3,933,501, No. 7 of specification 4,046.575
Compound example (9) described in columns ~8, 4,133,958
Compound examples (1) and 4 described in columns 5 and 6 of the specification,
401. Compound Example 1 described in column 5 of Specification No. 752
, and the following compounds a) to g).

Among the above couplers, those having a nitrogen atom as the leaving atom are particularly preferred.

Examples of magenta couplers that can be used in the present invention include oil-protected couplers of indacylon type or cyanoacetyl type, preferably 5-pyrozolone type and pyrazoloazole type couplers such as 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 representative examples thereof include U.S. Pat. Same second
, 343,703, 2,600,788, 2,908,573, 3,062.653, 3,152.896 and 3,936.015
It is written in the number etc.

As the leaving group for the pyrazolone coupler of the two-equivalent coupler, a nitrogen atom leaving group as described in US Pat. No. 4,310,619 or an arylthio group as described in US Pat. No. 4,351.897 is preferred.

Furthermore, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369.879, preferably pyrazolo(5,1-c)(1,2,4) triazoles as described in U.S. Pat. No. 3,725.067, Research Disclosure 24220
(June 1984) and Research Disclosure 24230 (19
Examples include the pyrazolopyrazoles described in June 1984). Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds have the following general formula (M-1)
, (M-2) or (M-3).

Here, R31 represents a diffusion-resistant group having a total carbon number of 8 to 32, and R3□ represents a phenyl group or a substituted phenyl group. R33 represents a hydrogen atom or a substituent. Z
represents a group of nonmetallic atoms necessary to form a 5R acyl ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a fused ring).

×2 represents a hydrogen atom or a leaving group. For details of the substituents of R33 and the substituents of the azole ring, see, for example, U.S. Patent No. 4,540,654, column 2, 4
It is described in the 1st line to the 8th column, 27th line.

Among pyrazoloazole couplers, U.S. Pat.
The imidazo N, 2-b) pyrazoles described in U.S. Pat.

In addition, pyrazolotriazole couplers in which a branched alkyl group is directly connected to the 2, 3 or 6 position of the biradurotriazole ring as described in JP-A-61-65245, and pyrazolotriazole couplers as described in JP-A-61-65246 pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxytuunyl sulfonamide halast group as described in JP-A No. 61-147254, and European Patent (Publication) No. It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group in the 6-position as described in No. 226,849.

Specific examples of these couplers are listed below.

(Left below) The most typical cyan couplers are phenolic cyan couplers and naphthol cyan couplers.

As a phenolic cyan coupler, US patents 2 and 3
No. 69,929, No. 4,518,687, No. 4,51
As described in No. 1,647 and No. 3,772,002, etc.
There are compounds (including polymer couplers) that have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position; typical examples include Canadian Patent No. 625,
Coupler of Example 2 as described in '822, U.S. Pat. No. 3,7
Compound (1) described in No. 72.002, No. 4.5645
Compounds (I-4) and (1-5) described in No. 90, compounds (1), (2), and (
3), (24), and the compound (C-2) described in No. 62-70846.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772,162, No. 2,895,826, No. 4,
No. 334,011, No. 4,500゜653 and JP-A-5
9-164555, and a representative example thereof is the compound (■) described in U.S. Patent No. 2895.8.26.
, Compound 07) described in No. 4557.999, No. 4,
Compounds (2) and 02) described in No. 565.777, No. 4
Compound (4) described in , 124.396, 4.61
Examples include the compound (1-1,9) described in No. 3564.

As a phenolic cyan coupler, U.S. Pat.
, No. 327,173, No. 4,564.586, No. 4,
No. 430.423, Japanese Patent Application Laid-Open No. 61390441, and Japanese Patent Application No. 1983. -100222, in which a nitrogen-containing heterocycle is condensed with a phenol nucleus, typical examples include couplers (]) and (3) described in U.S. Pat. No. 4,327.173, and U.S. Pat. Compounds (3) and Oω described in No. 4,564,586, compounds (1) and (3) described in No. 4,430,423, and the following compounds can be mentioned.

Other examples of phenolic cyan couplers include U.S. Pat. Nos. 4,333,999, 4,451,559, 4,
No. 444,872, No. 4,427.767, No. 4,5
No. 79.81.3, European Patent (EP) 067.689B
There are ureido couplers described in U.S. Pat. The coupler circle described in No. 4,444,872, the coupler (3) described in No. 4,427,767,
Coupler (6) and (2) described in No. 4,609,619
4), coupler (1) described in No. 4,579,813
(11), couplers (45) and (50) described in European Patent No. (BP) 067.689B1, JP-A-6142
Examples include coupler (3) described in No. 658.

Examples of naphthol-based cyan couplers include those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, U.S. Pat. No. 2313.586);
those having an alkylcarhamoyl group in the position (e.g., U.S. Pat. No. 2,474.293, U.S. Pat. No. 4,282,312);
Those with an arylcarbamoyl group at the 2-position (e.g., Japanese Patent Publication No. 14523/1983), and those with a carbonamide or sulfonamide group at the 5th position (e.g., JP-A-602374).
No. 48, No. 61-145557, No. 61-15364
No. 0), those with an aryloxy leaving group (e.g., U.S. Pat. No. 3,476,563), those with a substituted alkoxy leaving group (e.g., U.S. Pat. No. 4,296,199),
Those with a glycolic acid leaving group (e.g. Japanese Patent Publication No. 60-3
9217).

The coupler used in the present invention is oil-soluble and is generally dissolved in a high boiling point solvent, if necessary, in combination with a low boiling point solvent.
After emulsifying and dispersing this solution in an aqueous gelatin solution, it is preferable to add the dispersion to a silver halide emulsion. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, or a known anti-fading agent may be used in combination. I have no problem with that either. Furthermore, to explain in detail the method of adding the coupler used in the present invention, the coupler and, if necessary, a hydroquinone derivative, an ultraviolet absorber, or an anti-fading agent, etc., are simultaneously added using the following general formulas [XXI]I) to [XX■ ], and if necessary, ethyl acetate, butyl acetate, butyl propionate, cyclohexanol,
These high boiling point solvents and low boiling point solvents that are soluble in low boiling point solvents such as cyclohexanetetrahydrofuran may be used alone or in combination. ) an aqueous solution containing a hydrophilic binder such as gelatin containing an anionic surfactant such as alkylhenzenesulfonic acid and alkylnaphthalenesulfonic acid and/or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate; Mix and emulsify and disperse using a high-speed rotating mixer, colloid mill or ultrasonic dispersion device,
It can be used by being added to a silver halide emulsion.

General formula (XXI[l) P=0 General formula (XXIV) 0OW2 ON General formula (XXVI) General formula (XX side) General formula (XX side) O In the formula, Wl, W2 and w3 are each substituted or unsubstituted represents an alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W4 is Wl,
0-wl or 5-wl, n is an integer from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other (in the general formula (■), wl and w2
may be linked to each other to form a condensed ring.

W6 represents a substituted or unsubstituted alkyl group or aryl group, and the total number of carbon atoms constituting w6 is 12 or more.

The high-boiling coupler solvent that can be used in the present invention has the general formula (XX
In) ~ - General formula XX side) Compounds that are immiscible with water and have a melting point of 100 °C or lower and a boiling point of 140 °C or higher,
Any good solvent for the coupler can be used. The melting point of the high boiling coupler solvent is preferably below 80°C. The boiling point of the high boiling coupler solvent is preferably 160°C or higher, more preferably 170°C or higher.

If the melting point of the coupler solvent exceeds approximately 100'C, crystallization of the coupler tends to occur, and furthermore, the effect of improving color development tends to be poor.

The light-sensitive material of the present invention contains hydroquinone derivatives, aminephenol derivatives, amines, gallic acid derivatives, catechol derivatives,
It may also contain ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as organic antifading agents for cyan, magenta and/or yellow images, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxyhenzenes, aminophenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and alkyl Typical examples include ether or ester derivatives. Further, metal complexes such as (biszaritylaldoximer 1-)nickel complex and (bis-N,N dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are U.S. Patent No. 2.360.290,
2.418.61.3, 2.700 453
No. 2.701.197, No. 2.728,65
No. 9, No. 2. 732. No. 300, No. 2,735
．． No. 765, No. 3.982944, No. 4.430
, 425, British Patent No. 1.363,921, U.S. Patent No. 2.71.0801, U.S. Pat. is U.S. Patent No. 34323
No. 00, No. 3.573,050, No. 3.574.
No. 627, No. 3,698.909, No. 3.764
, 337, JP-A-52], 52225, etc., and spiroindanes are described in U.S. Patent No. 4.360.589,
P-alkoxyphenols are described in U.S. Pat. No. 2,735.
No. 765, British Patent No. 2.066.975, Japanese Unexamined Patent Publication No. 5
1-10539, Special Publication No. 57-19764, etc.
Hindered phenols are covered by U.S. Patent No. 3700.455.
No., JP-A No. 52-72225, U.S. Patent No. 4,228
．． No. 235 and Japanese Patent Publication No. 526623, gallic acid derivatives, methyleneoxyhenzenes, and aminophenols are disclosed in U.S. Pat. No. 3,457.079 and U.S. Pat. No. 4, respectively.
, 332.886, and Japanese Patent Publication No. 56-21144, hindered amines are disclosed in U.S. Patent No. 3.336135, U.S. Pat.
No. 889, No. 1,354,313, No. 1.410
, No. 846, Japanese Patent Publication No. 511420, Japanese Patent Publication No. 58-11
No. 4036, No. 59-53846, No. 59-7834
No. 4, etc., and ether and ester derivatives of phenolic hydroxyl groups are disclosed in U.S. Patent Nos. 4,155,765 and 4,1.
No. 74.220, No. 4,254.216, No. 4.
No. 264.720, JP-A No. 54-145530, No. 5
No. 5-6321, No. 58-1.05147, No. 59-
No. 10539, Japanese Patent Publication No. 57-37856, U.S. Patent No. 4,279,990, Japanese Patent Publication No. 53-3263, etc.; ．． No. 050,938, No. 4.241. .

No. 155, British Patent No. 2,027,731 (A), etc., respectively. These compounds usually have a concentration of 5 to 100% for each corresponding color coupler.
This objective can be achieved by co-emulsifying the compound with a coupler and adding it to the photosensitive layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer.

Among the anti-fading agents mentioned in item 1, spiroindanes and hindered amines are particularly preferred.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, Henztriazole compounds substituted with aryl groups (e.g., U.S. Pat. No. 3,533,
794), 4-thiazolidone compounds (e.g., U.S. Pat. Nos. 3314.794 and 3,352.68)
1), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705,805, JP-A-46-2784),
, 707.375), butadiene compounds (such as those described in U.S. Pat. No. 4.045229),
Alternatively, benzoxidole compounds (eg, those described in US Pat. No. 3,700,455) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes,
Included are styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

Details of useful oxonol dyes can be found in JP-A-62-2152.
It is described in the specification of No. 72, page 158, upper right column to page 163.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

The supports used in the present invention are usually cellulose nitrace films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, and polycarbonate films that are used in photographic materials. , other laminates of these, thin glass films, paper, etc. Baryta or α-olefin polymers, especially polyethylene, j
Paper coated or laminated with a polymer of α-olefin having 2 to 10 carbon atoms such as polypropylene or ethylene butene copolymer, vinyl chloride resin containing a reflective material such as TiOz, or paper with a roughened surface as shown in Japanese Patent Publication No. 4719068. A support such as a plastic film that has improved adhesion to other polymeric substances by oxidation also gives good results. Further, an ultraviolet curable resin can also be used.

These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. It is also possible to add dyes or pigments to make it colored and transparent.

Opaque supports include those that are inherently opaque, such as paper, and
Also included are transparent films to which dyes, pigments such as titanium oxide, etc. are added, and plastic films surface-treated by the method disclosed in Japanese Patent Publication No. 19068/1983. The support is usually provided with an undercoat layer. In order to further improve the adhesion, the surface of the support may be subjected to preliminary treatments such as corona discharge, ultraviolet irradiation, and fire treatment.

Color photosensitive materials applicable to the production of the color photographs of the present invention include ordinary color photosensitive materials such as color negative film, color paper, color reversal paper, color reversal film, etc. Color photosensitive materials for printing are particularly suitable.

A black and white developer and/or a color developer is used for the development of the photosensitive material of the present invention. The color developing solution is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-Nβ-hydroxyethylaniline, 3-methyl-4amino-N-edyl-N-β-methanesulfonamitoedylaniline, 3
-Methyl-4-amino N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-
Examples include 1-luenesulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as hengimidazoles, henzodiazoles or mercapto compounds are typically included. If necessary, various protective agents such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethylenediamine, catecholsulfonic acids, and triethylenediamine (1,4-diazabicyclo[22,2]octane) may be added. Stable agents, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as Hensyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, fogging agents such as dye-forming couplers, competitive couplers sodium boron hydride, An auxiliary developing agent such as 1-phenyl-3-birapritone, a viscosity imparting agent, various chelating agents such as aminopolycarboxylic acid, aminopolyphosponic acid, alkylbosponic acid, and phosphonic carboxylic acid, such as ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-11 diphosphonic acid, nitrilo-N,N,N-1-rimethylenephosphonic acid, ethylenediamine-N N N'N'-teI-ramedylenebosponic acid, ethylene glycol (0-
(hydroxophenyl acetic acid) and their salts are representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black-and-white developer contains known black-and-white developing agents such as dihydroxyhairzenes such as hydroquinone, 3-virapurins such as 1-phenyl-3-pyrazolidone, or N-methyl-p-amino N-ethyls. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 3i per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be reduced to less than zero. 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, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. further processing in one continuous bleach-fix bath;
Depending on the purpose, a fixing treatment may be performed before a bleach-fixing treatment, or a bleaching treatment may be performed after a bleach-fixing treatment.

Examples of bleaching agents include iron (■), Kohar 1-(III
), compounds of polyvalent metals such as chromium (■), copper (■),
Peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; iron(III) or kohal l-(1) organic AF.
salts, such as ethylenediaminetetraacetic acid, diethylene I.
Aminopolycarboxylic acids such as lyaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; Bromates, permanganates, nitrohairzenes, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. In addition, aminopolycarboxylic acid iron (III) complex salts also have the following properties in bleaching solutions:
It is also particularly useful in bleach-fix solutions.

The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron (m)tit salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lower. can.

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

Specific examples of useful bleach accelerators are described in U.S. Patent No. 3,893.858, West German Patent Box 1
．． No. 290.812, No. 2.059988, JP-A-5
1-32.736, 5357.831, 53-
37.418, 53-72,623, 5395
．． No. 630, No. 53-95, No. 631, No. 53-10.
No. 4232, No. 53-124, 424, No. 53-14
No. 1.623, No. 51-28,426, Research Disclosure+-No. 17. Compounds having a mercapto group or disulfide group as described in No. 129 (July 1978); thiazolidine derivatives as described in JP-A-50-140129; , No. 832, No. 53-32,735,
Thiourea derivatives described in U.S. Pat. No. 3,706,561;
Iodides described in West German Patent Box No. 235; polyoxyethylene compounds described in West German Patent Box No. 966.410 and West German Patent Box No. 2,748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and other JP-A No. 49-42 .434, 49-5
No. 9,644, No. 53-94927, No. 54-35,
No. 727, No. 55-26.506, No. 5B-163,
Compounds described in No. 940; bromide ions, etc. can be used.

Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in U.S. Pat. No. 3,893.858 and Western Patent No. 1.290.812.
The compounds described in JP-A No. 53-95.630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used.
In particular, ammonium thiosulfate salts are most widely used.

As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and Televisi
on Il:ngineers Volume 64, P, 24
It can be determined by the method described in 8253 (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. The problem arises. 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" by Hiroshi Horiguchi, "Microbial It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Society for Antibacterial and Antifungal Control.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds and 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C 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 No. 57-8.543, 5B-14, 8
All known methods described in No. 34, No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

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 other processes such as the grudge removal 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 compounds described in No. 7, No. 3.342.
No. 599, Su7tsu Nach Disclosure No. 14.850 and No. 15
．． Schiff base type compound described in No. 159, No. 13.924
Aldol compounds described in US Patent No. 3.719.4
Metal salt complex described in No. 92, JP-A-51-135.628
Examples include the urethane compounds described in No.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated. Typical compounds are described in JP-A No. 56-64.339, JP-A No. 57-14.4547, JP-A No. 58], JP-A No. 15.438, and the like.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, 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. can be achieved. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

(Example 1) A multilayer silver halogenide photosensitive material having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Example compound of the present invention (Cpdll) having an average molecular weight of about 60,000 for preparing the coating solution for the first layer
19g, yellow coupler (EXY-1) 10.2
27.2 CC of ethyl acetate and a high boiling point solvent (SOI
V-1) 77cc (8.0g) was added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in 185 CC of a 10% aqueous Seratin solution containing CCt.

This emulsified dispersion and emulsions EM-1 and EM-2 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the ceratin curing agent for each layer, 1-oxy-3,5-dichloro-8-triazine sodium salt was used.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/n()).The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper (the polyethylene on the first layer side contains a white pigment (TiO7) and a bluish dye.) -th layer (blue-sensitive layer) Monodispersed paper spectrally sensitized with a sensitizing dye (ExS-1) Silver chlorobromide emulsion (EMI) 0.16 sensitizing dye (ExS-
Monodisperse silver chlorobromide emulsion (EM2) spectrally sensitized by 1)
0.10 gelatin 1.
86 Color image stabilizer (Cpd-1) 0.02 Dispersion polymer (Cpd-11) 0. 08 Yellow Coupler (EXY-1) 0.83 Solvent (Sol
v-1 and 5olv-2 volume ratio 1; 1. )
0.35 Second layer (color mixing prevention layer) Gelatin 0,99 Monodisperse silver chlorobromide emulsion (EM3) spectrally sensitized with sensitizing dye (ExS-2, 3) 0.05 Sensitizing dye (ExS-
A monodisperse silver chlorobromide emulsion (EM4) spectrally sensitized with
) 0.11 gelatin 1.
80 magenta coupler (ExM-1) 0.39 color image stabilizer (Cpd-4) 0.20 color image stabilizer (
Cpd-5) 0.05 color image stabilizer (Cpd
-6) 0. 04 Solvent (Solv-3)
0.12 solvent (solv-4)
0.25 Fourth layer (UV absorption N) Gelatin 1.60 Ultraviolet absorber (Cp d-7/Cp d-8/Cpd-9=3/2
/6: weight ratio) 0.70 color mixing inhibitor (Cpd-3)
0.05 solvent (solv-5)
0.27 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (EM5) spectrally sensitized with sensitizing dyes (ExS-4, 5) 0.07 Sensitizing dyes (ExS-
Monodisperse silver chlorobromide emulsion (EM6) spectrally sensitized with
) 0.16 Gelatin 0.
92 Cyan coupler (ExC-1) 0.17 Cyan coupler (ExC-2) 0.15 Color image stabilizer (Cp d-5) 0. 01 color image stabilizer (
Cp d-6) 0. 01 Color image stabilizer (Cp
d-1) 0.03 ultraviolet absorber (Cpd-7
/Cpd-9/Cpd-12=3/4/2: weight ratio)
0.17 Solvent (Solv-2) 0.20
Sixth layer (ultraviolet absorption layer) Gelatin 0.54 ultraviolet absorption (Cp d-7/Cp d-8/Cpd-9=
115/3: Weight ratio) 0.21 Color mixing prevention agent (Cpd-
3) 0.02? Container (Solv-5)
0. 08 Seventh layer (protective layer) Gelatin 1.3 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
0.17 liquid paraffin
0.03 Also, at this time, Cpd-13 and Cpd-14 were used as the anti-irradiation dyes. Furthermore, each layer contains Alkanol
F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. As a stabilizer for silver halide, Cpd-15, Cpd-16
was used.

xY I ExM ■ ExC xC xS 5O3NII(C2H5) 3 6X], O-' mol/Ag mol 4X10-' mol/Ag mol xS 5O3NII (C211s) 3 8X1. O-5 mol/Ag mol x S ■ 1.8X10-5 mol/Ag mol x S pd -(-CH2--CH-)-V- Sa U3K pd pd pd pd pd pd pd cpd cpd Solv ((iso)CJuO) yP=0 olv Tricresyl phosphate C00CHz (Jl (Ctlls) C4H7pd cpd cpd H cpd Next, monodisperse silver chlorobromide emulsion (EM
A photosensitive material B was prepared by replacing I and EM2) with polydisperse silver chlorobromide emulsions (EM7 and EMS). However, in this case, EM
The silver equivalent coating amounts of -1 and EM-2 were made equal to the silver equivalent coating amounts of EM-7 and EM-8.

Next, the dispersing polymer (cpd-11) was removed from the first layer coating solution of photosensitive materials A, B, and B to prepare photosensitive materials C and D.

Furthermore, in the preparation of photosensitive material A, when preparing the coating solutions for the third and fifth layers, a dispersion polymer (Cpd-
11) and solvent (Solv-1 and 5olv-2, 1:1 (
Sensitive material E was prepared by adding the volume ratio)) to the same coating amount as that of the first layer coating solution.

Silver halide emulsion (EM-1) in the blue-sensitive emulsion layer of the present invention
was prepared as follows.

(1 liquid) n2o 100.0cc
15.5 g of NaC 25 g of gelatin (2 liquids) Sulfuric acid (IN) (3 liquids) Silver halide solvent shown below (1%) 0 cc of H3 (4 liquids) Add Br aCI H2O (5 liquids) AgNO.

Add H and O (6 liquids) Br aCI K2IrC16 (0,001%) Add 11゜0 and make 2.80 g 0.34 g 140 cc g 40 cc 67.20 g 8.26 g 0.7 cc 320 cc (7 liquid) AgN (h 12
Add 0 gII20 320 c
c (1st solution) was heated to 75°C, and (2nd solution) and (3rd solution) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously over a period of 9 minutes. After another 10 minutes, (liquid 6) and (liquid 7)
were added simultaneously over a period of 45 minutes.

After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust pH to 6.2, average particle size 1.
A monodisperse cubic silver chlorobromide emulsion was obtained with a coefficient of variation (standard deviation divided by average grain size: s/d) of 0.01 μm, 0.08 μm, and 80 sol% silver bromide.

Lithium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

The silver halide emulsion (EM2) of the blue-sensitive emulsion layer of the present invention and the silver halide emulsions (EM3-6) of the green-sensitive and red-sensitive emulsion layers of the present invention were also treated in the same manner as described above. and were prepared by varying the time.

Silver halide emulsion (4) of the blue-sensitive emulsion layer for comparison was prepared as follows.

(8 liquids) H2O 700cc NaCl 39.4 g Gelatin 28 g (9 r1() Sulfuric acid (1,N)], 0 cc (10
vrj,) KB, 78.4 gKz+
rCI+, (0,001%) 0.7c
Add cI+20 to 800 cc (1
]Liquid) 8gNOa
Add 140 g II20
Heat 800 cc (8 liquids) to 75°C, (9 liquids)
Add. Thereafter, (]0 liquid) was added over a period of 40 minutes. Furthermore, 1 minute after the start of addition of (10 liquids), (11
? &,) was added over a period of 40 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin, p+(
A polydisperse silver chlorobromide emulsion having an average grain size of 0.82 μm, a coefficient of variation of 0.27, and a silver bromide content of 80 mol % was obtained by combining the steps in Example 6 and 2. Sodium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

Silver halide emulsions for comparison (EM-7 and EM-8)
were also prepared by the same method as above, varying the amount of chemicals, temperature, and time.

Table 1 shows the average grain size, coefficient of variation, and halogen composition of silver halide emulsions EM-1 to EM-8.

(Margins below) Table ■ The photosensitive materials A, B, C, D, and E above were tested with a sensitometer (Fuji Photo Film Co., Ltd., F W I (type, light source color temperature 32).
00°K) to provide gradation exposure for sensitometry through blue, green, and red filters. The exposure at this time was carried out at an exposure time of 0.5 seconds and an exposure amount of 250 CMS.

Next, after processing with the color developer shown below for 1 minute and 0 seconds,
A load of 100g is applied to an iron nail with a diameter of 0.5mm and the length is 60cm.
The photosensitive material was scratched at a speed of . After this, color development was carried out for 2 minutes and 30 seconds, and then the following steps of bleaching, fixing and washing with water were carried out.

(Processing process) (Temperature) (Time) Developing solution 38°C 1.0 minutes + 2.5 minutes Bleach-fixing solution 38°C 1.5 minutes Washing with water 2B -35°C 3.0 minutes (Developing solution formulation) Color developing solution (A ) Nitrilotriacetic acid/3Na 2. Og benzyl alcohol 15 rrrl.

Diethylene glycol 10 Na2
SO32, Og KBr O, 5g hydroxylamine sulfate 3.0g 4-aminoni3-methyl-N-ethyl N-(β-(methanesulfonamide)ethyl2 p-phenylenediamine sulfate 5.0g Na2CO
:+ (Monohydrate salt) Add 30.0 g of water to make a total of 1000 mal
(PL+ 10.1) (Bleach-fix solution formulation) Ammonium thiosulfate (54wt%) 150mlN
a2SO315g NII4 (Fe (I[I) (EDTA))
55gEDTB・2Na
Add 4 g water to total amount
1000ml.

(pH 6,9) The degree of sensitization due to scratching observed in the sample obtained by the above treatment was evaluated as follows.

O: Sensitization due to scratching is not observed.

△... Slightly observed.

×... 　 　 　 　 　 　 　 　 　 　 　

Table 2 shows the evaluation results for photosensitive materials A to H.

(The following is a blank space) As is clear from the results in Table 2, only in the combination of the present invention, the degree of sensitization due to pressure during processing was significantly improved.

(Example 2) A multilayer silver halide photosensitive material F having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

(First layer coating liquid adjustment) Yellow coupler (ExY-1) 19. , Ig with 27.2 cc of ethyl acetate and high boiling point solvent (S01v-6) 7
．． 7cc (8.0g) was added and dissolved, and this solution was
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of sodium dodecyl Haenszel sulfonate. This emulsified dispersion and emulsion EM9 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1oxy-3,5-dichloro-3-triazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-2) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/rd). The silver halide emulsion represents the coated amount in terms of silver.

Support Polyethylene laminate I/Paper (The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye.) -th layer (blue-sensitive layer) Spectral sensitized with a sensitizing dye (ExS-7) Monodisperse silver chlorobromide emulsion (EM9) 0.27 gelatin
1.86 yellow coupler (E
xY-1) 0.82 Solvent (S o I v-6
) 0.35 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-3) 0.06? Container (
SoIv-3)
0.12 Fifth layer (green-sensitive layer) Monodisperse silver chlorobromide emulsion (EM-10) spectrally sensitized with sensitizing dyes (ExS-3, 6) 0.45 Geladine
1.24 magenta coupler (E
xM-2) 0.35 color image stabilizer (Cpd-4)
0.1.2 color image stabilizer (Cp d-10)
0.06 color image stabilizer (Cpd-20)
O,1,0 color image stabilizer (Cpd-21,)
0.01? Container (Solv-3)
0.25 solvent (S o I v-4)
0.25 Fourth layer (purple ray absorption layer) Gelatin 1.60 Ultraviolet absorber (Cpd-7/Cpd-9/Cpd-17=3/2
/6: Weight ratio) 0.
70 Color mixing inhibitor (Cp d-3) 0.05
Container (So I v-7)
0.42 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (Elvl-11) spectrally sensitized with sensitizing dye (ExS-4,5) 0.20 Gelatin
o692 cyan coupler (
ExC-3) 0.15 Soan Cobra (Ex
C-4) O, ], 88 color image stabilizer Cpd-7
/Cpd-9/Cpd-18-3/4/2: Weight ratio) 0.17 Color image stabilizer (Cpd-1) 0.02 Dispersion polymer (Cpd-11) 0.14 Solvent (S o I v
-6) 0.20 6th N (ultraviolet absorbing layer) Gelatin 0.54 ultraviolet absorber (Cpd-7/Cpd-9/Cpd-17= 11
5/3 weight ratio) 021 container (SoIv-7),
0.08 Seventh layer (protective layer) Acid-treated gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%)
0.17 liquid paraffin
0.03 Also, at this time, Cpl-12 and Cpd-13 were used as the anti-irradiation dyes. Further, in each layer, Alkanol
]04 Cpd-14 and Cpd-15 were used as stabilizers for fac F0 silver halide.

The symbols of the compounds used in this example have the same meanings as those in Example 1. Other compounds are shown below.

XM I created G. Further, from this sensitive material, the dispersing polymer (Cpd-11) in the fifth layer coating solution was removed to prepare a sensitive material H, and in addition, in the photosensitive material F, the dispersing polymer (Cpd-11) in the fifth layer coating solution was removed.
A photosensitive material I was prepared by removing pd-11).

Table 3 shows the profiles of emulsions EM-9 to EM-12 used.

The above photosensitive material F-I was exposed to light in the same manner as in Example 1, treated with the following color developing solution for 20 seconds, and then subjected to the same pressure as in Example 1. After that, after performing color development for 25 seconds,
The following bleach-fixing and stabilization treatments were performed.

These samples were evaluated in the same manner as in Example 1, and the results are shown in Table 4.

Processing process Single skin color development 35°C 20 seconds + 25 seconds Bleach fixing 30-36°C Stable for 45 seconds■
30~37°c Stable for 20 seconds ■ 30~37
°c 20 seconds stable■ 30~37°c
Stable for 20 seconds ■ 30-37°C Dry for 30 seconds 70-85°C for 60 seconds (Stable 4-tank countercurrent system from ■ to ■) The composition of each treatment solution is as follows.

(Color developer) Water 8
00 Ethylenediaminetetraacetic acid 2.0
g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-ethyl-
N-(β-methanesulfonamide 1 ethyl)-3-methyl-4-aminoaniline sulfate 5.0 gNN-diethylhydroxylamine, 1.2 g56-
1.2.4) Lysulfonic acid 0.3g Fluorescent brightener (4,4'-diaminostilhene type) 2.0g Add water 1000 pl! (25°C
)], 0.101 pages Yodo I-Wed 400
m1 Ammonium thiosulfate (70%) 100d Sodium sulfite 13 g Ethylenediaminetetraacetic acid iron (III) Ammonium 55 g Ethylenediaminetetraacetic acid di3 g Sodium glacial acetic acid 8 g Add water 1000 Biao pH (25°C)
5.5 Formalin (37%) 0.1 g Formalin-sulfite additive 0.7 g 5-chloro-2-methyl-4 isothiaprin-3-one 0.02 g 2-methyl-4-isothiaprin-3-one 0. 01 g copper sulfate
Add 0.005 water
1000 m1plB25°C)
4.0 (blank below) From the results in Table 4, it can be seen that only in the combination of the present invention, the degree of sensitization due to pressure during processing is extremely small.

Other polymers P-3P-59P-129, which were listed earlier using the dispersing polymer (Cpcl-11,) as an exemplary compound,
P-110, P-116P-128, P-61, P-5
6 and P-64 respectively, the same result was obtained.

(Effects of the Invention) The present invention makes it possible to reduce sensitization and desensitization due to pressure applied to the photosensitive material before and during the development process.

hand Continued Supplementary Positive book 1999 April 7th day

Claims (1)

[Claims] In a photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, diffusion resistance is achieved by forming a dye in the light-sensitive emulsion layer by coupling with an oxidized form of an aromatic primary amine color developing agent. at least one type of oil-soluble coupler is coexisting and dispersed with at least one type of water-insoluble and organic solvent-soluble single or copolymer,
A silver halide color photographic material comprising monodispersed silver halide grains.