JP2001133931A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive material using silver halide grains having a high silver chloride content, excellent in suitability to rapid processing and having improved pressure resistance. SOLUTION: The silver halide color photographic sensitive material has at least one yellow coupler-containing blue-sensitive silver halide emulsion layer, at least one magenta coupler-containing green-sensitive silver halide emulsion layer, at least one cyan coupler-containing red-sensitive silver halide emulsion layer, a 2nd protective layer comprising a non-photosensitive hydrophilic colloidal layer as the top layer and a 1st protective layer adjacent to the 2nd protective layer on the substrate side and adjacent to the blue-sensitive maximum sensitivity layer on the side farther form the substrate on the substrate. Flat platy silver halide grains each having as aspect ratio of >=2 and >=50 mol% silver chloride content occupy >=50% of the total projected area of silver halide grains in at least one of the emulsion layers. The elastic modulus of the 1st protective layer is 2-10 times that of the blue-sensitive layer having the maximum sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a light-sensitive material having excellent suitability for rapid processing and improved pressure resistance.

[0002]

2. Description of the Related Art In recent years, photographic light-sensitive materials have been required to have various performances. Tabular grains are suitable as silver halide emulsion grains from the viewpoints of sensitivity, graininess, sharpness and color sensitization efficiency. That is well known in the art. In addition, there is a high demand for a low replenishment of a processing solution without knowing that the demands for simplification and speeding up of development processing in recent years remain. For these requirements, it is advantageous to use silver halide grains having a high solubility and a high silver chloride content.For tabular grains having a high silver chloride content, European Patent 0534395A1, US Patent 5,264,337, JP-A-7-168296, etc. It is described in.

[0003] However, when a design is made by using tabular silver halide grains having a high chloride content as described above in order to impart rapid processing suitability to a photographic material, a new problem arises. Compared with silver halide grains containing high silver bromide, silver halide grains containing high silver chloride have low intrinsic sensitivity, so the blue-sensitive layer, green-sensitive layer,
In order to favorably balance the sensitivity of the red-sensitive layer, it is necessary to design the silver halide grains of the blue-sensitive layer relatively large. This greatly deteriorated the pressure resistance, particularly when a light-sensitive material designed such that a blue-sensitive layer was positioned above other color-sensitive layers, such as a general photographic light-sensitive material, was produced. When photosensitive material is transported through the camera,
Pressure fog may be generated due to external force received from the surface direction of the photosensitive material when passing through a processing apparatus. Such abrasion-like or push-like fog is most susceptible to the photosensitive layer disposed closest to the photosensitive material surface.

Japanese Patent Application Laid-Open No. 7-168296 discloses silver halide grains excellent in sensitivity, gradation and storage stability by improving the method for preparing silver halide grains containing high silver chloride. This publication does not disclose a method for solving the problem that arises when designing a photosensitive material in a multilayer structure and the deterioration in pressure property.

Japanese Patent Application Laid-Open No. H11-24202 discloses a technique for controlling the elastic modulus ratio between a protective layer and an emulsion layer as a technique for preventing a matting agent from penetrating into an emulsion layer. This method is different from a method for solving the problems that occur when a photographic light-sensitive material is to be realized by a multilayer film system using tabular grains containing high silver chloride in order to impart suitability.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material, and to provide a light-sensitive material which is excellent in rapid processing suitability and has improved pressure characteristics using silver halide grains containing high silver chloride. To do.

[0007]

(1) A blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a cyan coupler are provided on a support. A red-sensitive silver halide emulsion layer containing a second protective layer consisting of a non-photosensitive hydrophilic colloid layer as the outermost layer and a support adjacent to the second protective layer and adjacent to the blue-sensitive highest sensitivity layer from the support. In a silver halide color photographic light-sensitive material having a first protective layer on the far side, at least 50% or more of the total projected area of silver halide grains in one layer has an aspect ratio of 2 or more and a silver chloride content of 50 mol% or more. Wherein the elastic modulus of the first protective layer is at least 2 times and not more than 10 times the elastic modulus of the blue-sensitive layer having the highest sensitivity. Silver halide color photographic material.

(2) An ultraviolet absorber is emulsified and dispersed using at least one of a water-insoluble and organic solvent-soluble homo- or copolymer comprising a repeating unit having a —C (＝ O) — bond in the main chain or side chain. The silver halide color photographic light-sensitive material according to (1), wherein a dispersion obtained by the above-mentioned method is contained in the first protective layer.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The elastic modulus specified in the present invention can be measured by a known method. The elastic modulus according to the present invention is defined by the so-called Young's modulus, for example, LE Nielsen,
“Mechanical Properties of Polymers”, Van Nostra
nd Reinhold, New York, 1962. as determined by the initial slope of the stress-strain curve in a tensile-strain test.

The elastic modulus of the first protective layer of the present invention is not particularly limited except that it is at least 2 times and not more than 10 times the elastic modulus of the blue-sensitive layer having the highest sensitivity. From the viewpoint, it is preferably 2.5 times or more and 8 times or less, and more preferably 3 times or more and 6 times or less.

For the above purpose of the present invention, the first protective layer contains a hydrophilic colloid such as gelatin as a matrix material, and may be added with a polymer or inorganic oxide particles having a higher elastic modulus. As the inorganic oxide, for example, alumina particles, mica, clay, colloidal silica, titanium dioxide particles and the like are preferable. The amount of these additives is not particularly limited, but is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 20% by mass, and more preferably 2% by mass to 10% by mass, based on the gelatin contained in the same layer. % Is most preferred.

The tabular grains containing high silver chloride having an aspect ratio of 2 or more according to the present invention are not particularly limited in the layer to be used, but are preferably used in a blue-sensitive layer, and are preferably used in a blue-sensitive layer and a green-sensitive layer. More preferably, it is more preferably used for a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer. Aspect ratio is 2
As long as it is at least 3, it is preferably at least 3 and at most 20 and preferably at least 4 and 15
The following are more preferred.

From the viewpoint of rapid processing suitability, the silver chloride content is 50
Mol% or more may be sufficient, but 75 mol% or more is preferable, and 90 mol% or more is preferable.
Mole% or more is more preferable. When silver halide is contained in addition to silver chloride, the halogen composition is silver bromide and / or silver iodide.

Specific examples of the water-insoluble and organic solvent-soluble polymer comprising a repeating unit having a -C (= O)-bond in the main chain or side chain, which can be used in the present invention, will be described in detail below. Here, -C (= O)-
Being composed of a repeating unit having a bond means that it contains at least one repeating unit having a -C (= O)-bond. The term “water-insoluble” means that the solubility in water at 25 ° C. is 1% by mass or less, and the term “soluble in organic solvent” means that the solubility in ethyl acetate at 25 ° C. is 1% by mass or more.

(A) Vinyl Polymer As the monomer forming the vinyl polymer usable in the present invention, acrylic esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n- Butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-
Bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate,
Benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxy Ethyl 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 (addition mole number n = 9), 1-bromo -2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like. In addition, the following monomers can be used.

N-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate,
tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-
(3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate,
Furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate,
Dipropylene glycol 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,
Examples thereof include ω-methoxy polyethylene glycol methacrylate (additional mole number n = 6), allyl methacrylate, dimethylaminoethyl methyl methacrylate methacrylate, and the like.

Vinyl esters: Specific examples thereof include:
Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate,
Vinyl chloroacetate, vinyl methoxy acetate,
Vinyl phenyl acetate, vinyl benzoate, vinyl salicylate and the like; acrylamides; for example, acrylamide, methyl acrylamide, ethyl acrylamide,
Propyl acrylamide, butyl acrylamide, te
rt-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, Methacrylamides; for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxy Ethyl methacrylamide, Methylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide and the like; olefins: for example, dicyclopentadiene, ethylene, propylene , 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene and the like; styrenes: for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene Chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, methyl vinyl benzoate, etc .; Ethers: for example, methyl vinyl ether, butyl vinyl ether,
Hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like; butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, fumaric acid Dimethyl, dibutyl fumarate,
Methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-
Examples thereof include vinylpyrrolidone, acrylonitrile, methacrylonitrile, vinylidene chloride, methylenemalonnitrile, and vinylidene.

As the monomers (for example, the above-mentioned monomers) used in the polymer usable in the present invention, two or more kinds of monomers are used as comonomers for various purposes (for example, for improving the solubility). . Further, for the purpose of adjusting the solubility, monomers having an acid group as exemplified below are also used as comonomers as long as the copolymer does not become water-soluble.

Acrylic acid: methacrylic acid: itaconic acid:
Maleic acid: monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate; monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate; citraconic acid: styrene sulfonic acid:
Vinylbenzylsulfonic acid: vinylsulfonic acid: acryloyloxyalkylsulfonic acid such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid and the like; methacryloyloxyalkylsulfonic acid such as methacryloyloxymethylsulfonic acid, Methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid and the like; acrylamidoalkylsulfonic acids, for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutane Sulfonic acid and the like; methacrylamidoalkylsulfonic acid, for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-meth Riruamido 2-methylpropane sulfonic acid, 2-methacrylamide-2-methyl butanoic acid; These acids alkali metal (e.g., Na, K, etc.) may also be a salt or an ammonium ion.

Among the above-mentioned vinyl monomers and other vinyl monomers used in the present invention, hydrophilic monomers (here, those which become water-soluble when formed into a homopolymer) are used as comonomers. If used,
The proportion of the hydrophilic monomer in the copolymer is not particularly limited as long as the copolymer does not become water-soluble, but is usually preferably 40 mol% or less, more preferably 20 mol%.
Or less, more preferably 10 mol% or less. Also,
When the hydrophilic comonomer copolymerizable with the monomer that can be used in the present invention has an acid group, the proportion of the comonomer having an acid group in the copolymer is usually 20 from the viewpoint of image storability.
It is at most mol%, preferably at most 10%, most preferably when it does not contain such a comonomer.

The monomers that can be used in the present invention in the polymer include:
Preferred are methacrylates, acrylamides and methacrylamides. Usually, it is preferable to copolymerize two or more monomers, and particularly preferable is a copolymer of an acrylamide-based monomer and another monomer that can be used in the present invention or a methacrylate-based monomer and the present invention. It is a copolymer with other monomers. Of course, two or more polymers may be used in combination.

(B) Polyester Resin Obtained by Condensing Polyhydric Alcohol and Polybasic Acid As the polyhydric alcohol, HO—R ₁ —OH (R ₁ is a hydrocarbon chain having 2 to about 12 carbon atoms, especially Glycols having a structure of (aliphatic hydrocarbon chain) or polyalkylene glycol are effective, and as the polybasic acid, HOOC-
Those having R ₂ —COOH (R ₂ 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, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4
-Butanediol, isobutylene diol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Decanediol, 1,11-undecanediol,
Examples thereof include 1,12-dodecanediol, 1,13-tridecanediol, 1,4-diol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol, and sorbitol.

Specific examples of the polybasic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, and undecanedicarboxylic acid. , Dodecanedicarboxylic acid, fumaric acid, maleic acid,
Itaconic acid, citraconic acid, phthalic acid, isophthalic acid,
Examples thereof include terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohimeric acid, cyclopentadiene-maleic anhydride adduct, and rosin-maleic anhydride adduct.

(C) Others Polyester obtained by, for example, the following ring-opening polymerization

Embedded image

In the formula, m represents an integer of 4 to 7. -CH
_{The 2} -strand may be branched.

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

The molecular weight and the degree of polymerization of the polymer which can be used in the present invention have substantially no significant effect on the effects of the present invention. However, as the molecular weight increases, it takes time to dissolve in a co-solvent. In addition, since the solution viscosity is high, it is difficult to emulsify and disperse, and coarse particles are generated. As a result, problems such as a decrease in color developability and a cause of poor applicability are liable to occur. Reducing the viscosity of the solution by using a large amount of an auxiliary solvent as a countermeasure causes a new process problem. In view of the above, the viscosity of the polymer is preferably 5,000 mPas or less, more preferably 2,000 mPas, when 30 g of the polymer is dissolved in 100 ml of an auxiliary solvent to be used (hereinafter, ml is also referred to as “mL”). 000 mPas or less. The weight average molecular weight of the polymer usable in the present invention is preferably 1,000,000 or less.
It is 1,000 or more, more preferably 400,000 or less, 5,000 or more, and still more preferably 150,000 or less, 10,000 or more.

As the co-solvent for the polymer which can be used in the present invention, a general organic solvent can be used, but ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, butoxyethoxyethyl acetate and the like are preferably used. The ratio of the polymer of the present invention to the auxiliary solvent varies depending on the type of the 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 ultraviolet absorbent. Usually, the viscosity is sufficiently low so that a solution comprising at least an ultraviolet absorber (high boiling solvent) and two or three polymers dissolved in an auxiliary solvent is easily dispersed in water or an aqueous hydrophilic colloid solution. The required amount of co-solvent is used. The higher the degree of polymerization of the polymer, the higher the viscosity of the solution. Therefore, it is difficult to uniformly determine the ratio of the polymer to the co-solvent regardless of the type of the polymer, but it is usually about 1: 1 to 1:50 ( Weight ratio) is preferred.

[0030] No particular defined amount of the ultraviolet absorber is preferably from 0.01 to 2.0 g / m ^2, more preferably 0.2 to 1.0 g / m ^2.

The amount of the high-boiling organic solvent used as a dispersion medium for the ultraviolet absorber is not particularly limited. However, in order to dissolve the ultraviolet absorber preferably and to give preferable absorption characteristics (high-boiling organic solvent / ultraviolet absorber) Agent) 0.1-3.0 by mass ratio
Used in However, by using a polymer to disperse the ultraviolet absorber as in the present invention, if favorable solubility and absorption characteristics are obtained, a high-boiling organic solvent can be used at the above mass ratio of 0.1 or less. .

The dispersion medium that can be used as the high-boiling organic solvent is a usual dispersion medium used in silver halide photographic materials.

Examples of the high boiling point organic solvent include aryl phosphate esters, alkyl phosphate esters, phthalate esters, benzoate esters, lactate esters, citrate esters, fatty acid esters, carbonamides, Examples thereof include sulfonamide-based, ether-based, alcohol-based, phenol-based, carboxylic-acid-based, paraffin-based, and halogenated paraffin-based high-boiling organic solvents.

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

P-1) Polyvinyl acetate P-2) Polyvinyl propionate P-3) Polymethyl methacrylate P-4) Polymethyl methacrylate P-5) Polymethyl acrylate P-6) Vinyl acetate-vinyl alcohol copolymer (9
5: 5) (Hereinafter, all ratios are molar ratios) P-7) Poly-n-butyl acrylate P-8) Poly-n-butyl methacrylate P-9) Polyisobutyl methacrylate P-10) Polyisopropyl methacrylate.

P-11) Polyoctyl acrylate P-12) n-Butyl acrylate-acrylamide copolymer (95: 5) P-13) Stearyl methacrylate-acrylic acid copolymer (90:10) P-14) 1 2,4-butanediol-adipate polyester P-15) Ethylene glycol-sebacate polyester P-16) polycaprolactone P-17) polypropiolactone P-18) polydimethylpropiolactone P-19) n-butyl methacrylate N-vinyl-
2-Pyrrolidone copolymer (90:10) P-20) Methyl methacrylate-vinyl chloride copolymer (70:30).

P-21) Methyl methacrylate-styrene copolymer (90:10) P-22) Methyl methacrylate-ethyl acrylate copolymer (50:50) P-23) n-butyl methacrylate-methyl methacrylate-styrene copolymer Polymer (50:30:20) P-24) Vinyl acetate-acrylamide copolymer (8
5:15) 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-vinylsulfonamide copolymer (70:20:10) P- 35) Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) P-36) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35: 3)
5:30) P-37) n-butyl acrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (3
8:38:24) 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-42) n-Butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35: 35: 25: 5) P -43) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (35: 3
0:30) P-44) Polypentyl acrylate P-45) Cyclohexyl methacrylate-methyl methacrylate-n-propyl methacrylate copolymer (37:29:34) P-46) Polypentyl methacrylate P-47) Methyl methacrylate-n -Butyl methacrylate copolymer (65:35) P-48) Vinyl acetate-vinyl propionate copolymer (75:25) P-49) Sodium n-butyl methacrylate-3-acryloxybutane-1-sulfonate Copolymer (9
7: 3) P-50) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35: 35: 3)
0).

P-51) n-butyl methacrylate
Methyl methacrylate-vinyl chloride copolymer (37: 3
6:27) P-52) n-butyl methacrylate-styrene copolymer (90:10) P-53) Methyl methacrylate-N-vinyl-2-
Pyrrolidone copolymer (90:10) P-54) n-butyl methacrylate-vinyl chloride copolymer (90:10) P-55) n-butyl methacrylate-styrene copolymer (70:30) P-56) Poly (N-sec-butylacrylamide) P-57) Poly (N-tert-butylacrylamide) P-58) Diacetone acrylamide-methyl methacrylate copolymer (62:38) P-59) Polycyclohexyl methacrylate P-60 ) N-tert-butylacrylamide-methyl methacrylate copolymer (30:70).

P-61) Poly (N, N-dibutylacrylamide) P-62) Poly (tert-butyl methacrylate) P-63) Tert-butyl methacrylate-methyl methacrylate copolymer (70:30) P-64) Poly (N-tert-butyl methacrylamide) P-65) N-tert-butyl acrylamide-methylphenyl methacrylate copolymer (60:40) P-66) Methyl methacrylate-acrylonitrile copolymer (70:30) P -67) Methyl methacrylate-methyl vinyl ketone copolymer (38:72) P-68) Methyl methacrylate-styrene copolymer (75:25) P-69) Methyl methacrylate-hexyl methacrylate copolymer (70:30) P-70) Poly (Nn-butylmeth Tacrylamide).

P-71) Poly (N-iso-butylacrylamide) P-72) Poly (N-sec-butylacrylamide) P-73) Poly (N-tert-octylacrylamide) P-74) Poly (N- Phenyl-acrylamide) P-75) Poly (N, N-dibutyl-acrylamide) P-76) Polycyclohexyl methacrylate.

Representative examples of the ultraviolet absorber used in the present invention include 2- (2'-hydroxyphenyl) benzotriazole and benzophenone compounds. The former may be solid or liquid at room temperature, and these are known from JP-B-55-36984 and JP-B-55-12587.
And JP-A-58-214152 and JP-A-58-22184.
No. 4, No. 59-46646, No. 59-109055
No., JP-B-36-10466, 42-26187
Nos. 48-5496 and 48-41572, and U.S. Pat. Nos. 3,754,919 and 4,220,711, which can be used alone or in combination of two or more.

Some specific examples of the ultraviolet absorber used in the present invention are shown below, but the present invention is not limited to these.

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

The light-sensitive material of the present invention may be provided with at least one blue-sensitive, green-sensitive and red-sensitive photosensitive layer on a support. A typical example is to form a unit light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support, into a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer. Is a silver halide color photographic light-sensitive material. In the silver halide color photographic light-sensitive material of the present invention, the arrangement of the unit light-sensitive layers is generally arranged in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are DE 1,121,4
As described in No. 70 or GB 923,045, it is preferable to arrange two layers of a high-speed emulsion layer and a low-speed emulsion layer such that the sensitivity gradually decreases toward the support. Further, as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541, and 62-206543, a low-speed emulsion layer on the side farther from the support and a high-speed emulsion layer on the side closer to the support. Layers may be provided.

As a specific example, from the side farthest from the support,
High sensitivity blue photosensitive layer (BH) / Low sensitivity blue photosensitive layer (BL) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH.

As described in JP-B-55-34932, the blue-sensitive layer / GH / RH
They can also be arranged in the order of / GL / RL. JP-A-56-2
As described in 5738 and 62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, the layers may be arranged in the order of medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer from the side away from the support.

In addition, high-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order.

In the case of four or more layers, the arrangement may be changed as described above.

In order to improve color reproduction, US Pat. No. 4,663,271,
4,705,744, 4,707,436, JP-A-62-160448, 63-89
It is preferable to arrange a donor layer (CL) having a multilayer effect different in spectral sensitivity from the main photosensitive layer such as BL, GL, and RL described in the specification of 850 adjacent to or near the main photosensitive layer.

The silver halide emulsion other than the emulsion containing tabular silver halide grains according to the present invention will be described below.

As preferred photosensitive silver halide used in the present invention, silver chloride containing 50 mol% or more of silver chloride,
Silver iodochloride or silver iodochlorobromide is preferred.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23, “I. Emulsion preparation and types”, and the like.
No. 18716 (November 1979), p. 648, No. 307105 (November 1989)
Pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et P.)
hisique Photographiques, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF
Duffin, Photographic Emulsion Chemistry, Focal Pre
ss, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VL Zelikman, et a
l., Making and Coating Photographic Emulsion, Foca
l Press, 164).

US 3,574,628, US 3,655,394 and GB 1,4
The monodisperse emulsion described in 13,748 is also preferred.

Further, tabular grains having an aspect ratio of about 3 or more are particularly preferable and can be used in the present invention. Tabular grains may be (100) or (111) with major planes, and US Pat.
No. 30938, No. 5264337, No. 5292632
And the like. Japanese Patent Application Laid-Open No. 10-22182 discloses a particle having a main plane of (111).
No. 7, P38, line 14 to P45, line 20 can be prepared. The expression that the main plane is (100) indicates that 50% or more of the general evaluation surface of the silver halide grains is composed of silver halide grains composed of (100) occupying 50% or more of the total projected area. Similarly, the fact that the principal plane is (111) means that 50% or more of the estimated surface of silver halide grains is (11).
Silver halide grains composed of 1) have a total projected area of 50%.
It indicates that it accounts for more than%.

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

The emulsion used in the present invention may have dislocations. The tabular grains preferably have dislocations in the fringe. Examples of a method for introducing dislocations include a method of forming a high silver iodide or silver bromide layer by adding an aqueous solution of an alkali iodide, an alkali bromide, or the like, a method of adding AgI or AgBr fine particles, and a method described in JP-A-5-323487. Can be used.

The silver halide emulsion usable in the present invention may contain a polyvalent metal such as iridium, rhodium, ruthenium, lead, iron, magnesium, or calcium during or after grain formation. The polyvalent metal may be added in the form of a single salt, a metal complex salt, a polynuclear complex, or a polyvalent metal added to fine particles. When doping the above metal ions into silver halide grains, the method is described in US Pat. No. 3,761,276.
No. 4,395,478 and JP-A-59-21.
No. 6136 and the like.

In addition to the above-mentioned methods, the addition of metal ions is described in US Pat.
As described in JP-A-487752, fine silver halide grains may be doped and supplied.

The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside. Type emulsion. Among the internal latent image types, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, and 5 to 40 nm.
20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

US Pat. No. 4,626,498, JP-A-59-214852, described in US Pat. No. 4,082,553.
It is preferable to apply the silver halide grains and colloidal silver having the inside of the grains described in (1) to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. And its preparation method is described in US Pat.
14852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. Any of silver chloride, silver chlorobromide, silver bromoiodide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, particularly 0.05
~ 0.6 μm is preferred. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains has a grain size within ± 40% of the average grain size). Is preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide has an average grain size (average value of the circle equivalent diameter of the projected area).
It is preferably from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the layer containing fine silver halide grains.

The coated silver amount of the light-sensitive material of the present invention was 8.0 g / m ²
The following is preferred.

The photographic additives which can be used in the present invention are also described in RD, and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column Brightener page 24 page 647 page right column page 868 5. 5. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers Binder page 26 page 651 left column pages 873 to 874 7. 7. Plasticizer, page 27 page 650, right column, page 876 Lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 pages right column pages 876-877 Inhibitors 10. Matsuto 878-879.

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable.

Yellow coupler: Formula (I) of EP 502,424A,
Couplers represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); couplers represented by formula (I) of claim 1 of EP 568,037A; US 5,066,57
Coupler represented by general formula (I) in column 1, line 45 to 55 of column 6; Coupler represented by general formula (I) in paragraph 0008 of JP-A-4-274425; Claim 1 on page 40 of EP 498,381A1 (Especially D-35 on page 18); formula on page 4 of EP 447,969A1
Couplers represented by (Y) (especially Y-1 (page 17), Y-54 (41
P.)); US Pat. No. 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) (especially II-17, 19 (column 17), II-
24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257
[A-4] -63 (p. 134), [A-4] -73, -75 (p. 139); EP 486,965
M-4, -6 (p. 26), M-7 (p. 27); EP 571, 959A M-45 (p. 19);
JP-A-5-204106 (M-1) (p. 6); JP-A-4-3662631, paragraph 023
7 M-22.

Cyan coupler: CX-1, described in JP-A-4-04843
3,4,5,11,12,14,15 (pages 14-16); C-7,1 of JP-A-4-43345
0 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385, the general formula (Ia) or (Ib) ). Polymer coupler: P-1, P-5 of JP-A-2-44345 (page 11).

Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred.

Couplers for correcting unnecessary absorption of a coloring dye are described in formulas (CI), (CII) and (CII) described on page 5 of EP 456,257A1.
I), yellow colored cyan couplers represented by (CIV) (especially YC-86 on page 84), yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), EX- 7 (251
Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US 4,833,069, US 4,837,136
(2) (column 8), a colorless masking coupler represented by the formula (A) in claim 1 of WO92 / 11575 (especially the exemplified compounds on pages 36 to 45) are preferred.

Examples of compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP43
Compounds of formula (I) described on page 7, 6,938 A2 (especially D
-49 (page 51)), a compound represented by the formula (1) of EP 568,037A (especially (23) (page 11)), and a compound described in EP 440,195A2 on pages 5 to 6
Compounds represented by (I), (II) and (III) (especially I-
(1)); Bleaching accelerator releasing compound: Formula on page 5 of EP 310,125A2
Compounds represented by (I), (I ') (especially (60), (61) on page 1)
And the compound represented by formula (I) of claim 1 of JP-A-6-59411 (especially (7) (p. 7); Ligand releasing compound: US Pat. No. 4,555,47)
The compound represented by LIG-X described in claim 1 of claim 8 (especially, the compound on lines 21 to 41 of column 12); Leuco dye releasing compound: compounds 1 to 6 of columns 3 to 8 of US 4,749,641; Compound: a compound represented by COUP-DYE in claim 1 of US Pat. No. 4,774,181 (especially, compounds 1 to 1 in columns 7 to 10)
1); Development accelerator or fog release compound: US 4,656,
Compounds represented by formulas (1), (2) and (3) in column 3 of column 123 (especially (I-22) in column 25) and EP 450, 637A2, p.
ExZK-2 on line 38; Compound that releases a group that becomes a dye only after leaving: Compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y-1 to Y-19 in columns 25 to 36) .

The following additives are preferable as the additives other than the coupler. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3, 5, 16, 19, 25, 30, 42,49, 54, 55, 66,
81, 85, 86, 93 (pp. 140-144); Latex for impregnating oil-soluble organic compounds: Latex described in US Pat. No. 4,199,363; Oxidized developing agent scavenger: Column 2, US Pat. No. 4,978,606
Compounds of the formula (I) at lines 54 to 62 (especially I-, (1),
(2), (6), (12) (columns 4-5), formulas of lines 5-10 of column 2 of US 4,923,787 (especially compound 1 (column 3); stain inhibitor: pages 4-30 of EP 298321A) Formulas (I) to (III) on line 33,
Especially I-47, 72, III-1, 27 (pages 24 to 48); anti-fading agent: EP 29
A-6, 7, 20, 21, 23, 24, 25, 26, 30, 37, 40, 8321A
42, 48, 63, 90, 92, 94, 164 (pp. 69-118), US 5,122,444
Columns 25-38 II-1 to III-23, especially III-10, EP 47134
7A, pages 8-12, I-1 to III-4, especially II-2, US 5,139,931 columns 32 to 40, A-1 to 48, especially A-39,42; use of a color-enhancing or color-mixing inhibitor Material to reduce volume: EP 411324A 5
I-1 to II-15, especially I-46 on page 24; Formalin Scavenger: SCV-1 to 28, especially SCV-8 on page 24 to 29 of EP 477932A;
Hardener: H-1,4,6,8,14, US4, page 17, JP-A-1-214845
Compounds (H-1 to 54) represented by formulas (VII) to (XII) in columns 13 to 23 of 618,573, and compounds represented by formula (6) at the lower right of page 8 of JP-A-2-214852 (H-1 -76), especially compounds according to claim 1 of H-14, US 3,325,287; development inhibitor precursors:
JP-A-62-168139, P-24, 37, 39 (pages 6 to 7); US 5,019, 492
Compounds, especially 28, 29 of column 7;
Preservatives, fungicides: I-1 to II of columns 3 to 15 of US 4,923,790
I-43, especially II-1,9,10,18, III-25; Stabilizer, antifoggant: I-1 to (14) of columns 6 to 16 of US 4,923,793, especially I-1,
60, (2), (13), US Pat.
~ 65, especially 36: chemical sensitizer: triphenylphosphine
Selenide, Compound 50 of JP-A-5-40324; Dye: JP-A-3-13-1
A-1 to b-20 on pages 15 to 18 of 56450, especially a-1, 12, 18, 27, 35, 3
6, b-5, V-1 ~ 23 on pages 27 ~ 29, especially V-1, 33 ~ of EP 445627A
FI-1 to F-II-43 on page 55, especially FI-11, F-II-8, EP 457153A
III-36 on pages 17-28, especially III-1,3, microcrystalline dispersion of Dye-1-124 on 8-26 of WO 88/04794, 6- on EP 319999A
Compounds 1 to 22, especially compound 1, EP 519306A on page 11 of formula (1)
Or compounds D-1 to 87 (pages 3 to 28) represented by (3), US 4,2
Compounds 1 to 22 represented by the formula (I) of 68,622 (columns 3 to 1)
0), compounds (1) to (31) represented by formula (I) of US 4,923,788
(Columns 2-9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Tokuhei 2-32615, actual fairness
It is suitable for the film unit with lens described in 3-39784.

Suitable supports that can be used in the present invention include, for example, the aforementioned RD. No. 17643, page 28, the same RD. No. 18716, page 647 right column to page 648 left column, and RD. It is described in.

In the light-sensitive material of the present invention, the thickness from the light-sensitive silver halide layer closest to the support to the surface of the light-sensitive material is preferably 24 μm or less, more preferably 22 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes 15 seconds. Is defined. Film thickness is 25 ° C and relative humidity 55%
T _1/2 means the film thickness measured under humidity control (2 days), and T _1/2 is the value of A. Green et al.'S Photographic Science and Engineering (Photogr.Sci.En).
g.), Vol. 19, pp. 2,124-129. T _1/2
Can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm on the side opposite to the side having the emulsion layer. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder,
It is preferable to include a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD.
No. 18716, No. 18716, 651 left column to right column, and N
o. 307105, pages 880 to 881.

Next, a processing solution for a color negative film used in the present invention will be described. The color developing solution used in the present invention is described in JP-A-4-121739, page 9, upper right column, line 1 to
The compounds described in page 11, lower left column, line 4, can be used. Particularly, color developing agents for rapid processing include 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline and 2-methyl-4- [N
-Ethyl-N- (3-hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

These color developing agents are used in an amount of 0.0 per liter of a color developing solution (hereinafter, liter is also referred to as “L”).
It is preferable to use in the range of 1 to 0.08 mol, particularly
It is preferably used in the range of 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol. The replenisher of the color developing solution preferably contains 1.1 to 3 times the concentration of the color developing agent, particularly preferably 1.3 to 2.5 times the concentration.

As a preservative for the color developing solution, hydroxylamine can be used widely. However, when higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like can be used. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamines are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine.

The preservative is preferably used in an amount of 0.02 to 0.2 mol per liter, particularly 0.03 to 0.15 mol, and more preferably 0.03 to 0.15 mol.
It is preferable to use it in the range of 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution).

In the color developing solution, a sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in a range of 0.01 to 0.05 mol per liter, particularly preferably in a range of 0.02 to 0.04 mol. In the replenisher, it is preferable to use the replenisher at a concentration 1.1 to 3 times the above.

The pH of the color developing solution is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher is set to a high value in the range of 0.1 to 1.0 from these values. Preferably. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used.

The replenishment amount of the color developing solution is preferably from 80 to 1300 mL per m ² of the light-sensitive material, but from the viewpoint of reducing the environmental pollution load, the replenishment amount is preferably smaller, specifically from 80 to 600 m ^2.
L, and more preferably 80 to 400 mL.

The bromide ion concentration in the color developing solution is usually from 0.01 to 0.06 mol per liter. However, fog is suppressed while maintaining sensitivity, discrimination is improved, and graininess is improved. From the purpose, per 1L
It is preferably set to 0.015 to 0.03 mol. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions.

C = A−W / VC C: bromide ion concentration in the color developing replenisher (mol / L) A: target bromide ion concentration in the color developing solution (mol / L) W: 1 m ² photosensitivity Amount (mol) of bromide ions eluted from the light-sensitive material into the color developer when the material is color-developed. V: Replenishment amount (L) of the color-developing replenisher for 1 m ² of the light-sensitive material.

When the replenishment rate is reduced or when a high bromide ion concentration is set, as a method for increasing the sensitivity, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
It is also preferable to use a development accelerator such as a thioether compound represented by octanediol.

Compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. .

The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof are described in JP-A-5-72694 and JP-A-5-72694.
Preferred are those described in 5-173312, and in particular, 1,3-diaminopropanetetraacetic acid, and specific example 1 on page 7 of JP-A-5-73312.
Are preferred.

In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a solution having bleaching ability.
It is preferred to design with a mole to 0.15 mole. When the bleaching liquid is a bleaching liquid, 0.2 mol to 1 mol / L is used.
It is preferred to contain mole bromide, especially 0.3 to
It is preferable to contain 0.8 mol.

The replenisher of the solution having bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant.

CR = CT × (V1 + V2) / V1 + CP CR: Concentration of component in replenisher CT: Concentration of component in mother liquor (processing tank liquid) CP: Concentration of component consumed during processing V1: 1m Replenishment amount (mL) of replenisher having bleaching ability for photosensitive material ² (mL) V2: Amount (mL) brought in from the previous bath by 1 m ² of photosensitive material.

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, JP-A-53-9
It is also preferred to use the known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat.

The bleaching solution contains 50 to 1000 per m ² of the light-sensitive material.
It is preferable to replenish the bleaching replenisher of mL, especially 80 to
It is preferred to replenish 500 mL, more preferably 100-300 mL. Further, it is preferable to perform aeration on the bleaching solution.

The processing solution having a fixing ability is disclosed in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied.

In particular, in order to improve the fixing speed and the preservability, a processing solution having a fixing ability by using the compounds represented by the general formulas (I) and (II) of JP-A-6-301169, alone or in combination. Is preferably contained. In addition to the use of p-toluenesulfinic acid salts, the use of sulfinic acids described in JP-A-1-224762 is also preferable from the viewpoint of improving the preservation.

It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property. However, from the viewpoint of reducing environmental pollution, ammonium is reduced or reduced to zero. Is more preferred.

In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309590.

The replenishment rate of the replenisher in the bleach-fixing or fixing step is 100 to 1000 mL, preferably 150 to 700 mL, particularly preferably 200 to 600 mL, per m ² of the light-sensitive material.

In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be constituted by a plurality of processing tanks, and it is preferable that each tank be cascade-pipe to adopt a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally efficient, and the ratio of the processing time in the former tank and the latter tank is preferably in the range of 0.5: 1 to 1: 0.5. In particular, the range of 0.8: 1 to 1: 0.8 is preferable.

It is preferable that a free chelating agent not forming a metal complex is present in the bleach-fixing solution or the fixing solution from the viewpoint of improvement in preservation. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

Regarding the washing and stabilizing steps, the contents described in the above-mentioned JP-A-4-125558, page 12, right lower column, line 6 to page 13, right lower column, line 16 can be preferably applied. In particular,
EP 504,609 instead of formaldehyde
Azolylmethylamines described in 519,190 and JP-A-4-36
From the viewpoint of preserving the working environment, it is preferable to use the N-methylolazoles described in 2943, or to dimerize the magenta coupler to obtain a surfactant-free liquid containing no image stabilizer such as formaldehyde. .

In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution can be adjusted according to the photosensitive material 1
80 to 1000 mL per m ² is preferable, and particularly 100 to 500 mL, and more preferably 150 to 300 mL, is a preferable range in terms of both securing a washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment performed with such a replenishing amount, thiabendazole, 1, 1
2-benzoisothiazoline-3-one, 5-chloro-2-
It is preferable to use a known fungicide such as methylisothiazolin-3-one, an antibiotic such as gentamicin, or water deionized with an ion exchange resin.
It is more effective to use a combination of deionized water and a bactericide or antibiotic.

Further, the liquid in the washing or stabilizing liquid tank is
JP-A-3-46652, 3-53246, -355542, 3-121448,
It is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment described in the above-mentioned 3-126030, and in this case, the reverse osmosis membrane is preferably a low pressure reverse osmosis membrane.

In the process of the present invention, it is particularly preferable to carry out the correction of the evaporation of the processing liquid disclosed in the Invention Association's Published Technical Report, Publication No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the washing replenishing water.

As the treating agent used in the present invention, those described in page 3, right column, line 15 to page 4, left column, line 32 of the above-mentioned published technical report are preferable. In addition, as a developing machine used for this,
The film processor described on page 3, right column, lines 22 to 28 is preferred.

Specific examples of preferred processing agents, automatic developing machines, and evaporation correction methods for carrying out the present invention are described in the above-mentioned published technical report, from page 5, right column, line 11 to page 7, right column, last line. Have been.

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powder or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 describe tablets and JP-A-57-5
JP-A-48585 discloses a paste-like treatment agent, and any of them can be preferably used, but from the viewpoint of simplicity in use,
It is preferable to use a liquid that has been prepared in advance in a concentration for use.

The containers containing these treating agents are made of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, or the like, alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm and are used for containers, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

Next, the processing solution for the color reversal film used in the present invention will be described.

Regarding the processing for the color reversal film,
Aztec Co., Ltd. No. 6 (April 1, 1991), page 1, line 5 to page 10, line 5, and page 15, line 8 to line 24
It is described in detail in line 2 of the page, and any of the contents can be preferably applied.

In processing a color reversal film, an image stabilizer is contained in a conditioning bath or a final bath. Such image stabilizers include, in addition to formalin, sodium formaldehyde sodium bisulfite and N-methylolazole, and from the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferred. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, bleaching solution, fixing solution, washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.

As a preferred color reversal film treating agent containing the above contents, Eastman Kodak E-6
Examples of the treating agent include CR-56 treating agent manufactured by Fuji Photo Film Co., Ltd.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder.

The magnetic particles used in the present invention are γFe ₂ O
Ferromagnetic iron oxide such as ₃ , Co-coated γFe ₂ O ₃ , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb Ferrite, Ca ferrite, etc. can be used. Co-coated ferromagnetic iron oxide, such as Co-coated γFe ₂ O _3, is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably
3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 5
^{It is 4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Also JP-A-4-59911
No. 5,816,52 can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, or a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of
It is between 2,000 and 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based crosslinking agent, tolylene diisocyanate,
Isocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the reaction products of these isocyanates with polyalcohols (for example, the reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane) ), And polyisocyanates formed by condensation of these isocyanates, and the like, which are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm,
More preferably, it is 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , and more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, and 0.03 to 0.20.
Is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer may be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. Methods for applying the magnetic recording layer include air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray,
Dip, bar, extrusion, etc. are available,
The coating liquid described in JP-A-5-341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support preferably used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples described later, refer to Published Technical Report, Official Technical Publication No. 94-6023 (Invention Association; 1994.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, and terephthalic acid are used. Acids, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene-2,
6-naphthalate. The average molecular weight range is about 5,000
Or 200,000. The Tg of the polyester of the present invention is 50
° C or higher, and more preferably 90 ° C or higher.

Next, the polyester support has a winding habit.
The heat treatment temperature should be 40 ° C or higher and lower than Tg to reduce
More preferably, the heat treatment is performed at Tg-20 ° C. or higher and lower than Tg.
The heat treatment may be performed at a constant temperature within this temperature range,
The heat treatment may be performed while cooling. This heat treatment time is 0.
1 hour or more and 1500 hours or less, more preferably 0.5 hour or more
Less than 200 hours. The heat treatment of the support is performed in roll form.
Or may be carried out while being transported in web form.
Good. The surface is made uneven (for example, SnO_TwoAnd Sb_TwoO _FiveEtc.
(Apply conductive inorganic fine particles.)
No. Also, knurling is applied to the end and only the end is raised slightly.
To prevent cuts in the core
It is desirable. These heat treatments are performed on the surface after forming the support.
After treatment, after coating the back layer (antistatic agent, slip agent, etc.)
It may be carried out at any stage after the application. Preferred
Is after the application of the antistatic agent.

An ultraviolet absorber may be incorporated in this polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, regarding the undercoating method, a single layer or two or more layers may be used. As a binder for the undercoat layer,
Starting from copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethylene imine, epoxy resin, grafting Gelatin, nitrocellulose and gelatin are included.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acid and carboxylate, polymers including sulfonate,
Examples include cationic polymers and ionic surfactant compounds.

The most preferred antistatic agent is Zn.
O, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO _Two, MgO, BaO, Mo
O_Three, V_TwoO_FiveAt least one type of volume resistivity selected from
Ten⁷Ωcm or less, more preferably 10^FiveGrains that are Ω · cm or less
0.001 to 1.0 μm crystalline metal oxide or
Fine particles of these composite oxides (Sb, P, B, In, S, Si, C, etc.),
Furthermore, sol-like metal oxides or composite oxides thereof
Particles.

The content in the light-sensitive material is 5 to 500 mg / m^TwoBut
Preferably particularly preferably 10 to 350 mg / m ^TwoIt is. Conductive
Ratio of the amount of the crystalline oxide or its composite oxide to the binder
Is preferably 1/300 to 100/1, more preferably 1/100 to 100
/ 5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents a value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25
° C, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

Examples of the slipping agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, metal salts of higher fatty acids, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethylsiloxane and polydiethylsiloxane. Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrower, and the average particle size is 0.9 to 1.1 μm.
It is preferable that 90% or more of the total number of particles be contained during the doubling. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), Polystyrene particles (0.25 μm) and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic.

Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are disclosed in
37, 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded to impart light-shielding properties. The size of the patrone may be the same as the current 135 size, and in order to reduce the size of the camera, it is effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less.
The volume of the patrone case is 30 cm ³ or less, preferably 25 c
It is preferably at most m ³ . The weight of plastic used for patrone and patrone case is 5g ~ 15g
Is preferred.

Further, a patrone used in the present invention to feed a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
A different patrone may be used.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as an AP system), and NEXIA A manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film). NEXI
Films processed into the AP system format such as AF and NEXIA H (in order, ISO 200/100/400) and stored in a special cartridge can be mentioned. These AP system cartridge films are used by being mounted on a camera for an AP system such as an Epion series (Epion 300Z or the like) manufactured by Fuji Film. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super slim, which is a Fujicolor photograph run made by FUJIFILM.

The film photographed by the above is printed through the following steps in the minilab system.

(1) Acceptance (exposed cartridge film is received from customer) (2) Detach process (transfer the film from cartridge to intermediate cartridge for development process) (3) Film development (4) Retouch process (development (Return the used negative film to the original cartridge.) (5) Printing (Continuous automatic printing of three types of C / H / P prints and index prints on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Verification and shipping (collating cartridges and index prints with ID numbers and shipping with prints).

These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as minilab champion film processors
362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A / PP12
58AR / PP1258A / PP728AR / PP728A, and the recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII. For Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer L
P-1000W is used. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The AP system can also be enjoyed by a photo joy system centered on the Fuji Film Aladdin 1000 digital image workstation. For example, you can directly load a developed AP system cartridge film into the Aladdin 1000, or transfer image information from negative film, positive film, and print to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints with existing lab equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, the developed AP system cartridge film is replaced with a photo player AP manufactured by FUJIFILM.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To enter a film, print, or three-dimensional object into a computer, use Fujifilm PhotoVision FV-10 / FV.
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

In order to store the developed AP system cartridge film, the Fuji Color Pocket Album AP-5 POP L, AP-1 POP L, AP-1 POP KG or the cartridge file 16 is preferable.

[0154]

<Example 1> On a cellulose triacetate film support having an undercoat, layers having the following compositions were applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.

(Sample 101) First layer (first antihalation layer) Silver chlorobromide emulsion P silver 0.01 gelatin 0.89 ExC-1 0.002 ExC-3 0.002 Cpd-2 0.001 HBS -1 0.004 HBS-2 0.002.

Second layer (second antihalation layer) Gelatin 0.507 ExM-1 0.050 ExF-1 2.0 × 10 ^-3 HBS-1 0.074 Solid disperse dye ExF-2 0.030.

Third layer (intermediate layer) ExC-2 0.029 polyethyl acrylate latex 0.080 gelatin 0.310.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver chloroiodobromide emulsion A silver 0.353 ExS-1 3.8 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 4 × 10 ^-4 ExS-4 1.0 × 10 ^-4 ExS-12 2.7 × 10 ^-4 ExC-1 0.111 ExC-3 0.046 ExC-4 0.072 ExC-5 0.011 ExC -6 0.003 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.17 Gelatin 0.89.

Fifth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Chlorobromide Emulsion B Silver 0.38 Silver Chloroiodobromide Emulsion C Silver 0.44 ExS-1 4.8 × 10 ^-4 ExS-21 0.8 × 10 ^-5 ExS-3 2.8 × 10 ^-4 ExS-4 0.7 × 10 ^-4 ExS-12 1.8 × 10 ^-4 ExC-2 0.029 ExC-3 0.023 ExC- 4 0.15 ExC-5 0.016 ExC-6 0.007 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.16 Gelatin 1.18.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver chloroiodobromide emulsion D Silver 1.39 ExS-1 3.4 × 10 ^-4 ExS-2 1.4 × 10 ^-5 ExS-3 2 × 10 ^-4 ExS-4 0.5 × 10 ^-4 ExS-12 1.8 × 10 ^-4 ExC-3 0.09 ExC-6 0.025 ExC-7 0.010 ExY-5 0.008 Cpd -2 0.046 Cpd-4 0.077 HBS-1 0.25 HBS-2 0.12 Gelatin 2.12.

Seventh layer (intermediate layer) Cpd-1 0.089 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.83 Gelatin 0.89.

Eighth Layer (Layer Which Gives Layered Effect to Red Sensitive Layer) Silver Chlorobromide Emulsion E Silver 0.540 ExS-6 2.8 × 10 ^-4 ExS-10 5.9 × 10 ^-4 Cpd- 4 0.030 ExM-2 0.092 ExM-3 0.024 ExY-1 0.031 HBS-1 0.085 HBS-3 0.003 Gelatin 0.50.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Silver chloroiodobromide emulsion F silver 0.35 silver chloroiodobromide emulsion G silver 0.25 silver chloroiodobromide emulsion H silver 0.39 ExS-4 1.4 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 1.9 × 10 ^-4 ExS-7 3.7 × 10 ^-5 ExS-8 1.0 × 10 ^-4 ExS-12 1.0 × 10 ^-4 ExS-13 6.2 × 10 ^-4 ExM-2 0.33 ExM-3 0.044 ExC-7 0.003 HBS-1 0.28 HBS-3 0.01 HSB-4 0.27 gelatin 1.39.

Tenth Layer (Medium-Sensitive Green-Sensitive Emulsion Layer) Silver Chlorobromide Emulsion I Silver 0.48 ExS-4 2.3 × 10 ^-5 ExS-7 1.0 × 10 ^-4 ExS-8 3 × 10 ^-4 ExS-12 1.0 × 10 ^-4 ExS-13 8.2 × 10 ^-4 ExM-2 0.033 ExM-3 0.030 ExY-1 0.006 ExM-4 0.028 HBS -1 0.064 HBS-3 2.1 x 10 ^-3 gelatin 0.40.

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Silver chloroiodobromide emulsion I Silver 0.17 Silver chloroiodobromide emulsion J Silver 0.76 ExS-4 2.1 × 10 ^-5 ExS-7 1 0.0 × 10 ^-4 ExS-8 1.9 × 10 ^-4 ExS-12 1.0 × 10 ^-4 ExS-13 5.2 × 10 ^-4 ExC-6 0.004 ExM-1 0.013 ExM- 3 0.033 ExM-4 0.022 ExM-5 0.004 ExY-5 0.003 ExM-2 0.013 Cpd-3 0.004 Cpd-4 0.007 HBS-1 0.18 Polyethyl acrylate latex 0.099 gelatin 1.11.

Twelfth Layer (Intermediate Layer) Cpd-1 0.16 HBS-1 0.082 Gelatin 1.057.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Silver chloroiodobromide emulsion K silver 0.22 Silver chloroiodobromide emulsion L silver 0.34 silver chloroiodobromide emulsion M silver 0.14 ExS-9 1.0 × 10 ^-4 ExS-11 1.2 × 10 ^-4 ExS-14 4.2 × 10 ^-4 ExC-8 0.012 ExY-1 0.032 ExY-2 0.74 ExY-30. 12 ExY-4 0.005 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.24 Gelatin 1.41.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver chloroiodobromide emulsion N silver 1.16 ExS-9 1.6 × 10 ^-4 ExS-14 4.5 × 10 ^-4 ExY-20. 30 ExY-3 0.06 ExY-6 0.064 Cpd-2 0.075 Cpd-3 1.0 × 10 ^-3 HBS-1 0.10 Gelatin 0.90.

15th layer (first protective layer) UV-1 0.21 UV-2 0.13 UV-3 0.20 UV-4 0.025 F-18 0.009 HBS-1 0.12 HBS- 4 5.0 × 10 ^-2 gelatin 2.3.

Sixteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-30 .05 S-1 0.20 gelatin 0.75.

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-5, B-4 to B -6, F
-1 to F-19, and iron salts, lead salts, gold salts, platinum salts,
It contains palladium salts, iridium salts, ruthenium salts, rhodium salts, calcium salts and the like. Table 1 below shows the Br content, I content, grain size, and the like of the emulsions represented by the above abbreviations.

[0173]

[Table 1]

In Table 1, (2) Emulsions A to N were optimally subjected to gold sensitization, sulfur sensitization and selenium sensitization in accordance with Example 6 of JP-A-10-221827. (3) The main plane of the tabular grains was the (111) plane, which was prepared by changing the addition conditions, the amounts of the additives, and the like from Example 4 of JP-A-10-221827. The spectral sensitizing dye added depends on the compound described in each photosensitive layer. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) In all of the emulsions A to N, grains having an aspect ratio of 2 or more occupy 100% of the total projected area.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 mL and 3% of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 mL pot mill, and the dye ExF -2 and 500 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersing, take out the contents, 12.5
% Gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.

Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the fine dye particles was 0.45 μm.

The compounds used for forming the above layers are as shown below.

[0178]

Embedded image

[0179]

Embedded image

[0180]

Embedded image

[0181]

Embedded image

[0182]

Embedded image

[0183]

Embedded image

[0184]

Embedded image

[0185]

Embedded image

[0186]

Embedded image

[0187]

Embedded image

[0188]

Embedded image

[0189]

Embedded image

[0190]

Embedded image

[0191]

Embedded image

[0192]

Embedded image

[0193]

Embedded image

[0194]

Embedded image

The fifteenth layer of Sample 101 was changed as shown in Table 2 to prepare Samples 102 to 107. These coated samples were evaluated for pressure resistance by the following method.

[0196]

[Table 2]

The obtained coated sample was allowed to stand at 25 ° C. for 14 days under the condition of humidity control of 64%. 25 ° C, 64%
After the surface of the light-sensitive material was scanned with a record needle loaded with a load of 10 g under the condition of humidity control, the following developing process was performed. Streak-like fog generated by scanning the record needle was measured as yellow density. The result is sample 1
It was expressed as a relative value to 01. The smaller this value is,
It has excellent pressure resistance and is preferable.

It is apparent from Table 2 that the pressure resistance is preferably improved as compared with the sample of the comparative example.

The method of developing a sample is described below.

<Processing Step><Temperature><Time><Replenishment Amount ^* ><TankCapacity> Color Development 35 ° C. 45 seconds 161 mL 17 L Bleaching and Fixing 35 ° C. 45 seconds 215 mL 17 L Rinse 35 ° C. 20 seconds −10 L Rinse 35 ° C 20 seconds -10 L Rinse 35 ° C 20 seconds 360 mL 10 L Drying 80 ° C 60 seconds (* Replenishment amount per 1 m ^{2 of} photosensitive material) (Rinse → 3 tank countercurrent system)

<Color developer> <Tank solution> <Replenisher> Water 700 mL 700 mL Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-Dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5 g 0.5 g Triethanol Amine 12.0 g 12.0 g Potassium chloride 1.6 g-Potassium bromide 0.01 g-Potassium carbonate 27.0 g 27.0 g Fluorescent brightener (WHITBX 4B manufactured by Sumitomo Chemical) 1.0 g 2.5 g Sodium sulfite 0.1 g 0.2 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.0 g 10.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.1 g Add water 1000 mL 1000 mL pH (25 ° C) 10.05 10.45.

<Bleach-fixing solution> (The tank solution and the replenishing solution are the same) Water 600 mL Ammonium thiosulfate (700 g / L) 100 mL Ammonium iron (III) ethylenediaminetetraacetate 55 g 5 g ethylenediaminetetraacetic acid 40 g Ammonium bromide 40 g Nitric acid (67%) 30 g Add water to 1000 mL pH (25 °) (with acetic acid and aqueous ammonia) 5.8.

Example 2 Samples 101 to 10 of Example 1
7, the support used for sample 104 in Example 1 of US Pat. No. 5,597,682 instead of the cellulose triacetate film of the support, that is, column 21, line 54 of the specification. -An undercoat layer and a backing layer were provided by the method described in column 23 to line 29, and a heat-treated PEN support was used. Further, these samples were loaded into a packaging unit having a photographing function (Fujicolor Photo Run, a super slim manufactured by Fuji Photo Film Co., Ltd.), and evaluated in the same manner as in Example 1.

As a result, the same result as in Example 1 was obtained.

Example 3 Samples 101 to 10 of Example 1
9, Samples 201 to 209 were prepared by changing the emulsions A to P in Table 1 as shown in Table 3. These samples were prepared in Example 1.
When the evaluation was carried out in the same manner as described in Example 1, the sample of the present invention was excellent in pressure properties as in Example 1.

However, Samples 201 to 209 were slightly inferior in rapid processing properties, and the color development time was reduced from 45 seconds to 75 seconds in the processing method described in Example 1 in order to provide the same gradation as Samples 101 to 109. We changed and evaluated.

[0207]

[Table 3]

[0208]

According to the present invention, there is provided a light-sensitive material which is excellent in rapid processing suitability, has excellent pressure resistance, and suppresses abrasion and press fog generated during handling of the light-sensitive material. can do.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H016 BB02 BB04 BC02 BC03 BD04 BJ01 2H023 BA02 BA04 CD02 CE01 GA00 GA03

Claims (2)

[Claims] 1. A blue-sensitive silver halide emulsion layer containing at least one yellow coupler on a support.
A green-sensitive silver halide emulsion layer containing a magenta coupler, a red-sensitive silver halide emulsion layer containing a cyan coupler, a second protective layer comprising a non-photosensitive hydrophilic colloid layer as the outermost layer and a support side adjacent thereto A silver halide color photographic light-sensitive material having a first protective layer on the side farther from the support adjacent to the blue-sensitive highest sensitivity layer
50% of the total projected area of at least one layer of silver halide grains
The above is occupied by tabular silver halide grains having an aspect ratio of 2 or more and a silver chloride content of 50 mol% or more, and the elastic modulus of the first protective layer is the elastic modulus of the blue photosensitive layer having the highest sensitivity. A silver halide color photographic light-sensitive material, characterized in that it has a size of at least 2 times and not more than 10 times. 2. An ultraviolet absorber is emulsified and dispersed using at least one of a water-insoluble and organic solvent-soluble homo- or copolymer comprising a repeating unit having a —C (＝ O) — bond in a main chain or a side chain. 2. A silver halide color photographic light-sensitive material according to claim 1, wherein the dispersion obtained by the above-mentioned method is contained in the first protective layer.