JP2000098515A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material good in the neutrality of a black image hue even after long time storage by incorporating a specified coupler in at least one silver halide emulsion layer and at least each one kind of specified compound in at least one silver halide emulsion layer. SOLUTION: The silver halide photographic sensitive material contains each one of yellow, magenta, and cyan couplers, or a black forming coupler, respectively, in each one of silver halide emulsion layers, and at least one of the emulsion layers contains at least one kind of compound represented by formula I-III in which R1 is a tertiary alkyl group; R2 a primary alkyl group or the like; each of R3-R5 is an H atom or the like; R11 is an aliphatic or aromatic group or the like; each of R12 and R13 is an aliphatic group or the like; each of R21 and R24 is an aromatic group or the like; each of R22 and R23 is an H atom or the like; and X is a halogen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material, and more particularly, to a black-and-white silver halide photographic material which can be processed with a color developer.

[0002]

2. Description of the Related Art Conventionally, a black-and-white photographic image is formed by developing a silver halide with a black-and-white developing solution to form a silver image. In this black-and-white developer, a reducing agent such as hydroquinone or ascorbic acid is used to reduce the exposed silver halide to metallic silver.

Therefore, in order to develop a color print and a monochrome print in a developing lab, different developers and processors for color and black and white are required. For this reason, the profitability of the developing laboratory is deteriorated, and a problem occurs in securing the installation space.

In order to solve such a problem, it is desired to propose a black-and-white photosensitive material capable of color processing. To meet such demands, a method of obtaining a black-and-white image by a layer in which a yellow coupler, a magenta coupler and a cyan coupler are mixed is described in, for example, JP-A-6-505580.

However, when such a method is adopted, there is a problem that the neutrality of a black image is easily deteriorated and the hue is likely to be shifted from black. Further, when the formed image is stored under light irradiation, there is a problem that the neutrality of the black image is inferior.
There is also a problem that the white portion is easily deteriorated.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material in which the black and white hue of a black-and-white silver photographic light-sensitive material which can be color-processed has a good neutrality after storage over time. To do.

Another object of the present invention is to provide a black-and-white silver halide photographic light-sensitive material which has good whiteness and can be color-processed even after storage for a long time after image formation.

[0008]

The above object has been attained by the following constitution of the present invention.

1. In a silver halide photographic material having at least one silver halide emulsion-containing layer on a support, at least one silver halide emulsion-containing layer contains three couplers of a yellow coupler, a magenta coupler and a cyan coupler or A black-forming coupler is contained, and at least one silver halide emulsion-containing layer contains at least one of the compounds represented by the following general formulas [1], [2] and [3]. Silver halide photographic light-sensitive material.

[0010]

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In the formula, R ₁ represents a tertiary alkyl group, and R ₂ represents a primary or secondary alkyl group. However, R ₂ is not substituted by a phenyl group. R ₃ , R ₄ and R ₅
Is a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, an alkoxy group, a phenoxy group,
Represents a phenylthio group.

[0012]

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In the formula, R ₁₁ represents an aliphatic group, an aromatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, or an aromatic oxy group;
₁₄ represents a hydrogen atom, an aliphatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, or an aromatic oxy group, R ₁₂ and R ₁₃ each independently represent a hydrogen atom, Represents an aliphatic group or an aromatic group.

[0014]

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In the formula, R ₂₁ and R ₂₄ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, or an aromatic oxy group. R ₂₂ and R ₂₃ each independently represent a hydrogen atom, an aliphatic group, or an aromatic group;
X represents a halogen atom. However, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are not simultaneously hydrogen atoms.

2. In a silver halide photographic material having at least one silver halide emulsion-containing layer on a support, at least one silver halide emulsion-containing layer contains three couplers of a yellow coupler, a magenta coupler and a cyan coupler or A silver halide photographic material comprising a black-forming coupler and the silver halide emulsion-containing layer containing at least one water-insoluble and organic solvent-soluble polymer compound.

3. A silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a support, wherein at least one silver halide emulsion-containing layer has a blue-sensitive silver halide emulsion; One layer containing a silver halide emulsion contains three couplers of a yellow coupler, a magenta coupler and a cyan coupler or a black-forming coupler, and at least one layer containing a silver halide emulsion on a support contains an epoxy coupler. A silver halide photographic material characterized by containing a group-containing compound.

Hereinafter, the present invention will be described in detail.

In the present invention, at least one layer containing a silver halide emulsion contains three couplers of a yellow coupler, a magenta coupler, and a cyan coupler or a black-forming coupler. This is a coupler necessary for obtaining a black and white image in a color development process. Any of the three types of couplers may be used, but it is preferable to use a combination of couplers separately described below. When combined, it is prepared to have a substantially black and white image hue. As a black-forming coupler,
A compound having a single color-forming portion and capable of obtaining a black or black-like color (for example, 4- (isopropylcarbamoylmethoxy) -3-N-octadecylaminophenol)
And a compound having a plurality of color-forming portions and capable of obtaining a black or black-like color (for example, a copolymer having yellow, magenta, and cyan color-forming portions).

It is more preferable to obtain a black or black approximate image by combining and mixing three types of yellow coupler, magenta coupler, and cyan coupler, because the desired color adjustment can be easily performed.

In the first invention, at least one of the silver halide emulsion-containing layers contains the compound represented by the general formula [1], [2] or [3].

First, the compound represented by the general formula [1] will be described.

In the general formula [1] according to the present invention,
R ₁ represents a tertiary alkyl group (for example, a t-butyl group, a t-pentyl group, a t-octyl group, etc.), and is preferably a t-butyl group. R ₂ represents a primary or secondary alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, etc.), and is preferably a methyl group. However, R ₂ may be substituted by a substituent, but is not substituted by a phenyl group. R ₃ , R ₄ and R _{5 each} represent a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, a butyl group, a dodecyl group), an alkoxycarbonyl group (eg, an ethoxycarbonyl group), a phenoxycarbonyl group (eg, 2,
4-di-t-butylphenoxycarbonyl group and the like), alkoxy group (for example, 2-ethylhexyloxy group and the like),
A phenoxy group (for example, 4- (2-ethylhexyl) phenoxy group, 4-dodecyl-phenoxy group, etc.) and a phenylthio group (for example, 3-tbutyl-4-hydroxy-5-methylphenylthio group, etc.).

The groups represented by R ₁ to R ₅ may be substituted with a substituent. The compound represented by the general formula [1] is preferably a compound not containing a primary, secondary or tertiary amino group in the structural formula or a compound not containing an acylamino group. Compounds containing no primary, secondary or tertiary amino groups are more preferred. Further, the group represented by R ₄ is preferably an alkyl group.

The group represented by R ₄ is more preferably a group containing the following linking group.

[0026]

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(Wherein R ₆ , R ₆ ′, R ₇ , R ₇ ′, R ₈ ,
R ₈ ', R ₉ and R _9' are each a hydrogen atom, an alkyl group, a phenyl group. Among the compounds represented by the general formula [1], preferred compounds are compounds represented by the following general formulas [1A] and [1B].

[0028]

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In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ have the same meanings as R ₁ to R _{5 in the} general formula [1]. R ₁₁ represents an alkylene group (for example, an ethylene group or an isobutylene group).

Among the compounds of the general formulas [1A] and [1B], a more preferred compound is a compound represented by the general formula [1B].

Next, specific examples of the compound represented by the general formula [1] are shown, but the present invention is not limited thereto.

[0032]

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[0033]

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Next, the 1,2 diol compound represented by the general formula [2] and the halohydrin compound represented by the general formula [3] will be described.

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₂₁ , R ₂₂ , R
Examples of the aliphatic group represented by ₂₃ and R ₂₄ include linear, branched and cyclic alkyl groups (for example, n-butyl group, n-dodecyl group, 2-ethylhexyl group, 2-hexyldecyl group, t- A butyl group, a cyclopentyl group, a cyclohexyl group and the like, and a linear, branched and cyclic alkenyl group (for example, a propenyl group, a 1-methyl-2-hexenyl group and a 2-cyclohexenyl group).

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₂₁ , R ₂₂ , R
Examples of the aromatic group represented by ₂₃ and R ₂₄ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

Examples of the acyl group represented by R ₁₁ , R ₁₄ , R ₂₁ and R ₂₄ include an aliphatic carbonyl group and an aromatic carbonyl group, and include an aliphatic carbonyl group and an aliphatic carbonyl group. The aromatic group is as defined above.

The aliphatic group of the aliphatic oxycarbonyl group represented by R ₁₁ , R ₁₄ , R ₂₁ and R ₂₄ has the same meaning as described above.

The aromatic group of the aromatic oxycarbonyl group represented by R ₁₁ , R ₁₄ , R ₂₁ and R ₂₄ is as defined above.

The aliphatic groups of the aliphatic oxy groups represented by R ₁₁ , R ₁₄ , R ₂₁ and R ₂₄ are the same as those described above, and the aromatic groups of the aromatic oxy groups are the same as the above-mentioned aromatic groups. Represents

The above substituents may further have a substituent. Examples of the further substituted substituent include an aliphatic group, an aromatic group, a heterocyclic group, a hydroxyl group, a carboxyl group, a sulfo group, Phosphate group, nitro group, cyano group, acylamino group, acyloxy group, carbamoyl group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, acyl group,
Sulfonamide group, sulfamoyl group, sulfonate group, sulfonyl group, sulfinyl group, phosphonyl group, phosphate group, mercapto group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic thio group,
Examples thereof include an aromatic thio group, a heterocyclic thio group, and a halogen atom.

R ₁₁ and R ₁₂ , R ₁₁ and R ₁₃ , R ₁₁ and R ₁₄ , R
₁₂ and R ₁₃ , R ₂₁ and R ₂₂ , R ₂₁ and R _23, R ₂₁ and R ₂₄ , R
_The groups ₂₂ and R ₂₃ may be condensed with each other to form a ring in the molecule.

Among the substituents represented by R ₁₁ and R _21, preferred are an aliphatic group, an aliphatic oxycarbonyl group and an aromatic oxycarbonyl group, and particularly preferred is an aliphatic group.

Among the substituents represented by R ₁₄ and R _24, preferred are a hydrogen atom or an aliphatic group, and particularly preferred is a hydrogen atom.

Among the substituents represented by R ₁₂ , R ₁₃ , R ₂₂ and R _23, preferred are a hydrogen atom and an aliphatic group, and particularly preferred is a hydrogen atom.

Preferred among the halogen atoms represented by X are chlorine atoms or bromine atoms, and particularly preferred are chlorine atoms.

Among the 1,2-diol compounds represented by the general formula [2], a compound represented by the general formula [2-a] is particularly preferable.

[0048]

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In the formula, R ₁₀₁ represents an aliphatic group, an aromatic group or an acyl group, and n represents 0 or 1.

Among the halohydrin compounds represented by the general formula [3], a compound represented by the general formula [3-a] or [3-b] is particularly preferable.

[0051]

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In the formula, R ₂₀₁ represents an aliphatic group, an aromatic group or an acyl group, and m represents 0 or 1.

Formulas [2-a], [3-a] and [3-a]
b), the aliphatic group, aromatic group and acyl group represented by R ₁₀₁ and R ₂₀₁ are the same as those represented by R in general formulas [2] and [3].
Those described in ₁₁ and R ₂₂ is as defined above.

Specific examples of the compounds [2] and [3] of the present invention are shown below, but the present invention is not limited to these.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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In the second invention, the black image forming layer contains a water-insoluble and organic solvent-soluble polymer compound.

The water-insoluble and organic solvent-soluble polymer compound will be described below.

The water-insoluble and organic solvent-soluble polymers usable for the above purpose include (1) vinyl polymers and copolymers (2) polycondensates of polyhydric alcohols and polybasic acids (3) ring opening Polyester obtained by a polymerization method (4) Other polymers and the like. Hereinafter, (1)-
(4) will be described.

(1) Vinyl Polymer and Copolymer The monomers forming the vinyl polymer and copolymer include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, t-octyl acrylate, 2-chloroethyl acrylate, cyanoethyl acrylate, 2-
Acrylates such as acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, and phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isopropyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, sulfo Methacrylic acid esters such as propyl methacrylate, phenyl methacrylate, cresyl methacrylate, 2-hydroxyethyl methacrylate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl chloride acetate, vinyl methoxy acetate, vinyl phenyl acetate , Vinyl benzoate Vinyl esters such as vinyl salicylate, acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, t- butyl acrylamide, cyclohexyl acrylamide,
Acrylamides such as benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, N- (2-hydroxy-5-ethylsulfonylphenyl) acrylamide, methacrylamide, methylmethacrylamide,
Ethyl methacrylamide, propyl methacrylamide,
Butyl methacrylamide, t-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethyl methacrylamide, dimethylaminoethyl, phenyl methacrylamide, N- (3-hydroxyphenyl) methacrylamide Methacrylamides, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, butadiene, isoprene, olefins such as chloroprene, vinyl chloride, vinylidene chloride, styrene, methyl styrene, trimethyl styrene, ethyl styrene, chloro Styrenes such as methylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, and vinylbenzoic acid are exemplified. In addition, crotonic esters such as butyl crotonate, itaconic diesters such as diethyl itaconate, maleic diesters such as dimethyl maleate, fumaric diesters such as dimethyl fumarate, and allyl such as allyl acetate. Compounds, methyl vinyl ether, vinyl ethers such as methoxyethyl vinyl ether, vinyl ketones such as methyl vinyl ketone, vinyl pyridine,
Examples thereof include vinyl heterocyclic compounds such as N-vinyloxazolidone, glycidyl esters such as glycidyl acrylate, and unsaturated nitriles such as acrylonitrile.

The polymer compound used in the present invention may be a homopolymer of the above-mentioned monomers or, if necessary, a copolymer of two or more monomers. Further, the polymer used in the present invention may contain a monomer having an acid group shown below to such an extent that the polymer does not become water-soluble, but is preferably 20% or less, and more preferably contains no monomer at all. .

Examples of the monomer having an acid group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, monoalkyl maleate, citraconic acid, styrenesulfonic acid, vinylbenzylsulfonic acid,
Examples include acryloyloxyalkylsulfonic acid, methacryloyloxyalkylsulfonic acid, acrylamidoalkylsulfonic acid, methacrylamidoalkylsulfonic acid, acryloyloxyalkylphosphate, and methacryloyloxyalkylphosphate. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions.

As the monomers forming the polymer used in the present invention, acrylates, methacrylates, acrylamides and methacrylamides are preferred.

The polymer formed from the above monomers can be obtained by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a latex polymerization method. As the initiator used for these polymerizations, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, sodium 4,4'-azobis-4-cyanovalerate, and 2,2'-azobis (2-amidino Water-soluble azo compounds such as propane) hydrochloride and hydrogen peroxide can be used. Examples of the lipophilic polymerization initiator include azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexanone-1-carbonitrile), Lipophilic azo compounds such as dimethyl 2'-azobisisobutyrate, diethyl 2,2'-azobisisobutyrate, benzoyl peroxide,
Lauryl peroxide, diisopropyl peroxydicarbonate and di-t-butyl peroxide can be mentioned.

(2) 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-R
₂ —COOH (R ₂ represents a simple bond or has 1 carbon atom
To 12 hydrocarbon chains) are effective.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylene diol, 1,5-pentane Diol, neopentyl glycol, 1,6-hexanediol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Decanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythrit, mannitol, sorbit and the like.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cornic acid, azelaic acid, sebacic acid, decanedicarboxylic acid,
Dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohimeric acid, cyclopentadiene-maleic anhydride adduct,
Rosin-maleic anhydride adduct;

(3) Polyester Obtained by Ring-Opening Polymerization These polyesters include β-propiolactone, ε-
It can be obtained from caprolactone, dimethylpropiolactone and the like.

(4) Other Polymers Novolak resin, polycarbonate resin obtained by polycondensation of glycol or dihydric phenol with carbonate or phosgene, polyurethane resin obtained by polyaddition of polyhydric alcohol and polyisocyanate Or a polyamide resin obtained from a polyvalent amine and a polybasic acid.

The number average molecular weight of the polymer used in the present invention is not particularly limited, but is preferably 200,000 or less, more preferably 5,000 to 100,000.

The ratio (weight ratio) of the polymer of the present invention to the coupler is preferably from 1:20 to 20: 1, more preferably from 1:10 to 10: 1.

Specific examples of the polymer used in the present invention are shown below, but it should not be construed that the invention is limited thereto. (The composition of the copolymer is shown by weight ratio.) P-1 poly (N-sec-butylacrylamide) P-2 poly (Nt-butylacrylamide) P-3 diacetoneacrylamide-methyl methacrylate copolymer (25:75) P-4 polycyclohexyl methacrylate P-5 Nt-butylacrylamide-methyl methacrylate copolymer (60:40) P-6 poly (N, N-dimethylacrylamide) P-7 poly (t- (Butyl methacrylate) P-8 polyvinyl acetate P-9 polyvinyl propionate P-10 polymethyl methacrylate P-11 polyethyl methacrylate P-12 polyethyl acrylate P-13 vinyl acetate-vinyl alcohol copolymer (9
0:10) P-14 polybutyl acrylate P-15 polybutyl methacrylate P-16 polyisobutyl methacrylate P-17 polyisopropyl methacrylate P-18 polyoctyl acrylate P-19 butyl acrylate-acrylamide copolymer (95: 5) P -20 Stearyl methacrylate-acrylic acid copolymer (90:10) P-21 Methyl methacrylate-vinyl chloride copolymer (70:30) P-22 Methyl methacrylate-styrene copolymer (90:10) P-23 methyl Methacrylate-ethyl acrylate copolymer (50:50) P-24 butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:30) P-25 vinyl acetate-acrylamide copolymer (8
5:15) P-26 vinyl chloride-vinyl acetate copolymer (65: 3)
5) P-27 methyl methacrylate-acrylonitrile copolymer (65:35) P-28 butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38: 3)
8:24) P-29 methyl methacrylate-butyl methacrylate-isobutyl methacrylate-acrylic acid copolymer (37: 29: 25: 9) P-30 butyl methacrylate-acrylic acid copolymer (95: 5) P-31 methyl Methacrylate-acrylic acid copolymer (95: 5) P-32 benzyl methacrylate-acrylic acid copolymer (93: 7) P-33 Butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (3
5: 35: 25: 5) P-34 butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (40: 30: 3)
0) P-35 diacetone acrylamide-methyl methacrylate copolymer (50:50) P-36 methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) P-37 ethyl methacrylate-butyl acrylate copolymer (70: 30) P-38 diacetone acrylamide-butyl acrylate copolymer (60:40) P-39 methyl methacrylate-styrene methacrylate-diacetone acrylamide copolymer (40: 4)
0:20) P-40 butyl acrylate-styrene methacrylate-diacetone acrylamide copolymer (70:20:
10) P-41 Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) P-42 Methyl methacrylate-styrene-vinylsulfonamide copolymer (70:20:10) P-43 Methyl methacrylate- Phenyl vinyl ketone copolymer (70:30) P-44 butyl acrylate-methyl methacrylate-butyl methacrylate copolymer (35:35:30) P-45 butyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90 : 10) P-46 polypentyl acrylate P-47 cyclohexyl methacrylate-methyl methacrylate-propyl methacrylate copolymer (37:
29:34) P-48 Polypentyl methacrylate P-49 Methyl methacrylate-butyl methacrylate copolymer (65:35) P-50 Vinyl acetate vinyl propionate copolymer (75:25) P-51 Butyl methacrylate-3 -Acryloxybutane-1-sodium sulfonate copolymer (97:
3) P-52 butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) P-53 butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) P-54 butyl methacrylate-styrene Copolymer (82:12) P-55 t-butyl methacrylate-methyl methacrylate copolymer (70:30) P-56 poly (Nt-butyl methacrylamide) P-57 N-t-butylacrylamide-methyl Phenyl methacrylate copolymer (60:40) P-58 Methyl methacrylate-acrylonitrile copolymer (70:30) P-59 Methyl methacrylate-methyl vinyl ketone copolymer (38:72) P-60 Methyl methacrylate-styrene Copolymer (75:25 P-61 Methyl methacrylate-hexyl methacrylate copolymer (70:30) P-62 Butyl methacrylate-acrylic acid copolymer (85:15) P-63 Methyl methacrylate-acrylic acid copolymer (80:20) P- 64 methyl methacrylate-acrylic acid copolymer (90:10) P-65 methyl methacrylate-acrylic acid copolymer (98: 2) P-66 methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) P-67 butyl methacrylate-vinyl chloride copolymer (90:10) P-68 butyl methacrylate-styrene copolymer (70:30) P-69 1,4-butanediol-adipate polyester P-70 Ethylene glycol -Sebacic acid polyester P-71 polycaprolactam P-72 Polypropiolactam P-73 Polydimethylpropiolactone P-74 Nt-butylacrylamide-dimethylaminoethylacrylamide copolymer (85:15) P-75 Nt-butylmethacrylamide-vinylpyridine Polymer (95: 5) P-76 Diethyl maleate-butyl acrylate copolymer (65:35) P-77 Nt-butylacrylamide-2-methoxyethyl acrylate copolymer (55:45) P-78 ω-methoxy polyethylene glycol methacrylate (additional mole number n = 6) -methyl methacrylate (40:60) P-79 ω-methoxypolyethylene glycol acrylate (additional mole number n = 9) -Nt-butylacrylamide (25:75) ) P-80 Poly (2-methoxyethyl ac) Rate) P-81 poly (2-methoxyethyl methacrylate) P-82 poly [2- (2-methoxyethoxy) ethyl acrylate] P-83 2- (2-butoxyethoxy) ethyl acrylate-methyl methacrylate (58:42) P-84 poly (oxycarbonyloxy-1,4-phenyleneisobutylidene-1,4-phenylene) P-85 poly (oxyethyleneoxycarbonyliminohexamethyleneiminocarbonyl) P-86 N- [4- (4 ' -Hydroxyphenylsulfonyl) phenyl] acrylamide-butyl acrylate copolymer (65:35) P-87 N- (4-hydroxyphenyl) methacrylamide-Nt-butylacrylamide copolymer (5
0:50) P-88 [4- (4'-hydroxylphenylsulfonyl) phenoxymethyl] styrene (m, p mixture)-
Nt-butylacrylamide copolymer (15:85) In the third invention, at least one layer contains an epoxy group-containing compound.

The epoxy group-containing compound may be any compound having an epoxy group in the molecule, and examples thereof include the following compounds.

[0077]

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[0078]

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[0079]

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These compounds can be added to a photographic element by a known method. As one method, it can be added by an oil-in-water dispersion method as an oil protection method.

It is preferable to add these compounds in an amount of 0.01 to 1 mol per 1 mol of the coupler.

In the first to third aspects of the present invention, a further preferred embodiment is to further add a bisphenol-type antioxidant to the black image forming layer of the silver halide photographic light-sensitive material.

The composition of the silver halide photographic emulsion according to the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide and the like. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. From the viewpoint of rapid processing property and processing stability, the silver halide emulsion preferably contains 97 mol% or more, more preferably 98 to 99.9 mol%, of average silver chloride.

For obtaining the above silver halide emulsion, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing silver bromide at a high concentration may be epitaxy-bonded to silver halide emulsion grains, may be a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. May simply have regions with different compositions. The composition may change continuously or may change discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In the present invention, it is advantageous to include a heavy metal ion. Heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; and twelfth metals such as cadmium, zinc, and mercury. Group transition metals, and ions of lead, rhenium, molybdenum, tungsten, gallium, chromium, and the like. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex,
Examples of the ligand or ion include cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion,
Preferred are isothiocyanate ion, chloride ion, bromide ion and the like.

In order to make the silver halide emulsion contain heavy metal ions, the heavy metal compound is added to the silver halide emulsion during physical ripening before silver halide grain formation, during silver halide grain formation, and during physical ripening after silver halide grain formation. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, the heavy metal compound may be dissolved together with the halide salt and added continuously over the whole or a part of the grain forming step.

The amount of heavy metal ion added to the silver halide emulsion is from 1 × 10 ^-9 to 1 × 1 per mol of silver halide.
It is preferably from 0 to ² mol, and particularly preferably from 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737,
Octahedrons, tetradecahedrons, dodecahedrons, etc., by methods described in documents such as The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973). Can be produced and used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape are preferably used, but it is particularly preferred to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The particle size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. The range is 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of preferably 0.05 to 0.22, more preferably 0.05 to 0.15.
Particularly preferably, two or more monodispersed emulsions of 0.05 to 0.15 are added to the same layer. Where the coefficient of variation is
This is a coefficient indicating the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size referred to here is the diameter of spherical silver halide grains, In the case of particles having a shape other than a cubic or a spherical shape, the diameter represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at a time, or may be grown after seed particles have been produced. The method for producing the seed particles and the method for growing the seed particles may be the same or different.

The form of reacting the soluble silver salt with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but the method obtained by the simultaneous mixing method is preferable. . Further, as one form of the simultaneous mixing method, pA described in JP-A-54-48521 and the like are described.
g The controlled double jet method can also be used.

Also, JP-A-57-92523, JP-A-57-92523.
No. 92524, etc., a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt described in DE 2,921,164. And an apparatus for continuously adding an aqueous solution of a water-soluble halide while changing its concentration, Japanese Patent Publication No. 56-5017.
No. 76, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer is preferable.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect, and the like.
10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
A range of ^10-5 mol is desirable.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. Is preferably
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization of a silver halide emulsion includes:
A reduction sensitization method may be used.

The silver halide emulsion may contain a known antifoggant such as a fogging agent for the purpose of preventing fogging during the preparation process of the light-sensitive material, reducing performance fluctuation during storage, or fogging during development. Agents can be used. Preferred examples of the compound used for such purpose include a compound represented by the general formula [II] described in the lower column on page 7 of JP-A-2-14636, and more preferred specific compounds include II described on page 8 of the publication
a-1 to IIa-8, IIb-1 to IIb-7, 1
Compounds such as-(3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned.

These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, completion of the chemical sensitizing step, coating liquid preparing step and the like. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ⁻² mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 ~ × 10 ^{- Two} moles are more preferred.
Further, when added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ⁻⁹ to 1 × 10 ⁻³ per m ^2.
Molar amounts are preferred.

As the light-sensitive material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are preferable. It is preferable because it has spectral characteristics, does not affect the photographic characteristics of the photographic emulsion, and does not stain due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of an unprocessed sample of the light-sensitive material is 0.7 to 3.0, and more preferably 0.8 to 3.0. More preferably, it is 3.0.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the whiteness can be improved. The compound preferably used is a compound represented by the general formula [I] described in JP-A-2-232652.
I].

When the light-sensitive material of the present invention is used as a color light-sensitive material, 400 to 900 nm
Has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the wavelength range of The silver halide emulsion contains one or more sensitizing dyes in combination.

As the spectral sensitizing dye used in the present invention, any of known compounds can be used. Examples of the blue-sensitive sensitizing dye include BS-1 to BS-1 described on page 28 of JP-A-3-251840. BS-8 can be preferably used alone or in combination. Green photosensitive sensitizing dyes include:
GS-1 to GS-5 described on page 28 of the publication are preferable,
Further, as the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye,
Examples of the infrared-sensitive sensitizing dye include JP-A-4-285950.
And the dyes IRS-1 to IRS-11 described on pages 6 to 8 are preferably used. These infrared, red, green, and blue sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-6-6.
No. 6515, pages 15 to 17, compounds S-1 to S-
It is preferable to use 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like, or in water, or adding it as a solid dispersion. It may be added.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, particularly typical couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm,
Examples include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Examples of cyan couplers that can be preferably used include couplers represented by formulas [CI] and [C-II] described in the lower left column of page 5 of JP-A-4-114154. As a specific compound, the publication 5
There can be mentioned those described as CC-1 to CC-9 in the lower right column of page 6 to the lower left column of page 6.

Examples of the magenta coupler that can be preferably used include couplers represented by general formulas [MI] and [M-II] described in the upper right column of page 4 of JP-A-4-114154. Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. Among the above magenta couplers, more preferred are those represented by the general formula [MI]
A coupler represented by the general formula [M-
The coupler of the formula (I) wherein R _M is a tertiary alkyl group is particularly preferred because of its excellent light resistance. M described in the upper column on page 5 of the publication
C-8 to MC-11 are preferable because they are excellent in reproduction of colors ranging from blue to purple and red, and are also excellent in detail description.

As the yellow coupler which can be preferably used, there can be mentioned a coupler represented by the general formula [YI] described in the upper right column on page 3 of JP-A-4-114154. YC on the lower left column of page 3
-1 to YC-9. Among them, a coupler of the formula [Y-I] in which R _Y1 is an alkoxy group or a coupler represented by the formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow having a preferable color tone. Of these, YC-8 and YC-9 and JP-A-6-673881 described in the upper left column of page 4 of JP-A-4-114154 are particularly preferred.
Compounds represented by Nos. (1) to (47) on pages 3 to 14 can be exemplified. The most preferred compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

When an oil-in-water emulsion dispersion method is used to add a coupler or other organic compound used in a light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or more, if necessary. To dissolve in combination with a low boiling point and / or water-soluble organic solvent, and emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill,
A flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be included.

Examples of high boiling organic solvents which can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate and trioctyl phosphate. And the like are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

Alternatively, instead of using a high-boiling organic solvent, or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A-1 to A-1 described in JP-A-64-26854.
1 is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are
Usually, it is added to a coating solution containing a silver halide emulsion, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution to the coating are shorter, each being preferably within 10 hours. More preferably, within 3 hours and within 20 minutes.

It is preferable to use an anti-fading agent in combination with the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas [I] and [II] described in JP-A-2-66541, page 3, and phenols represented by general formula [IIIB] described in JP-A-3-174150. Amine compounds represented by the general formula [A] described in JP-A-64-90445;
General formulas (XII), (XIII) and (XI) described in No. 182741
V] and metal complexes represented by [XV] are particularly preferred for magenta dyes. Also, a compound represented by the general formula [I] described in JP-A-1-19649 and JP-A-5-1141.
The compound represented by the general formula [II] described in No. 7 is particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compounds such as compound d-11 described in the lower left column of page 9 of JP-A-4-114154 and compound A'-1 described in the upper left column of page 10 are used. be able to. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to prevent fog. Is preferably improved. As the compound for this, a hydroquinone derivative is preferred, and more preferably
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula [II] described in JP-A-4-133056, and the compounds II-1 to II-14 described on pages 13 to 14 of the same publication.
Compounds-1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog and to improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula [III-] described in JP-A-1-250944.
3], a compound represented by the general formula [III] described in JP-A-64-66646, and a compound represented by JP-A-63-18
No. 7240, UV-1L to UV-27L;
Compounds represented by the general formula [I] described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention. If necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, A hydrophilic colloid such as a single or a synthetic hydrophilic polymer such as a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener or a carboxyl group-active hardener alone or in combination. JP-A-61-249054, 61-
It is preferable to use the compounds described in US Pat. Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15764 is incorporated in the colloid layer.
It is preferable to add a preservative and an antifungal agent as described in No. 6. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

As the support used for the light-sensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, and a white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper and the like may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferred.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as fine silica powder, synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, oxide Zinc, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by weight or more, more preferably 15% by weight, in order to improve sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the variation coefficient described in the publication.

Further, it is more preferable that the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, because the effect of good gloss is obtained.
Also, in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment, ultramarine blue, oil-soluble dyes, etc. It is preferable to add a small amount of a bluing agent or a reddish agent.

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, on the surface of the support, directly or undercoating (adhesion, antistatic properties, dimensional stability on the surface of the support). , One or more undercoating layers for improving friction resistance, hardness, antihalation property, frictional properties and / or other properties).

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically focused on the photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. Printing may be performed by scanning while changing the light intensity.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display,
A light-sensitive material for color proof can be used. In particular, it is preferably applied to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-lauryl) aminotoluene CD-4: 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamido) ethylaniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline CD-8: N, N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N
-([Gamma] -hydroxypropyl) ethylaniline In the present invention, the use of the above compound is adjusted to pH 9.5 to 13.0, more preferably pH 9.5, from the viewpoint of rapid processing.
Used in the range of 8 to 12.0.

The processing temperature for color development in the present invention is 3
5-70 ° C is preferred. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution.

Conventionally, the color development time is generally 3 minutes 30 minutes.
Although it is performed in about seconds, in the present invention, it is preferably performed within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ion and benzotriazole, a preservative, a chelating agent and the like are used.

After the color development, the light-sensitive material is subjected to a bleaching process and a fixing process. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the washing process, a stabilizing process may be performed.

The developing apparatus used for processing the photosensitive material of the present invention may be a roller transport type in which the photosensitive material is transported by sandwiching the photosensitive material between rollers disposed in a processing tank. An endless belt system for conveying may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and a photosensitive material is conveyed and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

[0145]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, on the side to be coated with the emulsion layer, a molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed in a content of 15% by weight was laminated to produce a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material.

Fifth layer (protective layer) Addition amount g / m ² Gelatin 0.7 Fourth layer (ultraviolet absorbing layer) Gelatin 1.5 Ultraviolet absorber UV-1 4.0 Ultraviolet absorber UV-2 1.3 UV absorber UV-3 5.0 Third layer (red-sensitive layer) Gelatin 2.0 Yellow coupler Y-1 0.38 Magenta coupler M-1 0.14 Cyan coupler C-1 0.09 Cyan coupler C-2 0.26 DBP 0.83 Red-sensitive silver halide emulsion (Em-R) 0.39 AI-1 0.05 Second layer (green-sensitive layer) Gelatin 2.0 Yellow coupler Y-1 0.26 Magenta coupler M -1 0.09 Cyan coupler C-1 0.06 Cyan coupler C-2 0.18 DBP 0.57 Green-sensitive silver halide emulsion (Em-G) 0.26 AI-2 0.01 First layer (blue) Sensitive layer) Zera 0.5 Yellow coupler Y-1 0.05 Magenta coupler M-1 0.02 Cyan coupler C-1 0.01 Cyan coupler C-2 0.03 DBP 0.07 Blue-sensitive silver halide emulsion (Em-B ) 0.05 AI-2 0.03 Support polyethylene-laminated paper The amount of silver halide emulsion added was shown in terms of silver. (H-1) and (H-2) were added as hardeners. Surfactants (SU-1), (S
U-2) was added to adjust the surface tension. Further, an antifungal agent (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

SU-1: di (2-ethylhexyl) sulfosuccinate sodium salt SU-2: di (2,2,3,3,4,4, sulfosuccinate)
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium

[0149]

Embedded image

[0150]

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[0151]

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<Preparation of blue-sensitive, green-sensitive and red-sensitive silver halide emulsions> (Preparation of blue-sensitive silver halide emulsion)
(A solution) and (B)
Liquid) to 30 while controlling pAg = 7.3 and pH = 3.0.
The solution (C solution) and the (solution D) were added simultaneously over 180 minutes while controlling the pAg at 8.0 and the pH at 5.5. At this time, the control of pAg is described in
The control of pH was performed using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
As in the case of -1, the average particle diameter is 0.64 μm, and the coefficient of variation is 0.1.
07, a monodispersed cubic emulsion EMP-1B having a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

Next, a monodispersed cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole -1 was added in an amount of 2.0 × 10 ^-3 mol per mol of silver halide.

[0162]

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[0163]

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[0164] The sample prepared in this manner was used as the sample 101.
And Next, except that the compounds were added to the first, second, and third layers of Sample 101 in combinations shown in Table 1, Sample 10
Each sample similar to 1 was prepared.

These samples were subjected to white light wedge exposure and developed according to a standard method.

The development was carried out by the following development process.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80ml Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds 120ml Stabilization 30-34 ° C 60 seconds 150ml Dry Drying 60 to 80 ° C for 30 seconds The composition of the developing solution is shown below.

<Color developer tank solution and replenisher> Tank solution replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N -Ethyl-N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter. pH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

<Bleaching and Fixing Solution Tank Solution and Replenisher> Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4- Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

<Stabilizing Solution Tank Solution and Replenisher> o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopal SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make a total volume of 1 liter, and the pH was 7.7 with sulfuric acid or aqueous ammonia. Adjust to 5.

The black-and-white image sample formed after the treatment was exposed to sunlight for 20 days on an outdoor exposure table.

The hue of each sample at a reflection density of 1.0 was measured by a method of JIS Z-8729 and Z-8730 using a 607 type color analyzer (manufactured by Hitachi, Ltd.), and (a ^* , b) ^* ) = Color difference E from (0,0) was calculated and used as a measure of neutrality.

Separately, the degree of increase in the blue light reflection density of the white portion was measured using a PDA-65 densitometer (manufactured by Konica Corporation).

Table 1 shows the results.

[0175]

[Table 1]

[0176]

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With the black-and-white image sample of the present invention, an image having good neutrality and good whiteness was obtained even after storage over time.

[0178]

According to the present invention, an image having good neutrality and good whiteness was obtained even after storage over time.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a support, wherein at least one silver halide emulsion-containing layer contains a yellow coupler, a magenta coupler and a cyan coupler. And the at least one silver halide emulsion-containing layer contains at least one of the compounds represented by the following general formulas [1], [2] and [3]. A silver halide photographic light-sensitive material characterized in that: Embedded image [Wherein, R ₁ represents a tertiary alkyl group, and R ₂ represents a primary or secondary alkyl group. However, R ₂ is not substituted by a phenyl group. R ₃ , R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, an alkoxy group, a phenoxy group or a phenylthio group. [Chemical formula 2] [Wherein R ₁₁ represents an aliphatic group, an aromatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, or an aromatic oxy group, and R ₁₄ represents a hydrogen atom, an aliphatic Group, acyl group, aliphatic oxycarbonyl group,
It represents an aromatic oxycarbonyl group, an aliphatic oxy group or an aromatic oxy group, and R ₁₂ and R ₁₃ each independently represent a hydrogen atom, an aliphatic group or an aromatic group. [Chemical formula 3] [Wherein R ₂₁ and R ₂₄ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group, an aliphatic oxy group, or an aromatic oxy group. And R ₂₂ and R ₂₃ each independently represent a hydrogen atom, an aliphatic group, or an aromatic group, and X represents a halogen atom. However, R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄
Cannot be hydrogen atoms at the same time. ] 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a support, wherein at least one silver halide emulsion-containing layer has a yellow coupler, a magenta coupler and a cyan coupler. A silver halide photographic light-sensitive material, characterized in that the silver halide emulsion-containing layer contains at least one water-insoluble and organic solvent-soluble polymer compound. 3. A silver halide photographic material having at least one silver halide emulsion-containing layer on a support, wherein at least one silver halide emulsion-containing layer contains a blue-sensitive silver halide emulsion. And at least one layer containing a silver halide emulsion contains at least one of a yellow coupler, a magenta coupler and a cyan coupler or a black-forming coupler, and at least one layer of a silver halide emulsion on a support. A silver halide photographic light-sensitive material characterized in that the containing layer contains an epoxy group-containing compound.