JP2725096B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having a dyed layer, and relates to a hydrophilic material containing a dye which is photochemically inert and which is easily decolorized and / or eluted by photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer.

[0002]

2. Description of the Related Art In a silver halide photographic material, a photographic emulsion layer and other hydrophilic colloid layers are often colored in order to absorb light in a specific wavelength range. When it is necessary to control the spectral composition of the light to be incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, the filter layer may be located between them.

Light scattered when passing through or after transmission through a photographic emulsion layer is reflected at the interface between the emulsion layer and the support or on the surface of the photosensitive material on the side opposite to the emulsion layer and reenters the photographic emulsion layer. In order to prevent blurring or halation of an image based on the photographic emulsion layer, a colored layer called an antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support opposite to the photographic emulsion layer. When there are a plurality of photographic emulsion layers, an antihalation layer may be provided between the layers. In order to prevent a decrease in image sharpness due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation), the photographic emulsion layer is also colored.

These hydrophilic colloid layers to be colored usually contain a dye. This dye must satisfy the following conditions. (1) To have appropriate spectral absorption according to the purpose of use. (2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer should not be adversely affected in a chemical sense, such as a decrease in sensitivity, regression of a latent image, or fog. (3) No decolorization during the photographic processing or elution into the processing solution or washing water, leaving no harmful coloring on the processed photographic light-sensitive material. (4) Do not diffuse from the dyed layer to other layers. (5) It is excellent in stability over time in a solution or a photographic material and does not discolor.

[0005] In particular, when the coloring layer is a filter layer,
Alternatively, in the case of an antihalation layer on the same side of the support as the photographic emulsion layer, it is preferred that those layers are selectively colored and that the other layers are not substantially colored. Often needed. Otherwise, not only would it have a detrimental spectral effect on the other layers, but it would also destroy its effect as a filter layer or antihalation layer. However, when the layer containing the dye and another hydrophilic colloid layer come into contact with each other in a wet state,
It often occurs that some of the dye diffuses from the former to the latter. More efforts have been made in the past to prevent such dye diffusion.

[0006] For example, US Pat. No. 2,029,067 discloses a method in which a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye is coexisted in a layer as a mordant, and the dye is localized in a specific layer by interaction with dye molecules. , 548,564, 4,124,386, and 3,625,694.

However, the dye fixing / decoloring method using such a mordant requires the use of a large amount of the mordant with respect to the anionic dye, so that the thickness of the colored layer is inevitably thick. For example, when used as a filter layer of a photographic material, this increase in film thickness causes a problem that the sharpness (sharpness) of an obtained image is deteriorated.
In a system using a mordant, the fixation of a colored dye /
In addition to decolorization, it is necessary not to hinder the decolorization of the sensitizing dye used in the silver halide emulsion. Not at a satisfactory level.

Further, a method of dyeing a specific layer using a dye solid insoluble in water is disclosed in JP-A-56-12639 and JP-A-56-12639.
5-155350, 55-155351, 63
-27838, 63-197943, European Patent Nos. 15,601, 274,723, 276,56
Nos. 6, 299, 435 and U.S. Pat.
No. 0, world patent WO88 / 04794 and the like. Further, a method of dyeing a specific layer using metal salt fine particles having a dye adsorbed thereto is disclosed in U.S. Pat. No. 2,719,088,
Nos. 2,496,841 and 2,496,843, and JP-A-60-45237.

Although such a dyeing method is excellent in fixability / decolorization ability, its absorption is generally broad and often causes a problem when used as a filter dye for light of a specific wavelength, for example. Had become.

[0010] Japanese Patent Application Laid-Open No. 61-204630, 6
1-205934, 62-32460, 62-
No. 56958, No. 62-92949, No. 62-222
No. 248, No. 63-40143, No. 63-18474
Nos. 9 and 63-316852 disclose means for dispersing an oil-soluble dye together with a high-boiling organic solvent. However, the use of such a high-boiling organic solvent softens the coloring layer and lowers the film strength, so that a larger amount of gelatin is required, and consequently, the desire to reduce the film thickness is the opposite result. Bring.

On the other hand, JP-B-51-39853, JP-A-51-59943, JP-B-53-137131, and JP-A-53-137131.
No. 32552, No. 54-107941, No. 56-1
No. 26830, No. 58-149038, U.S. Pat.
199,363, 4,203,716, 4,9
No. 90,435, etc., a polymer latex in which a hydrophobic substance such as a dye in an organic solvent solution is added to an aqueous dispersion of a polymer (polymer latex) and impregnated to fill the hydrophobic substance. Is disclosed. This method does not have the above-mentioned problems due to the use of a high boiling point organic solvent due to the use of a polymer. Removal of the water-soluble auxiliary organic solvent used for the impregnation, which requires a large amount of polymer, is troublesome. The process itself has the disadvantage that it takes a long time and is complicated.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to selectively dye a specific layer without adversely affecting the dye-absorbing properties and the film strength, which is excellent in the suitability for production, and in the processing step. Another object of the present invention is to provide a silver halide photographic material containing a novel dye dispersion which decolorizes or elutes.

[0013]

SUMMARY OF THE INVENTION The object of the present invention is to emulsify and disperse a mixed solution containing at least one oil-soluble dye and at least one water-insoluble and organic solvent-soluble polymer. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer containing the dispersion obtained. A silver halide photographic material, wherein the water-insoluble and organic solvent-soluble polymer is a polymer having a repeating unit derived from a monomer having an anionic functional group. The present invention has been attained by a silver halide photographic material, wherein the oil-soluble dye is a compound represented by the following formula (I). General formula (I)

[0014]

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In the formula, X and Y each represent an electron-withdrawing group,
X represents an acidic nucleus bonded, Ar represents a phenyl group or a heterocyclic group, L ¹ , L ² , and L ³ each represent a methine group, and n represents 0, 1, or 2.

Hereinafter, the present invention will be described in detail.
The dye used in the present invention may be any of various well-known dyes. The structures of these dyes include arylidene compounds, heterocyclic arylidene compounds, anthraquinones, triarylmethanes, azomethine dyes, azo dyes, cyanines, merocyanines, oxonols, styryl dyes, phthalocyanines, indigo and others.
The dye used in the present invention is preferably water-insoluble and has a solubility in ethyl acetate of 10 g / l (40 ° C.) or more, particularly preferably 50 g / l (40 ° C.).
° C) or higher. The structure of the chromophore is not important.

The arylidene compound is a compound in which an acidic nucleus and an aryl group are linked by one or more methine groups. As the acidic nucleus, 2-pyrazolin-5-one, 2-pyrazolin-5-one,
Isoxazolin-5-one, barbituric acid, 2-thiobarbituric acid, benzoylacetonitrile, cyanoacetamide, cyanoacetanilide, cyanoacetate, malonate, malondianilide, dimedone, benzoylacetanilide, pivaloylacetoanilide, malononitrile 1,2-dihydro-6-hydroxypyridin-2-one, pyrazolidine-3,5-dione, pyrazolo [3,4-b] pyridin-3,6-dione, indane-1,3-dione, hydantoin, Thiohydantoin, 2,5-dihydro-furan-2-one and the like. The aryl group includes a phenyl group, which is preferably substituted with an electron-donating group such as an alkoxy group, a hydroxy group, or an amino group.

The heterocyclic arylidene compound is a compound in which an acidic nucleus and a heteroaromatic ring are linked by one or more methine groups. Examples of the acidic nucleus include those described above. Examples of the heteroaromatic ring include furan, thiophene, and pyrazole.

Anthraquinones are those in which anthraquinone is substituted by an electron donating group or an electron withdrawing group. Triarylmethanes represent compounds in which three substituted aryl groups (which may be the same or different) are bonded to one methine group. An example is phenolphthalein.

The azomethine dye is a dye in which an acidic nucleus and an aryl group are linked by an unsaturated nitrogen linking group (azomethine group). Acidic nuclei include those known as photographic couplers in addition to those described above. Indoanilines also belong to the azomethine dye.

The azo dyes are those in which an aryl group or a heteroaromatic ring group is linked by an azo group.

Cyanine represents two basic nuclei linked by one or more methine groups. Examples of the basic nucleus include quaternary salts such as oxazole, benzoxazole, thiazole, benzothiazole, benzimidazole, quinoline, pyridine, indolenine, benzoindolenine, benzoselenazole, and imidazoquinoxaline, and pyrylium.

The merocyanine dye refers to a dye in which the above-mentioned basic nucleus and acidic nucleus are linked by a double bond or linked by one or more methine groups. Oxonol dyes are those in which two of the above acidic nuclei are linked by one or more odd number of methine groups. The styryl dye represents the above-mentioned basic nucleus and an aryl group linked by two or four methine groups.

The phthalocyanine may be coordinated to a metal,
You don't have to. Indigo may be unsubstituted or substituted indigo, including thioindigo.

The dye of the present invention can be used for various purposes.

The dye of the present invention preferably has a dissociable group, and includes a hydroxyl group, a carboxy group and the like. Particularly preferred are a sulfonamide group, a sulfamoyl group, an acylsulfamoyl group, a sulfonylcarbamoyl group, and the like. It is a sulfonimide group.

Particularly preferred dyes for use in the present invention are those represented by formula (I). The general formula (I) will be described in detail. The electron-withdrawing groups represented by X and Y are a cyano group, a nitro group, an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, hydroxyethoxycarbonyl, t-amyloxycarbonyl), an aryloxycarbonyl (eg, phenoxycarbonyl, -Methoxycarbonyl), an acyl group (eg, acetyl, pivaloyl, benzoyl, propionyl, 4-methanesulfonamidobenzoyl, 4-methoxy-3-methanesulfonamidobenzoyl, 1-methylcyclopropylcarbonyl), a carbamoyl group (eg, N-ethyl Carbamoyl, N, N-dimethylcarbamoyl, piperidin-1-ylcarbonyl, N- (3-
Methanesulfonamidophenyl) carbamoyl), a sulfonyl group (for example, benzenesulfonyl, p-toluenesulfonyl), and the acidic nucleus linked by X and Y is 5
Alternatively, a 6-membered ring is preferable, and examples of the 5-membered ring include 2-pyrazolin-5-one, 2-isoxazolin-5-one, pyrazolidine-3,5-dione, 2,5-dihydrofuran-2-one, and indan. -1,3-dione is preferable, and as the 6-membered ring, for example, 1,2-dihydro-6-hydroxypyridin-2-one, barbituric acid, and thiobarbituric acid are preferable.

The phenyl group represented by Ar is preferably a phenyl group substituted with an electron donating group, and a dialkylamino group (for example, dimethylamino,
Di (ethoxycarbonylmethyl) amino, di (butoxycarbonylmethyl) amino, N-ethyl-N-ethoxycarbonylmethylamino, di (cyanoethyl) amino,
Preferred are piperidinyl, pyrrolidinyl, morpholino, N-ethyl-N-β-methanesulfonamidoethylamino, N-ethyl-N-β-hydroxyethyl), hydroxy group and alkoxy group (for example, methoxy, ethoxy, ethoxycarbonylmethoxy).

As the heterocyclic group represented by Ar, a 5-membered heterocyclic ring is preferable, and for example, furan and thiophene are particularly preferable.

The methine groups represented by L ¹ , L ² and L ³ may have a substituent, but are preferably unsubstituted methine groups.

Specific examples of the dye used in the present invention are described below, but the present invention is not limited to these.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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When an oil-soluble dye is used as a filter dye or an antihalation dye, any effective amount can be used, but the optical density is 0.05 to 3.5.
It is preferable to use it so that it may be within the range. The timing of addition may be any step before coating.

The oil-soluble dye of the present invention can be used in any of an emulsion layer and other hydrophilic colloid layers.

The dye used in the present invention is used as a dispersion with a water-insoluble and organic solvent-soluble polymer. The dispersion can be obtained by the following method. That is, the compound of the present invention is added and dissolved in a polymer solution dissolved in an auxiliary solvent, and then added to and dispersed in a hydrophilic colloid solution. In addition, a high-boiling organic solvent can be used in combination for the purpose of adjusting the dispersibility, spectral absorption characteristics, coatability and the like of the compound of the present invention. The ratio of the high boiling point organic solvent to the polymer can be arbitrarily set according to the purpose. Preferably it is 1.0 or less.

As the high boiling point solvent, US Pat.
As described in 2,027, for example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphate ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate) ,
Citrates (eg, tributyl acetyl citrate), benzoates (eg, octyl benzoate),
Alkyl amides (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg, tributyl trimesate) and the like can be used.

As the hydrophilic colloid, gelatin is a typical one, but any other conventionally known colloids usable for photography can be used.

Next, the polymer according to the present invention will be described. The polymer used for dispersing the dye in the present invention,
Any polymer may be used as long as it is water-insoluble and organic solvent-soluble, and is composed of at least one type of repeating unit.

(A) Vinyl Polymer As the monomer forming the vinyl polymer of 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-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ) Ethyl acrylate, ω-methoxypolyethylene glycol acrylate (addition mole number n =
9), 1-bromo-2-methoxyethyl acrylate,
Examples thereof include 1,1-dichloro-2-ethoxyethyl acrylate. In addition, the following monomers can be used.

Methacrylic esters: Specific examples thereof include methyl methacrylate, ethyl methacrylate,
n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl Methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2- Mud methacrylate,
4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate,
2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy Examples thereof include polyethylene glycol methacrylate (addition mole number n = 6), allyl methacrylate, dimethylaminoethyl methyl methacrylate chloride salt, 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, tert
-Butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide,
Dimethyl acrylamide, diethyl acrylamide, β
-Cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetoneacrylamide and the like;

Methacrylamides: for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacryl Amide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide,
Diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide and the like;

Olefins: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene and the like;
Styrenes: for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene,
Isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, methyl vinyl benzoate, etc .;

Vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like;

Others include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate,
Dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile, methylene malononitrile,
And vinylidene.

From the viewpoint of decolorization and / or elution in the treatment of the emulsion dispersion of the dye, copolymerization of a monomer having an anionic functional group is particularly preferred, and the following monomers can be mentioned as examples.

Acrylic acid; methacrylic acid; itaconic acid;
Maleic acid; monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate, etc .; monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate, etc .; citraconic acid; styrene sulfonic acid; vinylbenzyl sulfonic acid; vinyl sulfonic acid ;
Acryloyloxyalkylsulfonic acids, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, and the like; methacryloyloxyalkylsulfonic acid,
For example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid and the like; acrylamidoalkylsulfonic acid, for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid and the like; methacrylamidoalkylsulfonic acid, for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2 -Such as methylbutanesulfonic acid; these acids may be salts of alkali metals (e.g. Na, K, etc.) or ammonium ions.

Among the vinyl monomers mentioned above and other vinyl monomers used in the present invention, hydrophilic monomers (here, those which become water-soluble when made 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.
It is as follows.

The polymer of the present invention may be a homopolymer or a copolymer composed of two or more monomers.
As the monomers constituting the polymer, acrylate, methacrylate, styrene, acrylamide and methacrylamide in which homopolymers thereof are insoluble in water are particularly preferable.

In the particularly preferred embodiment of the copolymer of a monomer having an acid group, the amount of the anionic functional group-containing monomer to be introduced should be such that the polymer does not become water-soluble, However, in the case of a carboxylic acid-containing monomer,
Preferably it is 40 mol% or less, particularly preferably 30 mol% or less in the copolymer. In the case of a sulfonic acid-containing monomer, it is preferably 15 mol% or less, particularly preferably 1 mol% or less.
0 mol% or less.

(B) Polyester 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, particularly Group hydrocarbon chains)
Glycols or polyalkylene glycols having the following structure are effective, and polybasic acids include 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,
1,12-dodecanediol, 1,13-tridecanediol, 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, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid,
Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid,
Examples thereof include citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohimeric acid, cyclopentadiene-maleic anhydride adduct, and rosin-maleic anhydride adduct.

(C) Other Polyesters obtained by, for example, the following ring-opening polymerization:

[0064]

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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 the polyester include β-propiolactone, ε-caprolactone, dimethylpropiolactone, and the like.

Two or more of the above-mentioned polymers of the present invention may be used in combination. The molecular weight and the degree of polymerization of the polymer of the present invention have substantially no significant effect on the effects of the present invention, but as the molecular weight increases, it takes time to dissolve in an auxiliary solvent, and the solution viscosity is high. As a result, it becomes difficult to emulsify and disperse, and coarse particles are generated. As a result, problems such as deterioration of dye absorption characteristics and poor coating properties 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. From the above viewpoint, the viscosity of the polymer is
The viscosity when 30 g of the polymer is dissolved in 100 cc of the auxiliary agent used is preferably 5000 cps or less, more preferably 2 cps.
000cps or less. The number average molecular weight of the polymer usable in the present invention is preferably 300,000 or less, particularly preferably 100,000 or less.

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, the solubility of the dye, and the like. Usually, an amount of the co-solvent necessary to obtain a sufficiently low viscosity so that a solution obtained by dissolving at least the dye and the polymer in the co-solvent is easily dispersed in water or an aqueous hydrophilic colloid solution is used. Is done. 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: 5.
A range of 0 (weight ratio) is preferred. The ratio (weight ratio) of the polymer of the present invention to the dye is preferably from 1:20 to 20: 1, more preferably from 1:10 to 10: 1.

Some specific examples of the polymer used in the present invention are described below, but the present invention is not limited to these. Specific examples Polymer species (parentheses indicate molar ratio) P-1 to 5 Methyl methacrylate-acrylic acid copolymer P-1 (97: 3) P-2 (95: 5) P-3 (90:10) P-4 (80:20) P-5 (70:30) P-6 Methyl acrylate-acrylic acid copolymer (90:10)

P-7 n-butyl acrylate-acrylic acid copolymer (93: 7) P-8,9 Methyl methacrylate-methacrylic acid copolymer P-8 (90:10) P-9 (85:15) P-10 n-butyl methacrylate-methacrylic acid copolymer (95: 5) P-11 methyl methacrylate-ethyl methacrylate-methacrylic acid copolymer (50: 42: 8) P-12 methyl methacrylate-benzyl methacrylate-methacrylic acid Copolymer (20:70:10) P-13 N-tert-butylacrylamide-n-butylacrylate-acrylic acid copolymer (44: 50: 6)

P-14-16 Methyl methacrylate-2-acrylamido-2-methylpropane sodium sulfonic acid copolymer P-14 (99: 1) P-15 (97: 3) P-16 (95: 5) P- 17 Methyl methacrylate-methacrylic acid-2-acrylamide-2-methylpropanesulfonic acid sodium copolymer (90: 7: 3) P-18 n-butyl methacrylate-3-acryloxybutane-1-sulfonic acid sodium copolymer Coalescing (97: 3)

P-19 Polyvinyl acetate P-20 Polyvinyl propionate P-21 Polymethyl methacrylate P-22 Polyethyl methacrylate P-23 Polyethyl acrylate P-24 Vinyl acetate-vinyl alcohol copolymer (9
5: 5) P-25 poly n-butyl acrylate P-26 poly n-butyl methacrylate P-27 polyisobutyl methacrylate P-28 polyisopropyl methacrylate

P-29 polydecyl methacrylate P-30 n-butyl acrylate-acrylamide copolymer (95: 5) P-31 poly (2-tert-butylphenyl acrylate) P-32 poly (4-tert-butylphenyl) Acrylate) P-33 n-butyl methacrylate-N-vinyl-2
-Pyrrolidone copolymer (90:10) P-34 methyl methacrylate-vinyl chloride copolymer (70:30) P-35 methyl methacrylate-styrene copolymer (90:10) P-36 methyl methacrylate-ethyl acrylate Polymer (50:50) P-37 n-butyl methacrylate-methyl methacrylate-styrene copolymer (50:30:20) P-38 Vinyl acetate-acrylamide copolymer (8
5:15)

P-39 methyl methacrylate-acrylonitrile copolymer (65:35) P-40 diacetone acrylamide-methyl methacrylate copolymer (50:50) P-41 methyl methacrylate-cyclohexyl methacrylate copolymer (50:50) P-42 methyl methacrylate-phenyl vinyl ketone copolymer (70:30) P-43 n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35: 3)
5:30)

P-44 n-butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37: 3
6:27) P-45 n-butyl methacrylate-styrene copolymer (90:10) P-46 methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) P-47 n-butyl methacrylate- Styrene copolymer (70:30) P-48 poly (N-sec-butylacrylamide) P-49 poly (N-tert-butylacrylamide) P-50 diacetone acrylamide-methyl methacrylate copolymer (62:38) P-51 polycyclohexyl methacrylate-methyl methacrylate copolymer (60:40)

P-52 N-tert-butylacrylamide-methyl methacrylate copolymer (40:60) P-53 poly (Nn-butylacrylamide) P-54 poly (tert-butylmethacrylate) -N-
tert-butyl acrylamide copolymer (50:50) P-55 tert-butyl methacrylate-methyl methacrylate copolymer (70:30) P-56 poly (N-tert-butyl methacrylamide) P-57 N-tert- Butylacrylamide-methyl methacrylate copolymer (60:40)

P-58 methyl methacrylate-styrene copolymer (75:25) P-59 methyl methacrylate-hexyl methacrylate copolymer (70:30) P-60 poly (benzyl acrylate) P-61 poly (4-biphenyl) Acrylate) P-62 poly (4-butoxycarbonylphenyl acrylate) P-63 poly (sec-butyl acrylate) P-64 poly (tert-butyl acrylate) P-65 poly [3-chloro-2,2-bis- ( Chloromethyl) propyl acrylate] P-66 poly (2-chlorophenyl acrylate) P-67 poly (4-chlorophenyl acrylate) P-68 poly (pentachlorophenyl acrylate) P-69 poly (4-cyanobenzyl acrylate)

P-70 poly (cyanoethyl acrylate) P-71 poly (4-cyanophenyl acrylate) P-72 poly (4-cyano-3-thiabutyl acrylate) P-73 poly (cyclohexyl acrylate) P-74 poly ( 2-ethoxycarbonylphenyl acrylate) P-75 poly (3-ethoxycarbonylphenyl acrylate) P-76 poly (4-ethoxycarbonylphenyl acrylate)

P-77 poly (heptyl acrylate) P-78 poly (hexadecyl acrylate) P-79 poly (hexyl acrylate) P-80 poly (isobutyl acrylate) P-81 poly (isopropyl acrylate) P-82 poly (3 -Methoxybutyl acrylate) P-83 poly (2-methoxycarbonylphenyl acrylate) P-84 poly (3-methoxycarbonylphenyl acrylate) P-85 poly (4-methoxycarbonylphenyl acrylate) P-86 poly (2-methoxyethyl) Acrylate) P-87 poly (4-methoxyphenyl acrylate)

P-88 poly (3-methoxypropyl acrylate) P-89 poly (3,5-dimethyladamantyl acrylate) P-90 poly (3-dimethylaminophenyl acrylate) P-91 polyvinyl-tert-butyrate P-92 Poly (2-methylbutyl acrylate) P-93 Poly (3-methylbutyl acrylate) P-94 Poly (1,3-dimethylbutyl acrylate) P-95 Poly (2-methylpentyl acrylate) P-96 Poly (2- Naphthyl acrylate) P-97 poly (phenyl acrylate) P-98 poly (propyl acrylate)

P-99 poly (m-tolyl acrylate) P-100 poly (o-tolyl acrylate) P-101 poly (p-tolyl acrylate) P-102 poly (N, N-dibutylacrylamide) P-103 poly ( Isohexylacrylamide) P-104 Poly (isooctylacrylamide) P-105 Poly (N-methyl-N-phenylacrylamide) P-106 Poly (adamantyl methacrylate) P-107 Poly (benzyl methacrylate) P-108 Poly (2- Bromoethyl methacrylate) P-109 Poly (sec-butyl methacrylate)

P-110 Poly (hexyl methacrylate) P-111 Poly (2-hydroxypropyl methacrylate) P-112 Poly (4-methoxycarbonylphenyl methacrylate) P-113 Poly (3,5-dimethyladamantyl methacrylate) P-114 Poly (dimethylaminoethyl methacrylate) P-115 Poly (3,3-dimethylbutyl methacrylate) P-116 Poly (3,3-dimethyl-2-butyl methacrylate) P-117 Poly (3,5,5-trimethylhexyl methacrylate) ) P-118 poly (octadecyl methacrylate) P-119 poly (tetradecyl methacrylate) P-120 poly (4-butoxycarbonylphenyl methacrylamide)

P-121 poly (tert-butyl methacrylate) P-122 poly (2-chloroethyl methacrylate) P-123 poly (2-cyanoethyl methacrylate) P-124 poly (2-cyanomethylphenyl methacrylate) P-125 poly (4-cyanophenyl methacrylate) P-126 poly (cyclohexyl methacrylate) P-127 poly (dodecyl methacrylate) P-128 poly (pt-butylstyrene)

P-129 n-butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (35:35:30) P-130 poly-3-pentyl acrylate P-131 cyclohexyl methacrylate-methyl methacrylate-n-propyl methacrylate copolymer Coalescing (3
7:29:34) P-132 Polypentyl methacrylate P-133 Methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-134 Vinyl acetate-vinyl propionate copolymer (75:25)

P-135 Poly (butylchloroacrylate) P-136 Poly (butylcyanoacrylate) P-137 Poly (cyclohexylchloroacrylate) P-138 Poly (ethylchloroacrylate) P-139 Poly (4-carboxyphenylmethacrylamide) ) P-140 Poly (4-ethoxycarbonylphenylmethacrylamide) P-141 Poly (4-methoxycarbonylphenylmethacrylamide) P-142 1,4-Butanediol-adipate polyester P-143 Ethylene glycol-sebacate polyester P −144 polycaprolactone

The silver halide emulsion used in the present invention is:
Silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride are preferred. As the hydrophilic colloid, gelatin is typical, but any other conventionally known colloids usable for photography can be used.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. The number and order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light and a multilayer silver halide color photographic light-sensitive material. In general, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer, The color-sensitive layer and the blue-sensitive layer are provided in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-light-sensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A-61-43748, JP-A-59-11343
No. 8, No. 59-113440, No. 61-20037, couplers as described in the specification of No. 61-20038, DIR compounds and the like may be contained, and a color mixing inhibitor is used as usually used. May be included. A plurality of silver halide emulsion layers constituting each unit photosensitive layer preferably employ a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in JP-A-06543 and the like, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / 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. Also Tokunoaki
As described in JP-A-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738, 62-63936
As described in the specification, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even in the case of comprising three layers having different sensitivities, as described in JP-A-59-202464, a medium-speed emulsion is provided in the same color-sensitive layer from the side away from the support. Layers / high-speed emulsion layers / low-speed emulsion layers. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers.

In order to improve color reproducibility, US Pat.
Nos. 663,271, 4,705,744, 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, or RL is disposed adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about
Fine particles having a diameter of 0.2 μm or less or large-sized particles having a projected area diameter of about 10 μm may be used, and a polydispersed emulsion or a monodispersed emulsion may be used. Silver halide photographic emulsions usable in the present invention include, for example, Research Disclosure (RD) N
o. 17643 (December 1978), pp. 22-23, "I. Emulsion Production (Emu
lsion preparation and types) ”and No. 18716
(November 1979), 648 pages, No.307105 (November 1989), 863
865 pages, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions", by Zelikman et al., Published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964).

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
No. 48, 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it 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 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 the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

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 described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more types of emulsions having at least one characteristic different from one another in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion.
They can be mixed and used in the same layer. U.S. Patent No.
No. 4,082,553, silver halide grains having a fogged surface, U.S. Pat. It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged inside 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. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat.
No. 9-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains whose insides are fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is
It is preferably from 0.01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is ± 40% of the average grain size). %).

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. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives which can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, page 866-868 Strong Color sensitizer 〜page 649 right column 4. Brightening agent page 24 page 647 right column page 868 5. Fogging prevention page 24-25 page 649 right column 868-870 agent, stabilizer 6.Light absorber, 25- Page 26 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7.Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image 25 Page 650 Page Left column 872 Stabilizer 9. Hardener page 26 page 651 left column 874-875 10. Binder page 26 page 651 left column 873-874 11. Plasticizer, page 27 page 650 right column page 876 Lubricant 12. Coating aid Pp. 26-27 650 right column 875-876 Surfactant 13. Stat. 27 page 650 right column 876-877 Inhibitor 14. Matsuto 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add a compound capable of reacting with formaldehyde described in US Pat. No. 4,411,987 or US Pat. . U.S. Pat.No. 4,740,454
No. 4,788,132, JP-A-62-18539, JP-A-1-28
It is preferable to include a mercapto compound described in No. 3551. In the light-sensitive material of the present invention, compounds described in JP-A-1-06052, which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by development processing Is preferably contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure Nos. 17643, VII-CG, and VII-CG and No. 30710.
5, VII-CG.
As a yellow coupler, for example, U.S. Patent No. 3,933,50
No. 1, No. 4,022,620, No. 4,326,024, No. 4,4
No. 01,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Patent No.
No. 3,973,968, No. 4,314,023, No. 4,511,649,
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 and EP 73,63.
No. 6, U.S. Pat.Nos. 3,061,432, 3,725,067,
Research Disclosure No.24220 (June 1984
), JP-A-60-33552, Research Disclosure No.24230 (June 1984), JP-A-60-43659, 61-7
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
No. 4,500,630, U.S. Pat.No. 4,540,654, U.S. Pat.
Those described in 4,556,630, International Publication WO88 / 04795 and the like are particularly preferred. Cyan couplers include phenolic and naphthol couplers and are described in U.S. Pat.
No. 52,212, No. 4,146,396, No. 4,228,233, No.
No. 4,296,200, No. 2,369,929, No. 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication No. 3,329,729, European Patent No. 12
No. 1,365A, No. 249,453A, U.S. Pat.No. 3,446,622
No. 4,333,999, 4,775,616, 4,45
No. 1,559, No. 4,427,767, No. 4,690,889, No.
Preferred are those described in 4,254,212, 4,296,199 and JP-A-61-42658. Further, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556, and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
No. 3,451,820, No. 4,080,211 and No. 4,367,282,
Nos. 4,409,320, 4,576,910, UK Patent 2,1
02,137 and EP 341,188A.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,
No. 570, European Patent No. 96,570, German Patent (public) No. 3,
Those described in No. 234,533 are preferred. Colored couplers to correct unwanted absorption of coloring dyes
No. 30743, Disclosure No. 17643, No. 30710
5, VII-G, U.S. Pat.No. 4,163,670, JP-B-57-3
No. 9413, U.S. Pat.Nos. 4,004,929, 4,138,258,
Those described in British Patent No. 1,146,368 are preferred. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers releasing a development inhibitor are described in RD 17643, VII-F and the patents described in Nos. 307105 and VII-F, JP-A-57-151944, JP-A-57-154234, and JP-A-57-154234. No. 60-184248, 6
3-37346, 63-37350, U.S. Pat.No. 4,248,962,
Those described in No. 782,012 are preferred. RDNo.1144
The bleaching accelerator releasing couplers described in JP-A Nos. 9,241241 and JP-A-61-201247 are effective for shortening the processing time of a processing step having bleaching ability. The effect is great when it is added to a photosensitive material using. Couplers that release a nucleating agent or development accelerator imagewise during development are described in GB 2,097,140.
No. 2,131,188, JP-A-59-157638, JP-A-59-170
Those described in No. 840 are preferred. In addition, JP-A-60-1070
No. 29, No. 60-252340, JP-A-1-44940, No. 1-45687
The redox reaction with the oxidized form of the developing agent described in No.
Compounds that release fogging agents, development accelerators, silver halide solvents and the like are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include the competitive couplers described in US Pat. No. 4,130,427 and the like, US Pat.
Nos. 38,393, 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds Or a DIR redox-releasing redox compound, a coupler releasing a dye capable of recoloring after detachment described in European Patent Nos. 173,302A and 313,308A, a ligand releasing coupler described in U.S. Pat. -75747 Leuco dye releasing couplers, U.S. Pat.
No. 181 which emits a fluorescent dye.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, dichloropropyl
2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylase) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline); and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, the boiling point is about 30 ℃ or more, preferably 50 ℃
An organic solvent having a temperature of about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol and JP-A-63-257747, JP-A-62-272248,
And JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or fungicides such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the aforementioned R
D. No. 17643, page 28, No. 18716, page 647, right column, 648
No. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and more preferably 16 μm or less. Particularly preferred. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al.
(Photogr.), 19 Certificates, No. 2, by using a 124 type described on pages to 129 Swellometer (swelling meter) can be measured, T _1/2 in color developer 30 90% of the maximum swelling film thickness reached when treated at ℃, 3 minutes and 15 seconds is defined as the saturated film thickness, and it is defined as the time required to reach 1/2 of the saturated film thickness.
The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 1
50-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ Can be calculated according to the film thickness. The photosensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a μm hydrophilic colloid layer (referred to as a back layer). The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. 17643, pages 28 to 29, No. 18716, page 651, left column to right column, and No. 307105, pages 880 to 881, can be used for development. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. As the color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N- Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in combination of two or more depending on the purpose. The color developing solution is an alkali metal carbonate,
PH buffers such as borates or phosphates, and development inhibitors or antifoggants such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. General. Also, as required, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphones Acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Typical examples thereof include ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is performed, color development is usually performed after black and white development. Known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷ [volume of processing solution (cm ³ )] The opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. It is. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. Reducing the aperture ratio is not only a step of color development and a step of black-and-white development, but also various subsequent steps, for example, bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Representative bleaching agents include organic complex salts of iron (III) such as amino diamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are preferable from the viewpoint of rapid processing and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually from 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, JP-A-53-57831
Nos. 53-37418, 53-72623, 53-95630, 53
-95631, 53-104232, 53-124424, 53-141
No. 623, No. 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July, 1978);
No. 45-8506, JP-A-52-20832 and JP-A-53-32735, U.S. Pat. No. 3,706,561
No. 1,127,715, thiourea derivatives described in US Pat.
Iodide salts described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in Nos. 410 and 2,748,430; polyamine compounds described in JP-B No. 45-8836; and other JP-A Nos. 49-40,943, 49-59,644 and 53-94,92.
No. 7, 54-35,727, 55-26,506, 58-163,940
Compounds described in (1); bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Pat.
3,858, West German Patent No. 1,290,812, JP-A-53-95,630
Are preferred. Further, U.S. Pat.
The compounds described in 834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
-5, specifically, acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. Examples of preservatives for the fixing solution and the bleach-fixing solution include sulfites, bisulfites, carbonyl bisulfite adducts and EP No. 294.
The sulfinic acid compounds described in 769A are preferred. Furthermore,
It is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains pH.
For the adjustment, a compound having a pKa of 6.0 to 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole is used.
It is preferable to add 1 to 10 mol / l.

The total time of the desilvering step is preferably as short as possible, as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material described in JP-A-62-183460, or a method of stirring using a rotating means described in JP-A-62-183461. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 60-191258 and 60-191259. Japanese Patent Laid-Open No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a transport means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture a.
nd Television Engineers, Vol. 64, pp. 248-253 (May, 1955). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved by
The method for reducing calcium ions and magnesium ions described in JP-A-62-288,838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology"
(1982) The Fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986) edited by the Japan Society of Industrial Technology, Japan Society of Bacteria and Fungi. The pH of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. Washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, application, etc.
In general, 20 seconds to 10 minutes at 15 to 45 ° C, preferably 25 to 40 ° C
Selects a range of 30 seconds to 5 minutes. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization treatment, any of the known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Described metal salt complex, JP-A-53-135
Urethane compounds described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438. Various processing solutions in the present invention are 10 ° C
Used at 5050 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, the silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.No. 4,500,626,
The invention can also be applied to a photothermographic material described in European Patent No. 210,660A2.

[0111]

【Example】

Example 1 (Preparation of Dispersion a) 30 g of Compound D-14 was dissolved by heating in a mixed solvent of 30 cc of tricresyl phosphate and 120 ml of ethyl acetate, and 10% bone gelatin containing 3 g of sodium dodecylbenzenesulfonate was used. A dispersion a was prepared by emulsifying and dispersing in 800 g of the aqueous solution using a household mixer.

(Preparation of Dispersion b) After dissolving 1.9 g of Compound D-14 in 60 ml of acetone, latex (sodium methyl acrylate-2-acrylamido-2-methylpropanesulfonate copolymer) was stirred with stirring. Copolymerization ratio = 95: 5, 20
wt%) to 38 g. Next, acetone was removed under reduced pressure while heating to 50 ° C. using a rotary evaporator. This was filtered and dispersed in 75 g of a 10% aqueous solution of bone gelatin to prepare a dispersion b. When the amount of latex was 9.5 g (latex / dye ratio = 1), the impregnation was not sufficient, and the dispersion was stopped.

(Preparation of Dispersion c) 22 ml of water,
3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethanesulfonate and p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10)
0.5 g was placed in a 70 ml ball mill dispersion container, and 1.0 g of compound D-14 and 50 ml of zirconium oxide beads (diameter: 1 mm) were added, and the contents were dispersed for 3 hours. Take out the contents, filter and then 1
The resultant was dispersed in 40 g of a 0% gelatin aqueous solution to obtain a dispersion c.

(Preparation of Dispersion d) Dispersion a was prepared except that 35 g of polymer P-15 of the present invention was used in place of tricresyl phosphate in the preparation of dispersion a.
A dispersion d was obtained by the same operation as described above.

(Preparation of Samples) Samples 101 to 104 shown in Table 1 were prepared by applying the following composition on an undercoated cellulose triacetate film support. In addition,
In preparing the second dye layer, the dispersion was used, a surfactant required for coating was added, and an aqueous gelatin solution was further added so that the dry film thickness of each sample became the same.

(Sample 101) First layer: gelatin undercoat layer Gelatin: 1.5 g / m ² tricresyl phosphate 0.3 g / m ² Second layer: dye layer Gelatin: 1.5 g / m ² compounds D-14 0.21 g / m ² tricresyl phosphate 0.25 g / m ² Third layer: protective layer Gelatin 1.5 g / m ² 6-hydroxy-2,4-dichloro -S-triazine sodium 0.18 g / m ²

The absorption spectrum of each of the obtained samples was measured, and the absorption characteristics at the half-width and the long-wave end (λmax + 50) were measured.
The ratio of the absorption value at nm / the absorption value at λmax) was evaluated.
Further, the strength of the coating film was evaluated as follows. That is, 0.
A load of 0 to 100 g was continuously applied to a 1φ sapphire needle to scratch the coated film, and the film strength was evaluated by the load at which the film was broken. Table 1 shows the results. Table 1 shows that the sample 104 according to the present invention has excellent absorption characteristics and excellent film strength.

[0118]

[Table 1]

Example 2 The dye / polymer (weight ratio) of Sample 104 was changed to D-2 / P-
11 (1), D-5 / P-3 (1), D-7 / P-16
(0.7), D-11 / P-133 (2), D-38 /
Samples 105 to 109 were prepared in exactly the same manner except that the sample was changed to P-13 (1). The same evaluation as in Example 1 was performed, and it was found that the absorption characteristics and film quality were excellent as in Sample 104. Further, the sample 101 and the samples 104 to 10
For No. 9, the decolorizing property of the dye was evaluated. Processing is
According to the following.

Process Treatment time Treatment temperature Alkaline buffer 2 minutes 38 ° C. Water washing 30 seconds 38 ° C. Drying The composition of the alkaline buffer is as follows. Sodium sulfite 2.0 g Sodium carbonate 25.4 g Sodium bicarbonate 13.4 g Water was added to adjust to 2.0 liters pH 10.0

[0121] The ratio of the yellow density after processing for yellow density before treatment ^{_{(D B o) (D B}} ) and (D _B ^o / D _B) was evaluated as a measure of bleaching properties. Table 2 shows the results. As is clear from Table 2, the samples according to the present invention have very little residual color and exhibit excellent decolorization.

[0122]

[Table 2]

Example 3 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 301 as a multilayer color photosensitive material. (Composition of photosensitive layer) The number corresponding to each component indicates the coating amount in units of g / m ² , and the silver halide indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 301) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40

Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.18 EX-3 0.020 EX-12 2.0 × 10 ^-3 U-10 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third layer (first red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 sensitizing Dye III 3.1 × 10 ^-4 EX-2 0.17 EX-10 0.020 EX-14 0.17 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 060 gelatin 0.87

Fourth layer (second red-sensitive emulsion layer) Emulsion D silver 0.80 sensitizing dye I 3.5 × 10 ^-4 sensitizing dye II 1.6 × 10 ^-5 sensitizing dye III 5.1 × ^10-4 EX-2 0.20 EX-3 0.050 EX-10 0.015 EX-14 0.20 EX-15 0.050 U-1 0.070 U-2 0.050 U-30. 070 Gelatin 1.30

Fifth Layer (Third Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 Sensitizing Dye I 2.4 × 10 ^-4 Sensitizing Dye II 1.0 × 10 ^-4 Sensitizing Dye III 3.4 × 10 ^-4 EX-2 0.097 EX-3 0.010 EX-4 0.080 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63

Sixth layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80

Seventh layer (first green-sensitive emulsion layer) Emulsion C silver 0.30 sensitizing dye IV 2.6 × 10 ^-5 sensitizing dye V 1.8 × 10 ^-4 sensitizing dye VI 6.9 × 10 ^-4 EX-1 0.015 EX-6 0.13 EX-7 0.020 EX-8 0.025 EX-16 0.015 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth layer (second green-sensitive emulsion layer) Emulsion D silver 0.55 sensitizing dye IV 2.1 × 10 ^-5 sensitizing dye V 1.5 × 10 ^-4 sensitizing dye VI 5.8 × 10 ^-4 EX-6 0.047 EX-7 0.018 EX-8 0.018 EX-16 0.054 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50

Ninth Layer (Third Green Sensitive Emulsion Layer) Emulsion E Silver 1.30 Sensitizing Dye IV 4.6 × 10 ⁻⁵ Sensitizing Dye V 1.0 × 10 ⁻⁴ Sensitizing Dye VI 4.0 × 10 ^-4 EX-1 0.013 EX-11 0.060 EX-13 0.025 HBS-1 0.15 HBS-2 0.05 Gelatin 1.25

Tenth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.055 EX-5 0.12 HBS-1 0.08 Gelatin 0.60

Eleventh Layer (First Blue-Sensitive Emulsion Layer) Emulsion C Silver 0.18 Sensitizing Dye VII 8.6 × 10 ^-4 EX-8 0.042 EX-9 0.72 HBS-1 0.28 Gelatin 1.10

12th layer (second blue-sensitive emulsion layer) Emulsion D silver 0.45 sensitizing dye VII 7.4 × 10 ^-4 EX-9 0.15 EX-10 7.0 × 10 ^-3 HBS-1 0.050 gelatin 0.78

Thirteenth Layer (Third Blue-Sensitive Emulsion Layer) Emulsion F Silver 0.70 Sensitizing Dye VII 2.8 × 10 ^-4 EX-9 0.20 HBS-1 0.070 Gelatin 0.69

Fourteenth Layer (First Protective Layer) Emulsion G Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

15th layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-30 .10 S-1 0.20 gelatin 1.20

Further, all layers have storability, processability, pressure resistance,
W-1, W-2, W-3, B-4, B-5, B-
6, F-1, F-2, F-3, F-4, F-5, F-
6, F-7, F-8, F-9, F-10, F-11, F
-12, F-13, F-14, F-15, F-16, and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

[0140]

[Table 3]

[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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Sample 201 was prepared in the same manner as in Sample 201 except that the dispersion d of Example 1 was used instead of the yellow colloidal silver in the tenth layer of Sample 301, so that the application amount of compound D-14 was 0.25 g. A sample 302 was prepared in the same manner as described above.

The sample thus obtained was exposed to white light through an optical wedge, and then processed using an automatic developing machine according to the method described below. Until it was three times larger). Processing method (A) Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 33 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 25 ml 40 liter Water wash 2 minutes 10 seconds 24 ° C 1200 ml 20 liter Fixing 4 minutes 20 seconds 38 ° C 25 ml 30 liters Rinse (1) 1 minute 05 seconds 24 ° C From (2) to (1) 10 liter countercurrent piping Rinse (2) 1 minute 00 seconds 24 ° C 1200 Milliliter 10 liter Stability 1 minute 05 seconds 38 ° C 25 ml 10 liter Drying 4 minutes 20 seconds 55 ° C Replenishment rate per 35 mm width 1 m length Next, the composition of the processing solution is described. (Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylani Phosphate sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.10 (Bleaching solution) Mother liquor (g) Replenisher (g) Sodium ferric ethylenediaminetetraacetate trihydrate 100. 0 120.0 Disodium ethylenediaminetetraacetic acid salt 10.0 10.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 ann Near water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7 (fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution (70%) 170.0 mL 200.0 mL Add water 1.0 L 1.0 L pH 6.7 6.6 (Stable liquid) Mother liquor (g Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.3 0.45 disodium ethylenediaminetetraacetate 0.05 0.08 water 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0

After the treatment, the density of each sample was measured, and the density (D _B (min)) of the fogged portion of the blue-sensitive layer was read as a relative value (ΔD _B (min)) with respect to the sample 301, and the decolorization property of the dye was measured. Applied for evaluation. Further, the sensitivity of the green-sensitive layer was set to (fog +0.
2) is represented by the logarithmic value of the reciprocal of the exposure amount giving
It was evaluated by a relative value (ΔS _0.2 ) to 1. As a result, for the sample 302, ΔD _B (min) = 0.0 and ΔS _0.2 = 0.07. In the sample according to the present invention, D
Give _B (min). That is, it shows that the decolorization is excellent. In the sample of the present invention, the sensitivity of the green-sensitive layer can be significantly increased. This is due to the excellent absorption characteristics of the dye of the present invention.

Example 4 In the sample 302 of Example 3, the compound D-
14 and the same dye / polymer (weight ratio) as prepared in Example 2 in place of polymer P-14, ie D-2
/ P-11 (1), D-5 / P-3 (1), D-7 / P
-16 (0.7), D-11 / P-133 (2), D-
Samples 401 to 405 were prepared in exactly the same manner except that the sample was replaced with 27 / P-13 (1), and the same evaluation as in Example 3 was performed. Both gave the same good results as sample 302.

Claims (3)

(57) [Claims] 1. A hydrophilic colloid layer containing a dispersion obtained by emulsifying and dispersing a mixed solution containing at least one oil-soluble dye and at least one water-insoluble and organic solvent-soluble polymer. A silver halide photographic material characterized by having one layer. 2. The halogenated compound according to claim 1, wherein the water-insoluble and organic solvent-soluble polymer is a polymer having a repeating unit derived from a monomer having an anionic functional group. Silver photographic photosensitive material. 3. The silver halide photographic material according to claim 1, wherein the oil-soluble dye is a compound represented by the following general formula (I). General formula (I) In the formula, X and Y each represent an electron-withdrawing group or an acidic nucleus bonded by XY, Ar represents a phenyl group or a heterocyclic group, L ¹ , L ² , and L ³ each represent a methine group; n is 0,
Represents 1 or 2.