JPH08201975A - Silver halide photographic sensitive material containing dispersed fine solid particles - Google Patents

Abstract

PURPOSE: To keep uniformity of a coated surface and to enhance film strength by incorporating the dispersed fine solid particles of a specified compound in a coating fluid for a photosensitive or nonphotosensitive hydrophilic colloidal layer. CONSTITUTION: The silver halide photographic sensitive material having the photosensitive or nonphotosensitive hydrophilic colloidal layer having the silver halide photographic emulsion formed on a support is prepared by using the coating fluid containing the dispersed fine solid particles of at least one kind of compound represented by the formula and these particles has been subjected to a heat treatment process at >=40 deg.C and this coatig fluid is prepared in a pH of <=4.5. In the formula, D is a group having a chromophore: X is a dissociaable proctor or a group having it combined directly with D or via a divalent a bonding group with D; and y is an integer of 1-7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material and a method for preparing a coating solution thereof, and more particularly to a silver halide photographic light-sensitive material having improved uniformity and film strength of a coated material and a method for preparing a coating solution thereof.

[0002]

2. Description of the Related Art In general, silver halide photographic light-sensitive materials are halogenated in order to absorb light of a specific wavelength for the purpose of adjusting sensitivity, improving safety of safelight, and improving sharpness by preventing irradiation and halation. A method of adding a dye to a silver emulsion layer or another hydrophilic colloid layer is widely known.

The dyes used for such purposes have the following properties: (1) they are completely decolorized during the photographic processing in order to leave no harmful coloring on the photographic material after processing, or Easily eluted from the photographic light-sensitive material. (2) No chemical adverse effect on the silver halide emulsion in the light-sensitive material, for example, no change in sensitivity or fog. (3) It has an appropriate spectral absorption according to the purpose of use. Are needed.

The following dyes are mentioned as photographic dyes which satisfy all the above conditions. That is, British Patents 506,385, 1,177,429, 1,278,621, and
1,311,884, 1,338,799, 1,385,371, 1,46
7,214, 1,533,102, 1,553,516, JP 48-8
5,130, 49-114,420, 55-116,233, 59-111,
640, JP-A-3-7932, U.S. Pat.No. 2,533,472, 3,
247,127, 3,379,533, 3,469,985, 4,078,9
Oxonol dyes and other azo dyes described in No. 33, anthraquinone dyes, arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, cyanine dyes and the like.

Since these dyes are water-soluble, they diffuse from the dye addition layer to all layers in the photographic material. Therefore, in order to improve the sharpness of an intended dye image, a large amount of dye must be added to a specific layer in order to diffuse into another layer. It is easily expected that the addition of such a large amount of dye will greatly reduce the sensitivity and further increase the non-coloring property of the unexposed portion due to the residual color of the dye or the like after photographic processing.

By reducing the addition amount of the dye, the above residual color is reduced, but the sharpness is deteriorated, which is contrary to the high image quality of the color light-sensitive material. Therefore, there has been proposed a light-sensitive material in which a specific hydrophilic colloid layer is selectively colored, as opposed to a light-sensitive material using a dye that diffuses in all layers as described above.

For example, a means for keeping a dye in a specific hydrophilic colloid layer in a solid dispersion state is disclosed in JP-A-64-40827, European Patent Nos. 0,015,601B1, 0,276,566A1, and W088-04794.
No.

[0008]

However, a silver halide light-sensitive material using such a dye dispersion is a precipitate generated by agglomeration of dye particles in a coating liquid for a hydrophilic colloid layer containing the dye dispersion. Streaks on the coated product due to the above, uneven coating surface due to uneven coating due to high viscosity of the coating liquid, etc., and the coating film strength of the coated product deteriorates as the coating liquid is left in a dissolved state. It turns out that there is a problem such as.

Therefore, the object of the present invention is to provide a halogenated product having excellent film strength, even if the coating is applied to a support after the coating surface is kept uniform and the coating liquid is left in a dissolved state. A silver photographic light-sensitive material and a method for preparing a coating solution thereof are provided.

[0010]

As a result of earnest studies, the present inventor has found that the above problems can be solved by the following constitution. (1) Hydrophilic for forming a silver halide light-sensitive material having a photosensitive hydrophilic colloid layer having at least one layer of photosensitive silver halide emulsion and at least one non-photosensitive hydrophilic colloid layer on a support In the method for preparing a coating liquid for a photosensitive colloid layer, the coating liquid for a photosensitive or non-photosensitive hydrophilic colloid layer contains at least one solid fine particle dispersion of a compound represented by the following general formula (I), and A method for preparing a photographic coating solution, wherein at least one kind of solid fine particle dispersion is a dispersion that has been subjected to a heat treatment step at 40 ° C. or higher, and the pH of the coating solution for the hydrophilic colloid layer is 6.5 or less.

[0011]

[Chemical 6]

(In the formula, D represents a compound having a chromophore, X represents a dissociative proton bonded to D directly or through a divalent linking group or a group having a dissociative proton, and y is 1 to 1). It represents an integer of 7.) (2) The method for preparing a photographic coating solution according to the above 1, wherein at least one compound of the general formula (I) is a compound represented by the following general formula (II) or (III).

[0013]

[Chemical 7]

(In the general formula (II), A ¹ represents an acidic nucleus,
Q represents an aryl group or a heterocyclic group, L ¹ , L ² , L ³
Each represent a methine group, and m represents 0, 1 or 2. However, the compound of the general formula (II) has a water-soluble group in the molecule,
Carboxylic acid group, sulfonamide group, sulfamoyl group,
Sulfonylcarbamoyl group, acylsulfamoyl group,
It has 1 to 7 groups selected from the group consisting of phenolic hydroxyl groups and enol groups of oxonol dyes. )

[0015]

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(In the general formula (III), A ¹ and A ² each represent an acidic nucleus, L ¹ , L ² and L ³ each represent a methine group, n represents 0,
Represents 1, 2 or 3. However, the compound of the general formula (III) has, as a water-soluble group in the molecule, a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group,
It has 1 to 7 groups selected from the group consisting of an acylsulfamoyl group, a phenolic hydroxyl group and an enol group of an oxonol dye. (3) The photographic coating liquid as described in 1 or 2 above, wherein at least one kind of the solid fine particle dispersion subjected to the heat treatment is prepared together with a compound represented by the following general formula (IV-a) or (IV-b). Preparation method.

[0017]

[Chemical 9]

[0018]

[Chemical 10]

(In the general formulas (IV-a) and (IV-b), a and b each represent a value of 5 to 500.) (4) The heat treatment step of the solid fine particle dispersion is performed at pH 6.5 or less. The method for preparing a photographic coating solution described in 1, 2, or 3 above. (5) The method for preparing a photographic coating solution as described in 4 above, wherein the heat treatment step of the solid fine particle dispersion is performed at a pH of less than 4.5. (6) A photographic light-sensitive material obtained by coating a photosensitive hydrophilic colloid layer coating solution containing a photosensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer coating solution on a support. The photosensitive or non-photosensitive coating liquid for the hydrophilic colloid layer contains at least one solid fine particle dispersion of a compound represented by the following general formula (I), and at least one of the solid fine particle dispersions has a temperature of 40 ° C. or higher. A silver halide photographic light-sensitive material which is a dispersion which has been subjected to a heat treatment step, and which has a pH of 6.5 or less for preparing a coating solution for a hydrophilic colloid layer containing the solid fine particle dispersion.

[0020]

[Chemical 11]

(In the formula, D represents a compound having a chromophore, X represents a dissociative proton bonded to D directly or through a divalent linking group or a group having a dissociative proton, and y is 1 to 1). Represents an integer of 7.) (7) The silver halide photographic light-sensitive material according to the above 6, wherein at least one of the compounds of the general formula (I) is a compound represented by the following general formula (II) or (III).

[0022]

[Chemical 12]

(In the general formula (II), A ¹ represents an acidic nucleus,
Q represents an aryl group or a heterocyclic group, L ¹ , L ² , L ³
Each represent a methine group, and m represents 0, 1 or 2. However, the compound of the general formula (II) has a water-soluble group in the molecule,
Carboxylic acid group, sulfonamide group, sulfamoyl group,
Sulfonylcarbamoyl group, acylsulfamoyl group,
It has 1 to 7 groups selected from the group consisting of phenolic hydroxyl groups and enol groups of oxonol dyes. )

[0024]

[Chemical 13]

(In the general formula (III), A ¹ and A ² each represent an acidic nucleus, L ¹ , L ² and L ³ each represent a methine group, n represents 0,
Represents 1, 2 or 3. However, the compound of the general formula (III) has, as a water-soluble group in the molecule, a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group,
It has 1 to 7 groups selected from the group consisting of an acylsulfamoyl group, a phenolic hydroxyl group and an enol group of an oxonol dye. (8) The silver halide photograph as described in 6 or 7 above, wherein at least one kind of the solid fine particle dispersion subjected to the heat treatment is prepared together with a compound represented by the following general formula (IV-a) or (IV-b). Photosensitive material.

[0026]

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[0027]

[Chemical 15]

(In the general formulas (IV-a) and (IV-b), a and b represent a value of 5 to 500.) (9) The heat treatment step of the solid fine particle dispersion is carried out at pH 6.5 or less. The silver halide photographic light-sensitive material as described in 6, 7, or 8 above. (10) The silver halide photographic light-sensitive material as described in 9 above, wherein the heat treatment step of the solid fine particle dispersion is performed at a pH of less than 4.5.

That is, the present invention can achieve the object by the above constitution. In the present invention, each component is
It is considered to have at least the following operational effects. When the solid fine particle dispersion represented by the formula (I) is heat-treated at 40 ° C. or higher, generation of streaks parallel to the coating direction is suppressed.

When the coating liquid for the hydrophilic colloid layer containing the solid fine particle dispersion has a pH of 6.5 or less,
The film strength of the coating material is improved. Furthermore, by combining the heat treatment of the solid fine particle dispersion at 40 ° C. or higher and the pH of the coating solution preparation to 6.5 or lower, the effect of improving the uniformity of the coated surface more than expected (preventing generation of lines and unevenness) is obtained. The film strength can be obtained.

When the solid fine particle dispersion is prepared in the presence of the dispersing agent represented by the formula (IV-a) or (IV-b), the coating surface uniformity is further improved. Further, if the pH during the preparation of the coating liquid is further lowered, the film strength of the coated product is further improved. When the solid fine particle dispersion is heat-treated at a pH of less than 4.5, the coating surface uniformity is further improved and the film strength of the coating material is further improved.

Next, the compound represented by the following general formula (I) will be explained. The compound represented by formula (I) of the present invention is typically a dye. The dye represented by the formula (I) is characterized in that it has dissociative hydrogen or the like in its molecular structure.

The compound having a chromophore in D can be selected from among many well known dyes. These compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes,
Mention may be made of indoaniline dyes.

X represents a dissociative hydrogen bonded to D directly or via a divalent linking group or a group having a dissociative hydrogen. Divalent linking group between X and D is an alkylene group, an arylene group, a heterocyclic _{residue, -CO -, - SO n -} (n
= 0, 1, 2), -NR- (R represents a hydrogen atom, an alkyl group, an aryl group), -O-, and a divalent group combining these linking groups, and they are an alkyl group. It may have a substituent such as an aryl group, an alkoxy group, an amino group, an acylamino group, a halogen atom, a hydroxyl group, a carboxy group, a sulfamoyl group, a carbamoyl group or a sulfonamide group. Preferred examples - (CH _{2)
n - (n = 1,2,3),} - CH 2 CH (CH 3) CH
_2- , 1,2-phenylene, 5-carboxy-1,3-
Phenylene, 1,4-phenylene, 6-methoxy-1,
3-phenylene, -CONHC ₆ H ₄ -, and the like.

The dissociative hydrogen or a group having a dissociative hydrogen represented by X is not dissociated when the dye represented by the formula (I) is added to the silver halide photographic light-sensitive material of the present invention. And has the property of rendering the dye of formula (I) substantially water-insoluble, and dissociates to render the compound of formula (I) substantially water-soluble in the step of developing the photosensitive material. Have characteristics. Examples of the group having a dissociative hydrogen represented by X include a group having a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group and the like. Examples of the dissociative hydrogen represented by X include hydrogen of the enol group of the oxonol dye.

The preferable range of y is 1 to 5, and the particularly preferable range is 1 to 3.

Among the compounds represented by the formula (I), preferred are those in which the group having a dissociative hydrogen in X is a group having a carboxylic acid group, and particularly an aryl group substituted with a carboxyl group. Compounds are preferred. Further, among the compounds represented by the formula (I), more preferred are the compounds represented by the general formula (II) or the general formula (III).

The general formulas (II) and (III) will be described in detail below. The acidic nucleus represented by A ¹ and A ² is preferably one derived from a cyclic ketomethylene compound or a compound having a methylene group sandwiched by electron withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolo Pyridine, hydroxypyridone, pyrazolidinedione and 2,5-dihydrofuran can be mentioned. These may have a substituent.

The compound having a methylene group sandwiched by electron withdrawing groups can be represented as Z ¹ CH ₂ Z ² .
Here, Z ¹ and Z ² are —CN, —SO ₂ R ¹¹ , and
-COR ¹¹ , -COOR ¹² , -CONHR ¹² , -SO ₂
NHR ¹² or -C [= C (CN) ₂ ] R ¹¹ is represented. R
¹¹ represents an alkyl group, an aryl group, or a heterocyclic group,
R ¹² represents a hydrogen atom or a group represented by R ¹¹ , and these may each have a substituent.

Examples of the aryl group represented by Q include a phenyl group and a naphthyl group. Each of these may have a substituent. Examples of the heterocyclic group represented by Q include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine,
Mention may be made of quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxodiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and coumarone. it can.
Each of these may have a substituent.

The methine group represented by L ¹ , L ² and L ³ is
It may have a substituent and the substituents may be linked to each other to form a 5- or 6-membered ring (eg, cyctopentene, cyclohexene).

The substituent which each of the above-mentioned groups may have is not particularly limited as long as it is a substituent which does not substantially dissolve the compounds of formulas (I) to (III) in water of pH 5 to pH 7. Absent. For example, the following substituents can be mentioned. Carboxylic acid group, sulfonamide group having 1 to 10 carbon atoms (eg, methanesulfonamide, benzenesulfonamide,
Butanesulfonamide, n-octanesulfonamide), an unsubstituted or alkyl- or aryl-substituted sulfamoyl group having 0 to 10 carbon atoms (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, naphthylsulfamoyl, butyl) Sulfamoyl), a sulfonylcarbamoyl group having 2 to 10 carbon atoms (eg, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), an acylsulfamoyl group having 1 to 10 carbon atoms (eg, acetylsulfamoyl, propionyl) Sulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), a chain or cyclic alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclo) Pentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl,
2-methoxyethyl, benzyl, phenethyl, 4-carboxybenzyl, 2-diethylaminoethyl), an alkenyl group having 2 to 8 carbon atoms (for example, vinyl, allyl),
An alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, butoxy), a halogen atom (for example, F, Cl,
Br), an amino group having 0 to 10 carbon atoms (for example, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino), an ester group having 2 to 10 carbon atoms (for example, methoxycarbonyl), and 1 to 10 carbon atoms. Amido group (eg, acetylamino, benzamide), carbon number 1
A carbamoyl group having 10 to 10 (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl), an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl, hydroxyphenyl, 4-carboxyphenyl, 3
-Carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), an aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, 4-carboxyphenoxy, 3-methylphenoxy, Naphthoxy), carbon number 1
8 alkylthio groups (eg, methylthio, ethylthio, octylthio), arylthio groups having 6 to 10 carbon atoms (eg, phenylthio, naphthylthio), 1 to 1 carbon atoms
10 acyl groups (eg acetyl, benzoyl, propanoyl), sulfonyl groups having 1 to 10 carbon atoms (eg,
Methanesulfonyl, benzenesulfonyl), carbon number 1 to
10 ureido groups (eg, ureido, methylureido), urethane groups having 2 to 10 carbon atoms (eg, methoxycarbonylamino, ethoxycarbonylamino), cyano groups, hydroxyl groups, nitro groups, heterocyclic groups (eg, 5-carboxy) Benzoxazole ring), pyridine ring, sulfolane ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine ring, furan ring).

Among the compounds represented by the general formula (III), more preferred are the compounds represented by the general formula (V). The compound represented by the general formula (V) has hydrogen of an enol group as dissociative hydrogen.

[0044]

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In the general formula (V), R ¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ² represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, --COR ⁴ or --SO. ₂ represents R ⁴ , R ³ is a hydrogen atom, cyano group, hydroxyl group, carboxyl group, alkyl group, aryl group, -C
_{^{O 2 R 4, -OR 4,}} -NR 5 R 6, -CONR 5 R 6, -N
^{R 5 COR 4, -NR 5 SO} 2 R 4 or -NR ⁵ CONR,
⁵ R ⁶ (here, R ⁴ represents an alkyl group or an aryl group, and R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group, or an aryl group). L ¹ , L ² and L ³ each represent a methine group. n represents 1 or 2.

Examples of the alkyl group of R ¹ include an alkyl group having 1 to 4 carbon atoms, a 2-cyanoethyl group, a 2-hydroxyethyl group and a carboxybenzyl group, and an aryl group is a phenyl group, a 2-methylphenyl group, 2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,6-dicarboxyphenyl group,
A 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 2-chloro-4-carboxyphenyl group, a 4-methylsulfamoylphenyl group can be mentioned, and a heterocyclic group is represented by the following chemical formula 17. The groups mentioned may be mentioned.

[0047]

[Chemical 17]

Examples of the alkyl group of R ² include an alkyl group having 1 to 4 carbon atoms, a carboxymethyl group, a 2-hydroxyethyl group and a 2-methoxyethyl group, and an aryl group is a 2-carboxyphenyl group and a 3-carboxyphenyl group. Examples thereof include a carboxyphenyl group, a 4-carboxyphenyl group, and a 3,6-dicarboxyphenyl group, and the heterocyclic group is represented by the following chemical formula 1.
The groups described in 8 are listed, -COR ⁴ includes an acetyl group, and -SO ₂ R ⁴ includes a methanesulfonyl group.

[0049]

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Examples of the alkyl group of R ³ , R ⁴ , R ⁵ and R ⁶ include alkyl groups having 1 to 4 carbon atoms. R ³ , R ⁴ , R
Examples of the aryl group of ⁵ and R ⁶ include a phenyl group and a methylphenyl group. In the present invention, R ¹ is preferably a carboxyl-substituted phenyl group (eg, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, 3,6-dicarboxyphenyl).

The general formula (I) used in the present invention is described below.
Specific examples of the compounds represented by (3) to (III) and (V) are described below, but the invention is not limited thereto.

[0052]

[Chemical 19]

[0053]

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[0054]

[Chemical 21]

[0055]

[Chemical formula 22]

[0056]

[Chemical formula 23]

[0057]

[Chemical formula 24]

[0058]

[Chemical 25]

[0059]

[Chemical formula 26]

[0060]

[Chemical 27]

[0061]

[Chemical 28]

[0062]

[Chemical 29]

[0063]

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[0064]

[Chemical 31]

[0065]

Embedded image

[0066]

[Chemical 33]

[0067]

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[0068]

Embedded image

[0069]

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[0070]

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[0071]

[Chemical 38]

The dyes used in the present invention are those described in International Patent WO
88/04794, European Patent EP027472
3A1, 276566, 299435, JP-A-52-92716, 55-155350, 5
5-155351, 61-205934, 48
-68623, U.S. Pat. Nos. 2,527,583, 348.
No. 6897, No. 37465939, No. 3933798
No. 4130429, No. 4040841, No. 3-282244, No. 3-7931, and No. 3-167.
It can be synthesized according to the method described in the specification or publication such as No. 546 or according to the method.

The solid fine particle dispersion of the dye of formula (I) used in the present invention can be prepared by a known method.
Details of the production method are described in functional pigment application technology (published by CMC, 1991) and the like. Media distribution is one of the common methods. In this method, a dye in a wet state with water or an organic solvent called dye powder or its wet cake is made into an aqueous slurry, and a known pulverizer (for example, ball mill, vibration ball mill, planetary ball mill, vertical sand mill, roller mill, pin mill, Grind by mechanical force in the presence of dispersion media (steel balls, ceramic balls, glass beads, alumina beads, zirconia silicate beads, zirconia beads, Ottawa sand, etc.) using a coball mill, caddy mill, horizontal sand mill, attritor, etc.) To do. Of these, the average diameter of the beads is preferably 2 mm to 0.3 m
m, more preferably 1 mm to 0.3 mm, and even more preferably 0.5 mm to 0.3 mm. In addition to these, jet mills, roll mills, homogenizers,
A method of crushing with a colloid mill or a dissolver or a method of crushing with an ultrasonic disperser can also be used.

Further, as disclosed in US Pat. No. 2,877,0012, after dissolving in a homogeneous solution, a poor solvent is added to cause solid fine particles to break out.
As disclosed in No. 43, a method of precipitating solid fine particles by lowering the pH after dissolving in an alkaline solution can also be used.

When these solid fine particle dispersions are prepared, it is preferable to add a dispersion aid. Examples of the dispersion aid that has been conventionally disclosed include alkylphenoxyethoxy sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate ester salt, alkyl sulfosuccinate, sodium oleylmethyl taurate, and naphthalene sulfonic acid. Formaldehyde degenerate, polyacrylic acid, polymethacrylic acid, maleic acid acrylic acid copolymer, anionic dispersant such as carboxymethyl cellulose, cellulose sulfate, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Nonionic dispersants, cationic dispersants, and betaine dispersants are mentioned.

More preferred are polyalkylene oxides represented by the above general formula (IV-a) or (IV-b). In the formulas (IV-a) and (IV-b), a and b each represent a value of 5 to 500. Preferred a and b values are 10 to 200, and more preferred a and b values are 50 to 150, respectively. It is preferable that the values of a and b are in this range from the viewpoint of improving the uniformity of the coated surface.

In the above dispersion aid, the ratio of the polyethylene oxide part is preferably 0.3 to 0.
9, more preferably 0.7 to 0.9, further preferably 0.8 to 0.9, and the average molecular weight of the polyalkylene oxide is preferably 1,000 to 3
10,000, more preferably 5,000 to 40,000
00, more preferably 8,000 to 20,000. Further, the HLB (hydrophilic / lipophilic balance) of the above dispersion aid is preferably 7 to 30, more preferably 12
To 30 and more preferably 18 to 30.

A value within the above range is preferable in terms of improving the uniformity of the coated surface. These compounds are commercially available, for example, Pluronic manufactured by BASF.

The general formula (IV-
Specific examples of the compound represented by a) or (IV-b) will be described.

[0080]

[Chemical Formula 39]

The amount of the above-mentioned dispersion aid used with respect to the dye of the present invention is preferably 0.05 to 0.5, more preferably 0.1 to 0.3 by weight ratio. When the amount used is in this range, it is preferable in terms of improving the uniformity of the coated surface. Further, polyvinyl alcohol, polyvinylpyrrolidone, for the purpose of stabilizing and lowering the viscosity of the solid fine particle dispersion during preparation.
Hydrophilic colloids such as polyethylene glycol, polysaccharides and gelatin may be allowed to coexist. The pH of the dispersion is preferably 2 to 8, more preferably 2 to 6.5.
Is.

The solid fine particle dispersion of the dye of the present invention is heat-treated before, during or after the dispersion by the method disclosed in JP-A-5-216166.

To provide a layer containing fine particles of a dye on a photographic light-sensitive material, the fine particles thus obtained are dispersed in an appropriate binder solution so that solid fine particles are present with a substantially uniform probability. After preparation, the coating liquid for the hydrophilic colloid layer containing the solid fine particle dispersion can be applied by coating on a desired support.

The binder is not particularly limited as long as it is a hydrophilic colloid that can be used in the light-sensitive emulsion layer and the non-light-sensitive layer, but gelatin or a synthetic polymer such as polyvinyl alcohol or polyacrylamide is usually used.

Gelatin is a preferred hydrophilic colloid. Since the dye used in the present invention can be used in both color photographic light-sensitive materials and black-and-white photographic light-sensitive materials, the coating amount of gelatin cannot be generally specified, but a layer containing a dye dispersion with respect to a support is used. The total gelatin coating amount on the same side is 2 g / m ^{2 to} 30 g / m ^2, more preferably 2.5 g
/ M ^{2 to 20} g / m ² . The amount of gelatin in the layer containing the dye dispersion is preferably 20 mg / m ^{2 to 3} g / m ² . In particular, from the viewpoint of accelerating the processing, it is preferable to reduce the coating amount of the hydrophilic colloid as much as possible. In one preferred embodiment, the layer containing the dye dispersion is provided between the support and the silver halide emulsion layer. The coating amount of the hydrophilic colloid in the dye layer can be 2.0 g / m ² or less. The silver halide photographic light-sensitive material of the present invention can be used as a double-sided light-sensitive material. Various types of gelatin are known, and lime-treated, acid-treated or various modified gelatins can be used.

The fine particles in the solid dispersion have an average particle diameter of 0.
005 μm to 10 μm, preferably 0.01 μm to 1 μm, more preferably 0.01 μm to 0.7
It is preferably μm. Within this range, it is preferable in terms of non-aggregation of fine particles and light absorption efficiency. The solid fine particle dispersion of the compound of the general formula (I) used in the present invention can be used alone or in combination with a plurality of solid fine particle dispersions.

Further, the hydrophilic colloid layer to which the solid fine particles are added may be a single layer or a plurality of layers.
For example, when a single solid fine particle dispersion is added to only one layer, when dividedly added into a plurality of layers, when a plurality of solid fine particle dispersions are simultaneously added to one layer, and when added to separate layers, etc. Examples include, but are not limited to:

The solid fine particle dispersion is preferably contained in various non-photosensitive hydrophilic colloid layers (for example, an antihalation layer, a yellow filter layer, etc.) according to its purpose, and a plurality of the nonphotosensitive layers are provided. In the light-sensitive material of the aspect described above, these plural layers can be contained. Further, the solid fine particle dispersion may be incorporated in an amount necessary for an antihalation layer, and may be added to a photosensitive silver halide emulsion layer for preventing irradiation.

The concentration of the dye in the solid fine particle dispersion of the present invention is suitably 0.1 to 50% by weight, preferably 2 to 30% by weight. When the dye concentration is in this range,
It is preferable in terms of the viscosity of the dispersion.

The compound of the general formula (I) used in the present invention is
By performing heat treatment before incorporating it into the photosensitive material,
The effect of the present invention can be obtained. As the heat treatment, a method performed before the step of finely dispersing the dye powder into a solid state such as heating the dye powder in a solvent, and without cooling when dispersing the dye in water or another solvent in the presence of a dispersant, Alternatively, there are a method in which dispersion is performed at a temperature and a method in which a liquid after dispersion and a coating solution are subjected to heat treatment, but it is particularly preferable to perform after dispersion.

When a plurality of solid fine particle dispersions of the compound represented by the formula (I) are used, at least one kind may be heat-treated.

The pH at the time of dispersion and during the heat treatment after dispersion may be any condition as long as the dispersion is present in a stable manner, preferably pH.
2.0 or more and 8.0 or less, more preferably 2.0 or more and 6.
5 or less, most preferably 2.5 or more and less than 4.5. p
When H is in this range, it is preferable from the viewpoint of improving the film strength of the coated material. The pH of the dispersion can be adjusted by using, for example, sulfuric acid, hydrochloric acid, acetic acid, citric acid, phosphoric acid, oxalic acid, carbonic acid, sodium hydrogencarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide or a buffer solution thereof. .

The temperature for the heat treatment varies depending on the heat treatment step, the size and shape of the powder or particles, the heat treatment conditions, the solvent, etc., and therefore cannot be unequivocally determined as long as the dye is not decomposed at 40 ° C. or higher. However, in the case of heat treatment with powder, 40 ° C. to 200 ° C. is suitable, preferably 50 ° C. to 150 ° C., and in the case of heat treatment in a solvent, 40 ° C. to 150 ° C. is suitable, preferably 5
0 ℃ to 150 ℃, 40 when heat treatment during dispersion
C. to 90.degree. C. is suitable, preferably 50.degree. C. to 90.degree. C., and when the dispersion after heat treatment is heat treated, 40.degree. C. to 100.degree. C. is suitable, preferably 50.degree.
5 ° C.

If the heat treatment is less than 40 ° C., the effect becomes poor, which is not preferable.

When the heat treatment is carried out in a solvent, the kind of the solvent is not limited as long as it does not substantially dissolve the dye (I), and examples thereof include water and alcohols (eg, methanol, ethanol, isopropyl alcohol). , Butanol, isoamyl alcohol, octanol, ethylene glycol, diethylene glycol, ethyl cellosolve), ketones (eg acetone, methyl ethyl ketone), esters (eg ethyl acetate, butyl acetate), alkylcarboxylic acids (eg acetic acid, propionic acid) , Nitriles (eg acetonitrile), ethers (eg dimethoxyethane, dioxane, tetrahydrofuran), amides (eg dimethylformamide) and the like.

Further, even when the dye is dissolved by these solvents alone, it can be used if the dye is not substantially dissolved by mixing with water or another solvent or adjusting the pH.

The time for heat treatment cannot be unequivocally stated. A lower temperature requires a longer time, and a higher temperature requires a shorter time. The heat treatment can be arbitrarily set so that the heat treatment can be realized within a range that does not affect the production process, but it is usually preferably 1 hour to 4 days. In the present invention, it is preferred that the compound represented by the following general formula (VI) is contained in the same photographic constituent layer together with the solid fine particle dispersion.

General formula (VI)

[0099]

[Chemical 40]

[In the formula (VI), R represents a hydrogen atom, a hydrophobic group or a hydrophobic polymer, P contains at least one of the following structural units A, B and C, and the degree of polymerization of P is 10
It represents a polymer of 3500 or less. n represents 1 or 2. m represents 0 or 1.

[0101]

Embedded image

Here, R ¹ represents --H or an alkyl group having 1 to 6 carbon atoms, R ² represents --H or an alkyl group having 1 to 10 carbon atoms, and R ³ represents --H or --CH ₃ . Represent, R
⁴ H, -CH _3, (including ammonium salt or a metal salt) -CH ₂ COOH or represents -CN, X is -H, -C
OOH (including ammonium group or metal salt) or -CO
Represents NH _2, Y is (including ammonium salt or a metal salt) -COOH, - (including ammonium salt or a metal _{salt) SO 3 H, - OSO 3} H ( including ammonium salt or a metal salt), - CH ₂ SO ₃ (including ammonium salt or a metal _{salt) H, - CONHC (CH 3} ) ( including ammonium salt or a metal salt) ₂ CH ₂ SO ₃ H or -CONHCH ₂ C
H ₂ CH ₂ N ⁺ (CH ₃ ) ₃ Cl ⁻ . ]

A typical example of the compound represented by the above general formula (VI) is a random or block copolymer of vinyl alcohol and vinyl ester, or vinyl containing a third monomer component having an anionic group such as a carboxyl group. A random or block copolymer of alcohol and vinyl ester modified at the terminal with an alkyl group or a hydrophobic polymer can be mentioned.

Compound (VI) preferably used in the present invention
Preferably has a relatively higher molecular weight than the surfactant conventionally used in the photographic field (molecular weight of 1000 or more). Further, the hydrophilic group of the conventional surfactant is a nonionic alkylene oxide group such as ethylene oxide, a carboxyl group, a sulfone group, an anionic group such as a phosphate group,
While it usually has one cationic group such as a quaternary ammonium group, the hydrophilic group of the compound (VI) has a repeating structure of a monomer unit containing an OH group, a repeating structure of an anionic group and a cation. It is necessary to have any one or more of the repeating structures of the functional group.

The compound (VI) is a coating aid, an antistatic agent,
It can also be used as a surface friction modifier and a surface hydrophobizing agent.

Examples of the hydrophobic group represented by R in the general formula (VI) include an aliphatic group (eg, alkyl group, alkenyl group, alkynyl group, etc.), aromatic group (eg, phenyl group, naphthyl group, etc.) and alicyclic group. Yes, these include those that have been replaced. As the substituent, an aliphatic group, an aromatic group, an alicyclic group, a heterocyclic group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an N-substituted sulfamoyl group, a carbamoyl group,
Examples thereof include an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxy group, an aryloxy group, an aralkyl group and an acyl group.

When the hydrophobic group represented by R in the general formula (VI) is an alkyl group, it has 3 to 70 carbon atoms, preferably 4 to 5 carbon atoms.
0, especially 8 to 24 is preferable. Furthermore, when R is a substituted or unsubstituted alicyclic group, aromatic hydrocarbon group or hydrophobic polymer, R has a greater effect of enhancing dispersion stability.

When R in the general formula (VI) is a hydrophobic polymer, polystyrene and its derivative, polymethacrylic acid ester (eg polymethylmethacrylate) and its derivative, polyacrylic acid ester and its derivative,
Water-insoluble vinyl polymers and vinyl copolymers typified by polybutene, polyvinyl acetate, and polyvinyl versatate, and water-insoluble polyoxyalkylenes such as polyoxypropylene and polyoxytetramethylene, and Examples thereof include water-insoluble polymers such as polyamide and polyester. In particular, polystyrene and its derivatives, polymethacrylic acid esters and their derivatives, polyacrylic acid esters and their derivatives, and polyvinyl chloride are preferably used. The degree of polymerization of the hydrophobic polymer is 2 or more and 50 or more.
It is 0 or less, preferably 2 or more and 200 or less, and more preferably 2 or more and 100 or less.

Specific examples of the case where R in the general formula (VI) is a hydrophobic group are shown below, but the invention is not limited thereto.

[0110]

Embedded image

[0111]

[Chemical 43]

[0112]

[Chemical 44]

[0113]

Embedded image

[0114]

Embedded image

[0115]

[Chemical 47]

[0116]

Embedded image

[0117]

[Chemical 49]

[0118]

Embedded image

Regarding the compound represented by the general formula (VI) of the present invention, P is a polymer containing at least one of the structural units A, B and C. Specific examples of the structural unit A include vinyl alcohol, α-methyl vinyl alcohol, α-propyl vinyl alcohol and the like. Examples of the structural unit B include vinyl acetate, vinyl formate, vinyl propionate and their α-substituted products.

Further, as the structural unit C, acrylic acid, methacrylic acid or crotonic acid (each containing an ammonium salt or a metal salt such as Na or K), maleic acid or itaconic acid (each a monoalkyl ester, an ammonium salt or Na) is used. , Metal salts such as K), vinylphosphonic acid, vinylsulfuric acid, acrylsulfonic acid, methacrylsulfonic acid, 2-acrylamido-3-methylpropanesulfonic acid or 2-methacrylamido-3-methylpropanesulfonic acid (each ammonium). Salt, or a metal salt such as Na or K), acrylamidopropyltrimethylammonium chloride or methacrylamideamidopropyltrimethylammonium chloride, and other monomer units that ionically dissociate in water.

Among them, the structural unit A contains a vinyl alcohol unit, the structural unit B contains a vinyl acetate unit, and the structural unit C contains a carboxylic acid (ammonium salt or a metal salt such as Na or K). ) Or sulfonic acid (including an ammonium salt or a metal salt such as Na or K) is a more preferable unit.

The content of the structural units A, B and C is not particularly limited, but when the content of the structural unit C is 1 mol% or less, the polymer represented by the general formula (VI) is water-soluble or water-soluble. In order to be dispersible, the content of structural unit A is 50 mol%
It is preferably ˜100 mol%.

General formula (VI) preferably used in the present invention
The compounds represented by include a wide range of compounds from water-soluble to water-dispersible. As long as the compound represented by the general formula (VI) is water-soluble or water-dispersible, there is no problem that P contains a structural unit other than the above structural units A, B and C. , For example ethylene, propylene, isobutene, acrylonylolyl, acrylamide, methacrylamide, N-vinylpyrrolidone, vinyl chloride or vinyl fluoride units.

The degree of polymerization of P is 10 to 3500, preferably 10 to 2000, more preferably 10 to 1000, and particularly preferably 10 to 500.

The lower alkyl group for R ² in the structural units A and B includes an alkyl group having 1 to 10 carbon atoms, and a methyl group is particularly preferable. Further, the alkyl group may be substituted with a hydroxyl group, an amide group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a sulfonamide group or the like.

As the binder used in the present invention, gelatin is most commonly used because of its photographic properties, production suitability and physical properties. When the compound represented by the general formula (VI) is mixed in gelatin at a ratio of 1% by weight or more, a compound having a composition compatible with gelatin is preferable. As such a compound, the structural unit B is 50 mol% or less,
When the structural unit C contains a carboxyl group and the number of the carboxyl group is one per unit, the content is 5 mol% or more, preferably 10 mol% or more, particularly preferably 15 mol% or more, and the carboxyl group is a unit. When the number is n, the content is preferably 1 / n. As the compound represented by the general formula (VI) which is particularly preferable from the viewpoint of compatibility with gelatin, the polymer A is vinyl alcohol having a content of 50 mol% or more, and the polymer B is vinyl acetate having 40 mol% or less, The polymer C is a polymer in which itaconic acid (including an ammonium salt or a metal salt such as Na or K) is 2 mol% or more.

General formula (VI) preferably used in the present invention
The compound represented by is different in the optimum chemical composition of P and R constituting the sensitive material, the molecular weight, etc., depending on the intended use of the sensitive material,
For any purpose, the weight ratio of P and R is 0.001 ≦ R
/ P ≦ 2, more preferably 0.01 ≦ R / P ≦ 1 is particularly preferable.

Specific examples of the compound represented by the general formula (VI) are shown in Table-A, but the invention is not limited thereto.

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

[Table 3]

[0132]

[Table 4]

The amount of the compound of the general formula (VI) used varies depending on the physical properties and amount of the solid fine particle dispersion used, but is usually 0.001 g / m ^{2 to} 10 g / m ² , preferably 0.002 g / m ^2.
a ^{g / m 2 ~5g / m 2} . The compound of general formula (VI) may be used as a dispersant when preparing a dispersion, may be allowed to coexist after dispersion, or may be allowed to coexist immediately before coating. The compound represented by the general formula (VI) is described in, for example, JP-A-62-28.
8643, 61-254237, 61-254.
No. 238, No. 61-254239, No. 61-2542
It can be synthesized by the method described in the publication such as No. 40. Further, when R in the polymer of the general formula (VI) is an alkyl group, it is available as a commercial product (for example, MP-103, MP-203 manufactured by Kuraray Co., Ltd.,
MP102 etc. are mentioned).

When preparing the coating solution for the hydrophilic colloid layer containing the solid fine particle dispersion of the present invention, the pH needs to be 6.5 or less. The preferred pH is 6.0 or less, and most preferably 5.5 or less. The lower limit of the pH is preferably 2.0 or higher, more preferably 2.5 or higher.
This can solve the problem of poor adhesion of the coated material.

When the coating liquid for hydrophilic colloid layer containing the solid fine particle dispersion of the present invention is prepared, the preparation temperature is 33.
C. or higher and 60.degree. C. or lower is preferable. The temperature is more preferably 33 ° C or higher and 50 ° C or lower, and most preferably 33 ° C or higher and 45 ° C or lower.

Next, the photographic layers and the like of the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention includes a color negative film, a reversal film, a color negative film for movies, a color positive film, a positive film for movies, a general-purpose color light-sensitive material for movies, a black and white negative film, a microfilm, and X-. It can be applied to black-and-white light-sensitive materials such as ray films.

There are no particular restrictions on various additives and development processing methods used when the present invention is applied to a black-and-white light-sensitive material. For example, JP-A-2-68539 and JP-A-5-11389.
The following relevant parts of JP-A No. 2-58041 and JP-A No. 2-58041 can be preferably used.

1. Silver halide emulsion and its production method
2-68539, page 8, lower right column, line 6 from bottom to page 10 upper right column, line 12 2. Chemical sensitization method: Page 10, upper right column, line 13 to lower left column 16
Line, selenium sensitization method described in JP-A-5-11389. 3. Antifoggant / stabilizer: JP-A-2-68539, No. 10
Page 17, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes: page 4, lower right column, line 4 to page 8, lower right column, and JP-A-2-58041, page 12, lower left column, line 8 to lower right column, line 19. 5. Surfactant / antistatic agent: JP-A-2-68539
Page 1, upper left column, line 14 to page 12, upper left column, line 9 and JP-A-2-5
No. 8041, page 2, lower left column, line 14 to page 5, line 12 6. Matting agent / Plasticizer / Slipping agent: page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower left column, line 13 to page 10, lower left column, line 3 Eye. 7. Hydrophilic colloid: JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16 8. Hardener: Page 12, lower left column, line 17 to page 13, upper right column 6
Line. 9. Development method: Same as page 15, upper left column, line 14 to same, lower left column 13
Line.

When the present invention is applied to a color photographic material, at least one photosensitive layer may be provided on the transparent support. As a typical example, at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is provided on a transparent support.
It is a silver halide photographic light-sensitive material. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, in the case of a reflective color light-sensitive material, the order of installation is reversed. Further, the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These include couplers and DIRs described below.
A compound, a color mixing inhibitor, etc. may be contained. The multiple silver halide emulsion layers constituting each unit photosensitive layer are DE 1,1
It is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in JP 21,470 or GB 923,045 so that the sensitivities are gradually lowered toward the support. Also,
JP-A-57-112751, 62-200350, 62-206541, 62-20
As described in each of the 6543 publications, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

The preferred silver halide used in the photographic light-sensitive material is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 0.5 to about 30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Further, preferred silver halides used for the reflective type light-sensitive material and the color positive film for motion pictures are silver chlorobromide and silver chloride, and particularly, the silver chloride content is 95 mol% or more and the rest is silver bromide (silver iodide) Are preferred.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No.17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and
No.18716 (November 1979), p.648, No.307105 (November 1989)
Mon), pp. 863-865, and "Graphics and Chemistry" by Graphide, published by Paul Montel (P. Glafkides, Chemie e.
t Phisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry, Focal
Press, 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 P
ress, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,41
The monodisperse emulsions described in 3,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14, 248
~ 257 (1970); US 4,434,226, 4,414,310, 4,4
It can be easily prepared by the method described in 33,048, 4,439,520 and GB2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned 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, or a type having a latent image both on the surface and inside. Must be a type of emulsion. Among the internal latent image types, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used, and the preparation method is described in JP-A-59-133542. . The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are RD No.17643 and RD No.187.
16 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

Silver halide grains whose surface is fogged as described in US Pat. No. 4,082,553, US Pat. No. 4,626,498, and JP-A-59-214852.
It is preferable to apply the internally fogged silver halide grains and colloidal silver described in (4) above to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is US 4,626,498, JP-A-59-2
14852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, especially 0.05.
˜0.6 μm is preferred. The grain shape may be regular grain or polydisperse emulsion, but monodispersity (at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferable that

The silver coating amount of the light-sensitive material of the present invention is 6.0 g / m 2.
^It is preferably ² or less, and most preferably 4.5 g / m ² or less.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, to page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Light absorber, pages 25 to 26, page 649, right column, page 873, filter dye, page 650, left column, ultraviolet absorber 6. Binder 26 pages 651 left column 873 to 874 7. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 8. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 9. Antistatic agent Page 27 Page 650 Right column Page 876-877 10. Matting agent pp. 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); A coupler represented by the general formula (I) of claim 1 of 307248; US 5,066,576.
The coupler represented by the general formula (I) on lines 45 to 55 of column 1 of the above; the coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; in claim 1 on page 40 of EP 498, 381A1. The couplers described (especially D-35 on page 18); EP 447,969 A1 4
Couplers represented by formula (Y) on page (especially Y-1 (page 17), Y-54
(P. 41)); US Pat. No. 4,476,219, column 7, lines 36-58, formula (II).
~ (IV) couplers (especially II-17, 19 (column 1
7), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57)
(Page 11, lower right), L-68 (Page 12, lower right), L-77 (Page 13, lower right)); EP
456, 257 A-4 -63 (134 pages), A-4 -73, -75 (139 pages); EP 4
86, 965 M-4, -6 (page 26), M-7 (page 27); JP-A-6-43611, paragraph 0024, M-45; JP-A-5-204106, paragraph 0036, M-1;
M-22 of paragraph 0237 of 4-362631. Cyan coupler: CX-1, 3, 4, 5, 11, of JP-A-4-204843
12, 14, 15 (pages 14 to 16); C-7, 10 (35 of JP-A-4-43345)
Page, 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. A coupler. Polymer coupler: P-1, P-5 of JP-A-2-44345 (page 11).

Examples of couplers in which the coloring dye has an appropriate diffusibility include US 4,366,237, GB 2,125570, EP 96,873B, D
Those described in E 3,234,533 are preferable. The coupler for correcting the unwanted absorption of the color forming dye is a yellow colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially page 84). YC-86),
Yellow colored magenta coupler ExM-7 described in the EP
(Page 202, EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 (column 8) described in US 4,833,069, CC-13 (column 10), US 4,837,136 (2 ) (Column 8),
The colorless masking couplers represented by formula (A) of claim 1 of W092 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred.

Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized product of a developing agent include the following. Development inhibitor releasing compound:
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of EP 378, 236A1 (particularly T-101 (page 30), T-104 (page 31), T-
113 (36 pages), T-131 (45 pages), T-144 (51 pages), T-158 (58 pages)),
EP 436,938 A2, page 7 of the compound represented by formula (I) (especially D-49 (page 51)), JP-A-5-307248 represented by formula (1) (especially (23) ), 5 of EP 440,195A2
Compounds represented by formulas (I), (II) and (III) described on pages 6 to 6 (particularly I- (1) on page 29); Bleach accelerator releasing compound: EP 310,1
Compounds represented by formulas (I) and (I ') on page 5 of 25A2 (especially 61
(60), (61) on page and compounds of formula (I) of claim 1 of JP-A-6-59411 (particularly (7) of paragraph 0022); Ligand-releasing compounds: described in claim 1 of US 4,555,478 A compound represented by LIG-X (in particular, a compound on lines 21 to 41 of column 12);
Leuco dye releasing compounds; compounds 1 to 6 in columns 3 to 8 of US 4,749,641; fluorescent dye releasing compounds: compounds represented by COUP-DYE in claim 1 of US 4,774,181 (especially column 7)
10 to compounds 1 to 11); development accelerator or fogging agent releasing compounds: compounds represented by formulas (1), (2) and (3) of column 3, US Pat. No. 4,656,123 (particularly (I-22 of column 25) ) And EP 450,63
7A2, ExZK-2, page 75, lines 36-38; compounds that release a dye group only after elimination: a compound of formula (I) in claim 1 of US 4,857,447 (especially Y- in columns 25-36). 1-Y
-19).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3, 5, JP-A-62-215272
16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93
(Pages 140-144); Latex for impregnation of oil-soluble organic compounds: U
Latex described in S 4,199,363; Oxidized developer scavenger: US Pat. No. 4,978,606, column 2, lines 54 to 62, formula (I)
A compound represented by the formula (especially I-, (1), (2), (6), (12) (columns 4 to 5), a formula of column 5, lines 5 to 10 of US 4,923,787 (especially compound 1 (column 3) ); Stain inhibitors: Formulas (I) to (III) on page 4, lines 30 to 33 of EP 298321A, especially I-47, 72, III-1, 27.
(Pages 24-48); Anti-fading agent: EP 298321A, A-6, 7, 20, 21,
23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 9
4, 164 (pages 69-118), US 5,122,444 columns 25-38 II-1
~ III-23, especially III-10, EP 471347A, pages 8-12, I-1 ~ I
II-4, especially II-2, US 5,139,931 columns 32-40 A-1-4
8, especially A-39, 42; Materials that reduce the amount of color-enhancing agent or color-mixing inhibitor used: I-1 to II- on pages 5 to 24 of EP 411324A
15, especially I-46; formalin scavenger: EP 477932A
24 to 29, SCV-1 to 28, especially SCV-8; Hardener: JP-A-1-
214845, page 17, H-1, 4, 6, 8, 14, US 4,618,573, columns 13 to 23, compounds represented by formulas (VII) to (XII) (H-1 to 5
4), compounds (H-1 to 76) represented by the formula (6) on the lower right side of page 8 of JP-A-2-214852, particularly compounds described in claim 1 of H-14, US 3,325,287; development inhibitor precursor: JP 62-16813
9 P-24, 37, 39 (pages 6-7); Compounds as claimed in claim 1 of US 5,019,492, in particular column 7 28-29; preservatives, fungicides: US 4,923,790 columns 3-15 I. -1 to III-43, especially II-1, 9, 10, 18, III-25; Stabilizer, antifoggant: U
S 4,923,793 columns 6-16 I-1 ~ (14), especially I-1, 60,
(2), (13), US 4,952,483 columns 25-32 compounds 1-6
5, especially 36: chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: JP-A-3-156
450 pages 15-18 a-1 to b-20, especially a-1, 12, 18, 27, 35,
36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, EP 445627A
FI-1 to F-II-43 on pages 33 to 55, especially FI-11, F-II-8, EP 45
7153A, pages 17-28, III-1 to 36, especially III-1, 3, W088 / 047
94, 8 to 26, Dye-1 to 124, microcrystalline dispersion, EP 319999A, pages 6 to 11, compounds 1 to 22, especially compound 1, EP 519306A formula
Compounds D-1 to 87 represented by (1) to (3) (pages 3-28), US
Compounds 1 to 22 (columns 3 to 10) represented by formula (I) of 4,268,622, compound (1) represented by formula (I) of US 4,923,788
To (31) (columns 2 to 9); UV absorber: compounds (18b) to (18r), 101 to 427 (6 to 6) represented by formula (1) of JP-A-46-3335.
Page 9), compounds (3) to (6) represented by formula (I) of EP 520938A.
6) (pages 10-44) and compounds of formula (III) HBT-1-10
(Page 14), compounds (1) to (3 represented by formula (1) of EP 521823A.
1) (columns 2-9).

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and 16 μm or less. Particularly preferred. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. It is defined as
The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is A. Green et al.'S Photographic Science and Engineering. (Photogr. Sci. Eng), Vol. 19, 2, 124-129. It can be measured by using a swellometer of the type described. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling ratio is
150 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) /
It can be calculated by the film thickness.

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

The support which can be used in the silver halide light-sensitive material of the present invention includes a glass plate, paper (paper obtained by laminating neutral paper or acid paper with a resin such as polyethylene or polyester, baryta paper, polypropylene paper). Etc.), plastic films or sheets (polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, polyesters such as cellulose triacetate and cellulose nitrate; resins such as polyvinyl chloride), etc.
Any transparent, semi-transparent, or reflective support can be used as long as it can be coated with the hydrophilic colloid layer.

[0158]

【Example】

Example 1 An undercoated polyethylene terephthalate film support (having a thickness of 120 μm and having a resin layer containing carbon fine particles coated on the side opposite to the emulsion surface so as to have a transmission density of 1.0) was prepared as follows. Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g
/ M ² ). The silver halide emulsion represents the coating amount in terms of silver halide.

First Layer (Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (amorphous bulk, average halogen composition I / Br = 1 mol% / 99 mol%, gold-sulfur sensitized emulsion B1 having an average grain size of 0.7 μm) And 0.4 μm gold-sulfur sensitized emulsion B2 1: 7 mixture (molar ratio of silver). 0.50 gelatin 1.66 yellow coupler (ExY) 1.10 solvent (Solv-1) 0.13 solvent (Solv) -2) 0.13 (Cpd-1) 0.0016 (Cpd-2) 0.0006 (Cpd-3) 0.006 (Cpd-4) 0.03 Second layer (color mixing prevention layer) Gelatin 0.40 (Cpd-5) 0.03 Solvent (Solv-3) 0.03 Solvent (Solv-4) 0.03

Third Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 25 mol% / 75 mol%, gold-sulfur sensitized emulsions R1 and 0 having an average grain size of 0.25 μm) 0.1 μm gold-sulfur 1: 3 mixture of silver sensitized emulsion R2 (silver molar ratio) 0.44 Gelatin 2.12. Cyan coupler (ExC) 0.97 (Cpd-6) 0.18 (Cpd-5) 0 .015 Solvent (Solv-5) 0.50 Solvent (Solv-6) 0.32 (Cpd-7) 0.0002 (Cpd-8) 0.003 (Cpd-2) 0.003 Fourth layer (preventing color mixture) Layer) Gelatin 0.40 (Cpd-5) 0.03 Solvent (Solv-3) 0.03 Solvent (Solv-4) 0.03 Fifth layer (low sensitivity green sensitive emulsion layer) Silver chlorobromide emulsion (cube) , Average halogen composition Br / Cl = 25 % / 75 mol%, gold-sulfur sensitized emulsion having an average grain size of 0.18 μm.) 0.39 Gelatin 1.04 Magenta coupler (ExM) 0.49 (Cpd-9) 0.001 (Cpd-5) 0 .010 Solvent (Solv-3) 0.12 (Cpd-10) 0.001 (Cpd-11) 0.002 (Cpd-12) 0.002 Sixth layer (high-sensitivity green-sensitive emulsion layer) Silver chlorobromide Emulsion (cubic, average halogen composition Br / Cl = 25 mol% / 75 mol%, gold-sulfur sensitized emulsion having an average grain size of 0.18 μm) 0.13 gelatin 0.25 magenta coupler (ExM) 0.12 (Cpd -9) 0.001 (Cpd-5) 0.010 Solvent (Solv-3) 0.03 (Cpd-10) 0.001 (Cpd-11) 0.001 (Cpd-12) 0.001 Seventh Shows a (protective layer) Gelatin 0.98 Polyvinyl alcohol acrylic modified copolymer 0.05 (metamorphic degree 17%) compound used herein liquid paraffin 0.02 below.

[0161]

[Chemical 51]

[0162]

Embedded image

[0163]

Embedded image

[0164]

[Chemical 54]

[0165]

[Chemical 55]

[0166]

[Chemical 56]

As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. To prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer.

[0168]

[Chemical 57]

Then, the compound of the general formula (I) (II-3,
III-4, V-1, V-4) were used to prepare solid fine particle dispersions dispersed by the dispersion methods shown in A to D below. Next, using these dispersions, a solid fine particle dispersion-containing coating liquid was prepared by the following method. Tables 1-1 and 1-2 show a list of the coating liquids containing the solid fine particle dispersion thus produced.

[0170]

[Table 5]

[0171]

[Table 6]

<Preparation Method of Solid Fine Particle Dispersion> Dispersion Method: Dispersion Method A: The total amount is adjusted while adjusting the pH so that pH = 6.2 by adding 48 g of the dispersion aid to 240 g of the compound of the general formula (I). After adding water to 4000 g, add 1.7 L of zirconia beads (0.5 mm), and use a flow type sand grinder mill (UVM-2) (made by AIMEX KK) to discharge L / min and It was crushed for 2 hours at a speed of 10 m / s. Then, it was diluted so that the sample concentration was 3 wt%.

This dispersion was heat-treated at 30 ° C. for 10 hours. B: The heat treatment temperature of the dispersion prepared as in A was 5
The temperature is 0 ° C. C: The heat treatment temperature of the dispersion prepared as in A above was 9
The temperature is 0 ° C. D: Prepared in the same manner except that the pH during the heat treatment in B above was 4.3.

<Preparation of coating liquid containing solid fine particle dispersion> 180 g of gelatin was dissolved in 1600 cc of water at 50 ° C. After setting the temperature of this gelatin aqueous solution to the temperatures shown in Table 1-1 and Table 1-2, the compounds shown in Table 1-1 and Table 1-2, the dispersion aid, and the solid fine particle dispersion 8 prepared by the above dispersion method
00 g and 0.7 g of the additive (P-2) were added and well stirred.

The temperature and pH at this time are shown in Table 1-1 and Table 1-
It was prepared while controlling so as to have the value shown in 2.
Next, with respect to Sample 101, the resin layer on the back surface of the support was removed, and instead of the conductive polymer (0.0
5 g / m ²⁾ and provided with a hydrophilic colloid layer containing tin oxide fine particles (0.23g / m ^2), Table 1-1 and Table 1-
2. Coating liquids 1 to 31 for a solid fine particle dispersion-containing layer according to 2,
A solid fine particle dispersion of the following composition (number is coating amount: g / m ² ) is newly added between the surface of the support and the first layer by using the coating liquid after leaving it in a dissolved state at 40 ° C. for 6 hours. Samples 102 to 132 (coating liquids 1 to 3) which differ only in that a containing layer is provided
1 immediately after preparation) and samples 102M-132M
(Using the coating liquids 1 to 31 left in a dissolved state at 40 ° C. for 6 hours as described above) were prepared as shown in Table 2-1 and Table 2-2.

[0176]

Embedded image

(Layer containing solid fine particle dispersion) Gelatin 1.03 Solid fine particle dispersion (as solid content) 0.204 Additive (P-2) 0.005

[0178]

[Table 7]

[0179]

[Table 8]

Samples prepared as described above (size,
A sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K) was used for 70 × 150 mm), and uniform exposure was performed through a color filter so as to give a gray color. At this time, the exposure time was 1 second and the exposure amount was 500 CMS. The exposed sample was processed according to the ECP-2B process published by Eastman Kodak Company and then evaluated as follows. (Evaluation of uniformity of coating surface) ・ Density of density due to coating unevenness: 35 × 15 mm for the above sample
It is divided into 20 equal parts and the central part of them is divided into X-RITE 31
The density was measured at 20 points for each sample with 0 (manufactured by X-RITE), and the difference between the maximum value and the minimum value of the gray density was taken. The smaller this value is, the less coating unevenness is, which is preferable. -Lines parallel to the coating direction: The number of lines parallel to the coating direction found in the above sample was visually counted. The smaller this value is, the less streaks are preferable.

The results of coating surface uniformity evaluation are shown in Table 2-1. (Evaluation of Membrane Strength) After incising the treated sample in parallel with a cutter knife, parallel incisions were also made in a direction perpendicular to the incision. That is, the notches were made in the lattice pattern. Polyester adhesive tape No. 31 (manufactured by Nitto Denko Corporation) was attached to the sample thus cut so as to prevent air from entering, and the adhesive tape was peeled off. At this time, the ratio of the peeling area of the coating film from the base to the area of the coating film on the adhesive tape (%: this value is 0
The closer it is, the stronger the film strength).

The results of the film strength evaluation are shown in Table 2-2. As shown in Tables 2-1 and 2-2, compared with Comparative Samples 102 to 104, the solid fine particle dispersion of the dye was heated at the temperature of the present invention as in Comparative Samples 105 to 107, so that the parallel to the coating direction. There is a tendency for the generation of lines to decrease,
It was not sufficient, and the film strength of the coating material after being left in a dissolved state of the coating solution was not improved.

However, when the samples 108 to 111 of the present invention were examined, the uniformity of the coated surface was improved, and, surprisingly, the film strength of the coated product after being left in the dissolved state of the coating liquid was improved. Such improvement in film strength was completely unexpected. Further, in Samples 113 and 114 in which the compound of the present invention is used as the dispersion aid of the solid fine particle dispersion of the dye in the combination of the present invention, the uniformity of the coated surface is improved, which is preferable.

Further, by further lowering the pH of the coating liquid as in Samples 116 to 118, the film strength of the coated product was improved. Further, in the combination of the present invention, samples 121 to 124 using the solid fine particle dispersion of the dye which is heat-treated under pH 4.5 show that the uniformity of the coated surface is improved and the dissolved state of the coating liquid is improved. The film strength of the coated material after being left for a long time was also improved.

That is, from the results of Table 2-1 and Table 2-2,
It can be seen that the coated product of the present invention has the best coating surface uniformity and film strength.

Example 2 An undercoated polyethylene terephthalate film support (thickness: 120 μm, a resin layer containing carbon fine particles was coated on the side opposite to the emulsion surface so as to have a transmission density of 1.0). Then, each layer having the composition as shown below was applied in multiple layers to prepare a sample 201 which is a multilayer color light-sensitive material. (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g
/ M ² ). The silver halide emulsion represents the coating amount in terms of silver halide.

First Layer (Blue Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 1 mol% / 99 mol%, gold-sulfur sensitized emulsions B1 and 0 having an average grain size of 0.7 μm) 0.4 μm gold-sulfur sensitized emulsion B2 in a 1: 3 mixture (silver molar ratio).) 0.50 gelatin 1.60 yellow coupler (ExY) 1.01 solvent (Solv-3) 0.26 (Cpd-13) ) 0.04 (Cpd-1 ') 0.0016 (Cpd-2) 0.0003 (Cpd-3) 0.002 (Cpd-4) 0.03 Second layer (color mixing prevention layer) Gelatin 0.56 ( Cpd-5) 0.01 Solvent (Solv-1 ') 0.006 Solvent (Solv-3) 0.02 Solvent (Solv-4') 0.0007 Solvent (Solv-5) 0.02

Third Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 25 mol% / 75 mol%, gold-sulfur sensitized emulsions R1 and 0 having an average grain size of 0.25 μm) 0.1 μm gold-sulfur 1: 3 mixture of silver sensitized emulsion R2 (silver molar ratio) 0.44 gelatin 2.55 cyan coupler (ExC ₂ ) 0.87 (Cpd-13) 0.46 (Cpd-5) 0.015 (Cpd-14) 0.10 Solvent (Solv-5) 0.28 Solvent (Solv-1 ′) 0.14 Solvent (Solv-2 ′) 0.14 Solvent (Solv-3) 0.14 ( Cpd-7) 0.0002 (Cpd-8) 0.003 (Cpd-2) 0.003 Fourth layer (color mixing prevention layer) Gelatin 0.56 (Cpd-5) 0.01 Solvent (Solv-1 ') 0.006 solvent (Solv-3) .02 solvent (Solv-4 ′) 0.0007 solvent (Solv-5) 0.02 fifth layer (green sensitive emulsion layer) silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 25 mol% / 75) 0.5% Gelatin 1.29 Magenta coupler (ExM) (Mole%, 1: 3 mixture of gold-sulfur sensitized emulsion G1 having an average grain size of 0.25 μm and 0.1 μm gold-sulfur sensitized emulsion G2). ) 0.61 (Cpd-9) 0.001 (Cpd-5) 0.012 Solvent (Solv-3) 0.15 (Cpd-10) 0.003 (Cpd-11) 0.002 (Cpd-12) 0.003 Sixth layer (protective layer) Gelatin 0.98 Acrylic modified copolymer of polyvinyl alcohol 0.05 (Degree of conversion 17%) Liquid paraffin 0.02 The compounds used here are shown below.

[0189]

Embedded image

[0190]

Embedded image

[0191]

[Chemical formula 61]

[0192]

Embedded image

[0193]

[Chemical formula 63]

[0194]

[Chemical 64]

As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In order to prevent irradiation, the same dye as that in Example 1 was added to the emulsion layer in the same amount.

[0196]

Embedded image

Next, with respect to Sample 201, the resin layer on the back surface of the support was removed, and instead, a hydrophilic colloid layer containing the same conductive polymer and tin oxide fine particles as used in Example 1 was provided. 1 and the coating liquids 1 to 31 for solid fine particle dispersion-containing layer shown in Table 1-2, and the coating liquids after being left in a dissolved state at 40 ° C. for 6 hours, the solid fine particle dispersion-containing layer having the following composition Samples 202 to 232 (used immediately after preparation of coating liquids 1 to 31) (samples: coating amount: g / m ² ) are newly provided between the support surface and the first layer 202M to 232M (using the coating liquids 1 to 35 left in a dissolved state as described above) were prepared in the same manner as in Example 1. (Layer containing solid fine particle dispersion) Gelatin 1.03 Solid fine particle dispersion (as solid content) 0.204 Additive (P-2) 0.005 These samples were also subjected to the same exposure / treatment as in Example 1. When the test (evaluation of uniformity of coated surface / evaluation of film strength) was performed, the same effect as in Example 1 was observed.

Example 3 On a subbed cellulose triacetate film support,
For the first layer, the sixth layer, and the tenth layer, immediately after the solid fine particle dispersion-containing coating liquids A to O shown in Table 3-1 were prepared, they were immediately used as shown in Table 3-2 and as shown below. Sample 3 which is a multilayer color light-sensitive material is obtained by coating each layer having the composition shown below in multiple layers.
01-305 were produced. The dispersion method and the preparation of the coating liquid are the same as in Example 1. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid fine particle dispersion (solid content) (Table 3-2) 0.070 HBS -1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid fine particle dispersion (solid content) (Table 3-2) 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid fine particle dispersion (solid content) (Table 3-2) 0.120 Oil-soluble dye ExF-2 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

Fourteenth layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coatability, W-1 to W-3, B-4 to B- are appropriately added to each layer. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0214]

[Table 9]

In Table 9, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

[0216]

[Chemical formula 66]

[0219]

Embedded image

[0218]

[Chemical 68]

[0219]

[Chemical 69]

[0220]

Embedded image

[0221]

Embedded image

[0222]

Embedded image

[0223]

Embedded image

[0224]

[Chemical 74]

[0225]

[Chemical 75]

[0226]

[Chemical 76]

[0227]

Embedded image

[0228]

Embedded image

[0229]

Embedded image

[0230]

Embedded image

[0231]

[Chemical 81]

The coating liquids A to O containing the solid fine particle dispersion shown in Table 3-1 were left in a dissolved state at 40 ° C. for 6 hours. As shown in Table 3-2, the 1st, 6th and 10th layers were used. Samples 301M to 305M coated with were prepared.

[0233]

[Table 10]

[0234] Example 1
After the same exposure as above, it was processed according to the CN-16FA process published by Fuji Photo Film Co., Ltd.
With respect to these samples, the coated surface uniformity evaluation and the film strength evaluation were performed in the same manner as in Example 1, and the results are shown in Table 3-2 and Table 3-3.

[0235]

[Table 11]

[0236]

[Table 12]

From Tables 3-1 to 3-3, it can be seen that the coated product of the present invention is excellent in both surface uniformity and film strength.

Example 4 A multilayer color light-sensitive material comprising each layer having the following composition using the coating solution containing the solid fine particle dispersion shown in Table 4-1 on a subbed 127 μm thick cellulose triacetate film support. Was prepared as a sample 401. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.90 g UV absorber U-1 0.10 g UV absorber U-3 0.040 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 g Solid fine particle dispersion (solid content) (Table 4-2) 0.10 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling point organic solvent Oil-3 0.10 g Dye D-4 0.80 mg

Third layer: intermediate layer Fine grained silver iodobromide emulsion (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) whose surface and inside are fogged
0.050g Yellow colloidal silver Silver amount 0.030g Gelatin 0.40g

Fourth Layer: Low Sensitivity Red Sensitive Emulsion Layer Emulsion A Silver amount 0.30 g Emulsion B Silver amount 0.20 g Gelatin 0.80 g Coupler C-1 0.15 g Coupler C-2 0.050 g Coupler C-3 0.050 g Coupler C-9 0.050 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High boiling point organic solvent Oil-2 0.10 g Additive P-1 0.10 g

Fifth layer: Medium-sensitive red-sensitive emulsion layer Emulsion B Silver amount 0.20 g Emulsion C Silver amount 0.30 g Gelatin 0.80 g Coupler C-1 0.20 g Coupler C-2 0.050 g Coupler C-3 0.20 g High boiling point organic solvent Oil-2 0.10g Additive P-1 0.10g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.10 g Coupler C-1 0.30 g Coupler C-2 0.10 g Coupler C-3 0.70 g Additive P-1 0.10 g

Seventh layer: intermediate layer Gelatin 0.60 g Additive M-1 0.30 g Color mixing inhibitor Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 5.0 mg High boiling organic solvent Oil -1 0.020 g

Eighth layer: intermediate layer A silver iodobromide emulsion whose surface and inside are fogged (average grain size: 0.06)
μm, coefficient of variation 16%, AgI content 0.3 mol%) Silver amount
0.020g Yellow colloidal silver Silver amount 0.020g Gelatin 1.00g Additive P-1 0.20g Color mixing inhibitor Cpd-A 0.10g Compound Cpd-C 0.10g

Layer 9: Low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.10 g Emulsion F Silver amount 0.20 g Emulsion G Silver amount 0.20 g Gelatin 0.50 g Coupler C-4 0.10 g Coupler C-7 0.050 g Coupler C-8 0.20 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg Compound Cpd-L 0.020 g High boiling point organic solvent Oil-1 0.10 g High boiling point organic Solvent Oil-2 0.10 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.30 g Emulsion H Silver amount 0.10 g Gelatin 0.60 g Coupler C-4 0.10 g Coupler C-7 0.20 g Coupler C-8 0.10 g Compound Cpd-B 0.030g Compound Cpd-D 0.020g Compound Cpd-E 0.020g Compound Cpd-F 0.050g Compound Cpd-L 0.050g High boiling organic solvent Oil-2 0.010g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.50 g Gelatin 1.00 g Coupler C-4 0.30 g Coupler C-7 0.10 g Coupler C-8 0.10 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg Compound Cpd-L 0.020 g High boiling point organic solvent Oil-1 0.020 g High boiling point organic solvent Oil-2 0.020 g

Twelfth layer: intermediate layer Gelatin 0.60 g Compound Cpd-L 0.050 g High boiling point organic solvent Oil-1 0.050 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.070 g Gelatin 1.10 g Anti-color mixing agent Cpd-A 0.010 g Compound Cpd-L 0.010 g High boiling point organic solvent Oil-1 0.010 g Solid fine particle dispersion (solid content) ) (Table 4-2) 0.050 g

14th layer: intermediate layer 0.60 g of gelatin

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.20 g Emulsion K Silver amount 0.30 g Gelatin 0.80 g Coupler C-5 0.20 g Coupler C-6 0.10 g Coupler C-10 0.40 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.30 g Emulsion M Silver amount 0.30 g Gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g

Layer 17: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.20 g Emulsion O Silver amount 0.20 g Gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g High boiling organic solvent Oil-2 0.10g

Eighteenth layer: First protective layer Gelatin 0.70 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30 g Formalin scavenger Cpd-H 0.40 g Dye D-1 0.15 g Dye D-2 0.050g Dye D-3 0.10g

Layer 19: Second protective layer Colloidal silver Silver amount 0.10 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1
Mol%) Silver amount 0.10 g Gelatin 0.40 g

20th layer: 3rd protective layer Gelatin 0.40 g Polymethyl methacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.10 g Silicone oil 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0260]

[Table 13]

[0261]

[Table 14]

[0262]

[Table 15]

[0263]

[Chemical formula 82]

[0264]

[Chemical 83]

[0265]

[Chemical 84]

[0266]

Embedded image

[0267]

[Chemical 86]

[0268]

[Chemical 87]

[0269]

Embedded image

[0270]

[Chemical 89]

[0271]

[Chemical 90]

[0272]

Embedded image

[0273]

Embedded image

[0274]

Embedded image

[0275]

Embedded image

[0276]

Embedded image

In coating the first and thirteenth layers, Table 4-
Immediately after preparing the solid fine particle dispersion-containing coating liquids a to l shown in No. 1, the samples 401 to 401 were used as shown in Table 4-2.
406 was produced. In addition, similarly, the coating liquids a to l are 40 ° C.
Samples 401M to 406M were prepared as shown in Table 4-2 after being left in a dissolved state for 6 hours. The dispersion method and the coating solution preparation method are the same as in Example 1.

[0278]

[Table 16]

[0279] Next, the sample prepared as described above was left unexposed and the CR image was published by Fuji Photo Film Co., Ltd.
Processed according to the -56 process. With respect to these samples, the coated surface uniformity evaluation and the film strength evaluation were performed in the same manner as in Example 1, and the results are shown in Table 4-2 and Table 4-3.

[0280]

[Table 17]

[0281]

[Table 18]

From Tables 4-1 to 4-3, it can be seen that the coating material of the present invention is excellent in both uniformity and film strength.

[0283]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which is excellent in the uniformity of the coated surface and excellent in the film strength of the coating material regardless of whether the coating solution is left in a dissolved state.

Claims (5)

[Claims] 1. A photographic light-sensitive material obtained by coating a support with a photosensitive hydrophilic colloid layer coating solution containing a photosensitive silver halide emulsion and a non-photosensitive hydrophilic colloid layer coating solution. The coating liquid for the photosensitive or non-photosensitive hydrophilic colloid layer contains at least one solid fine particle dispersion of a compound represented by the following general formula (I), and at least one of the solid fine particle dispersion is 40 ° C. or higher. A silver halide photographic light-sensitive material, which is a dispersion which has been subjected to the heat treatment step of 1. and has a pH of 6.5 or less for preparing a coating liquid for a hydrophilic colloid layer containing the solid fine particle dispersion. Embedded image (In the formula, D represents a compound having a chromophore, X represents a dissociative hydrogen bonded to D directly or via a divalent linking group or a group having a dissociative hydrogen, and y is an integer of 1 to 7. Represents.) 2. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the compounds of the general formula (I) is a compound represented by the following general formula (II) or (III). Embedded image (In the general formula (II), A ¹ represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, L ¹ , L ² and L ³ each represent a methine group, and m represents 0, 1 or 2. However, the compound represented by the general formula (II) has a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group and an enol group of an oxonol dye as a water-soluble group in the molecule. 1 to 7 groups selected from the group consisting of). (In the general formula (III), A ¹ and A ² represent acidic nuclei, L ¹ ,
L ² and L ³ each represent a methine group, and n represents 0, 1, 2 or 3. However, the compound of the general formula (III) is composed of a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group and an enol group of an oxonol dye as a water-soluble group in the molecule. It has 1 to 7 groups selected from the group. ) 3. At least one kind of solid fine particle dispersion subjected to the heat treatment is represented by the following general formula (IV-a) or (IV-
3. The silver halide photographic light-sensitive material according to claim 1, which contains the compound represented by b). [Chemical 4] Embedded image (In the general formulas (IV-a) and (IV-b), a and b each independently represent a value of 5 to 500.) 4. The pH of the heat treatment step of the solid fine particle dispersion is
The silver halide photographic light-sensitive material according to claim 1, 2 or 3, which is performed at 6.5 or less. 5. The heat treatment step of the solid fine particle dispersion is pH.
The silver halide photographic light-sensitive material according to claim 4, which is performed at less than 4.5.