JPH04324442A - Photographic hydrophilic colloidal composition and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the dispersion stability of a hydrophilic colloidal compsn. contg. a photographically useful compd. by mixing a dispersion of the photographically useful compd. prepd. in the presence of a specified compd. with a hydrophilic colloidal dispersion in the presence of a specified surfactant. CONSTITUTION:A dispersion of a hydrophobic photographically useful compd. prepd. in the presence of at least one kind of compd. represented by formula I is mixed with a hydrophilic colloidal dispersion in the presence of a surfactant contg. at least one among a polyoxyethylene group, a polyglycerol group and a polyol residue to obtain a hydrophilic colloidal compsn. In the formula I, each of R1 and R2 is H or hydrocarbon, at least one of R1 and R2 is >=6C hydrocarbon, each of L1 and L2 is a divalent combining group, L1 and L2 may be different from each other and M is H or a cationic group. The hydrophobic photographically useful compd. is a coupler, a filter dye, a UV absorber, etc. The photographic characteristics of a silver halide photographic sensitive material can be improved by using the colloidal compsn.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersion stabilizer, a hydrophilic colloid composition, and a photographic material containing the hydrophilic colloid, which are suitable for producing photographic materials.

0002

[Prior Art] Conventionally, many photographically useful compounds, that is, organic compounds that exhibit photographic properties, have been used in photographic light-sensitive materials, and many of them are hydrophobic (hereinafter referred to as hydrophobic organic compounds). . These organic compounds that are insoluble or sparingly soluble in water include couplers for color photography, dyes for filters, ultraviolet absorbers, antifoggants, and various development control agents. These compounds can be added to the photographic constituent layer in the form of an aqueous solution by imparting hydrophilic properties;
It is more usual to disperse and use a hydrophobic compound. Furthermore, recent photographic materials are composed of many constituent layers, and each constituent layer functions independently or in conjunction with each other, resulting in significant improvements in photographic properties. Therefore, it is desirable that the above-mentioned compound has appropriate hydrophobicity and is immobilized in a specific layer.

Conventionally, these hydrophobic organic compounds have been added to photographic layers by various methods. The main methods are as follows.

[0004] A method in which a hydrophobic organic compound is directly dissolved or dispersed in a hydrophilic colloid layer, or a method in which the hydrophobic organic compound is dissolved or dispersed in an aqueous solution or solvent and then used in an emulsion layer or a hydrophilic colloid layer, a suitable solvent, For example, methyl alcohol, ethyl alcohol, propyl alcohol,
Methyl cell solve, halogenated alcohol, acetone, methyl ethyl ketone, water, pyridine, etc., or a mixed solvent thereof, as described in JP-A No. 48-9715 and U.S. Patent No. 3,756,830. It can also be added in the form of In this case, various surfactants can also be included.

(2) A method in which a solution of a compound dissolved in an oil, ie, a substantially water-insoluble high-boiling solvent having a boiling point of 160° C. or higher, is added to a hydrophilic colloid solution for dispersion. This high boiling point solvent may include, for example, phthalic acid alkyl ester (as described in U.S. Pat. No. 2,322,027
For example, dibutyl phthalate, dioctyl phthalate)
, phosphate esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate) , alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate,
diethyl azelate), and trimesic acid esters (eg, tributyl trimesate). Further, organic solvents having a boiling point of about 30°C to about 150°C, such as lower alkyl azelates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. It is also possible to use solvents that are easily soluble in water, such as alcohols such as methanol and ethanol. Here, the ratio of the dye to the high boiling point organic solvent used is preferably 40 to 1/10 (weight ratio).

(2) A method of incorporating the dye of the present invention and other additives into a polymer latex composition filled with a hydrophilic colloid layer. Examples of the polymer latex include polyurethane polymers, polymers polymerized from vinyl monomers [suitable vinyl monomers include acrylic esters (e.g., methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, dodecyl acrylate, glycidyl acrylate). ), alpha-substituted acrylic esters (e.g. methyl methacrylate, butyl methacrylate, octyl methacrylate, glycidyl methacrylate), acrylamides (e.g. butylacrylamide, hexyl acrylamide), alpha-substituted acrylamides (e.g. butyl methacryamide, dibutyl methacryamide) ,
vinyl esters (e.g. vinyl acetate, vinyl butyrate),
Vinyl halides (e.g. vinyl chloride), vinylidene halides (e.g. vinylidene chloride), vinyl ethers (e.g. vinyl methyl ether, vinyl octyl ether), styrene, α-substituted styrene (e.g. α-
methylstyrene), nuclear substituted styrenes (eg hydroxystyrene, chlorostyrene, methylstyrene), ethylene, propylene, butylene, butadiene, acrylonitrile. These may be used alone or in combination of two or more, or may be mixed with other vinyl monomers as a minor component. Other vinyl monomers include, for example, itaconic acid, acrylic acid, methacrylic acid,
Examples include hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate, and styrene sulfonic acid. ] can be used.

[0007] These filled polymer latexes are disclosed in Japanese Patent Publication Nos. 51-39853, 59943/1983,
No. 3-137131, No. 54-32552, No. 54-
No. 107941, No. 55-133465, No. 56-1
No. 9043, No. 56-19047, No. 56-1268
It can be produced according to the method described in No. 30 and No. 58-149038. Here, the usage ratio of the dye and the polymer latex is preferably 40 to 1/10 (weight ratio).

(2) A method of dissolving a compound using a surfactant. Useful surfactants may be oligomeric or polymeric. For more information about this polymer,
Specification No. 19 of Japanese Patent Application No. 59-12766 (filed by Fuji Photo Film Co., Ltd. on January 26, 1988)
It is described on page 27.

(2) A method in which a hydrophilic polymer is used in place of the high-boiling point solvent or in combination with the high-boiling point solvent in (1) above. This method is described, for example, in US Pat. No. 3,619,195 and German Patent No. 1,957,467.

(2) A microcapsule method using a polymer having a carboxyl group, a sulfonic acid group, etc. in the side chain as described in JP-A-59-113434.

[0011] ■ A method as described in WO 88/04797 in which a solid is pulverized and dispersed in a binder. For example, there is a method using a sand mill or a ball mill. Furthermore, a hydrosol of a lipophilic polymer described in Japanese Patent Publication No. 51-39835, for example, may be added to the hydrophilic colloid dispersion obtained above.

However, in the various methods described above, the stability of the dispersion may not be sufficient, which may cause problems in the manufacturing process of photographic light-sensitive materials, or the degree of dispersion may not be sufficient and the desired photographic properties may not be obtained. Sometimes I can't. In addition, many of the above methods use polymeric compounds used as protective colloids,
For example, there was a problem in that the degree of dispersion and stability varied depending on the type and amount of gelatin.

Particularly in recent years, there has been a demand for a significant improvement in the photographic properties of light-sensitive materials, and from the viewpoint of improving sharpness, there has been a demand for thinner layers of light-sensitive materials. In order to make photosensitive materials thinner, it is necessary to stably prepare a dispersion of a hydrophobic photographically useful compound using as little polymeric protective colloid as possible. However, with the above conventional techniques, it is not possible to create a stable dispersion without a protective colloid, and when it is mixed with components containing other protective colloids such as silver halide emulsions, significant thickening and deterioration of the dispersion occur. caused it.

[0014]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a method for producing a stable dispersion of a hydrophobic compound without using a polymeric protective colloid. The second objective is to provide a method for making a dispersion of a hydrophobic compound that is stable when mixed with a polymeric protective colloid, and the third objective is to provide a photosensitive material that can reduce the amount of polymeric protective colloid. It is to provide.

[0015]

[Means for Solving the Problems] The above objects are (1) a hydrophobic photographic material prepared in the presence of at least one compound represented by the following general formula (I), (II) or (III); A compound dispersion is mixed with a hydrophilic colloid dispersion in the presence of a surfactant containing at least one of a polyoxyethylene group, a polyglycerol group, or a polyhydric alcohol residue in the molecule. This was achieved by using a photographic hydrophilic colloid composition. Here general formula (I)

[C4] General formula (II)

[C5] General formula (III)

embedded image The present invention will be described in detail below. Introduction General formula (I)
The compound will be explained in detail.

In general formula (I), R1 and R2
is preferably a saturated hydrocarbon group having 1 to 30 carbon atoms, particularly preferably a linear or branched alkyl group having 6 to 12 carbon atoms. In general formula (I), particularly preferred examples of R1 and R2 include both R1 and R2 having 6 to 6 carbon atoms.
10 alkyl groups, which may be linear or branched. In general formula (I), when R1 and R2 are hydrocarbon groups, examples of substituents that may be substituted include a halogen atom, an alkoxy group, an acyl group, a cyano group, and an aryl group. Preferred examples of divalent groups for L1 and L2 are:

[0017]

[C7]

Further, among these, compounds represented by the general formulas (IA) and (IB) are particularly preferably used.

[0019]

[Chemical formula 8]

[0020]

[Chemical formula 9]

[0021] Preferred specific examples of the compound represented by the general formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0022]

[Chemical formula 10]

[0023]

[Chemical formula 11]

[0024]

[Chemical formula 12]

[0025]

[Chemical formula 13]

These compounds used in the present invention are described in J.
Org. Chem. 26 4112 (1961)
and U.S. Patent Nos. 2,662,073 and 4,892,
Although it can be synthesized according to the method described in the specification of No. 806, a typical synthesis example is shown below.

Synthesis Example 1 (Synthesis of Compound I-1) 2,2-
Synthesis of dihexylpropanedinitrileDry DMSO
66.1 g (1.0 mol) of malononitrile dissolved in 200 ml of dry DMSO was slowly added to a slurry of 800 ml and 36 g (2.0 mol) of sodium hydride while stirring and cooling with water. Stir for 20 minutes after finishing.
minutes, then 330.1 g of hexyl bromide (2.
(0 mol) was added dropwise while cooling with ice (20°C, 1 hour). After the completion of stirring, the mixture was stirred at 30°C or lower for 2 hours and then at 50°C for 4 hours.

The reaction solution was poured into 3000 ml of ice water and stirred. Next, 2000 ml of ethyl acetate was added to extract and separate the oil. The separated ethyl acetate layer was further washed with water for two times.
Repeatedly. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off to obtain a yellow oily substance. The oily substance was distilled under reduced pressure to obtain 181 g of the desired product as a colorless oil. (boiling point 153-159°C/6mmHg).

Synthesis of 2,2-dihexylpropane-1,3 diamino 180.0 g of 2,2-dihexylpropane dinitrile (
0.77 mol) was dissolved in 300 ml of ethanol, about 5 g of Raney nickel (toluene dispersion) was added, and catalytic reduction was performed in an autoclave at 100° C. under a hydrogen pressure of 100 kg/m 2 for 6 hours. The catalyst was removed and ethanol was distilled off to obtain an oily substance. Distill the oily substance under reduced pressure to obtain the target product 1 as a colorless oil.
19g was obtained. (boiling point 153-160℃/7mmHg)
.

2,2-dihexyl-1,3-bis(1-
Synthesis of aminobutanesulfonate (Na) (Compound I
-1) 2,2-dihexyl-1,3-diamine 24.2
g (0.1 mol) is dissolved in 120 ml of toluene, and 27.2 g (0.2 mol) of butane sultone is added dropwise at 60° C. while stirring. Continue stirring at 60°C for 1 hour and at 110°C for 2 hours. Lower the temperature to 50°C and lysium methoxide 10.
Add 38.6 g of 8 g of methanol solution (28%),
Stir for 0 minutes. Next, 800 ml of methanol and 100 ml of ethanol were added, and the insoluble matter dissolved by heating was removed by filtration. After distilling off the solvent and concentrating, about 800 ml of acetonitrile
was added and crystallized to obtain 31 g of the target product. (However, it contained about 10% monosulfonated product).

[0031] Compounds of the general formula (I) used in the present invention other than those in the above synthesis example can also be synthesized in the same manner as in the above synthesis example. For example, the linking group L in general formula (I) is

In the case of [Chemical formula 14], malonic acid, malonic acid methyl ester, and malonic acid chloride are used in place of malononitrile in the above synthesis example, and in addition, alkanesultone, taurine, isethionic acid, aminobenzenesulfonic acid, and hydroxybenzenesulfonic acid are used. It can be synthesized in the same way by reacting.

Next, the compound of general formula (II) will be explained in detail. Preferred examples of R1 and R2 in general formula (II) include R1 and R2 both being an alkyl group having 6 to 16 carbon atoms, and R3 being a hydrogen atom or -(CH2)
nSO3M. Particularly preferably R3 is −(
CH2)nSO3M. Preferred examples of substituted hydrocarbons include -CH2CH2(OCH2CH2)a R
It is 4. R4 is a hydrocarbon group, for example C8
H17, C12H25,

[Image Omitted] etc. a is 1-3. Next, preferred specific examples of the compound represented by the general formula (II) used in the present invention will be shown, but the present invention is not limited thereto.

[0033]

[Chemical formula 16]

[0034]

[Chemical formula 17]

[0035]

[Chemical formula 18]

These compounds used in the present invention are synthesized by reacting tartaric acid with a long-chain alcohol to synthesize a diester, reacting this with sultone or sulfamic acid, and treating with NaOH water to form an alkyl sulfonate. , alkyl tartrate sodium or alkyl tartrate sodium sulfate can be obtained. Next, a synthesis example will be shown.

Synthesis Example 2 (Synthesis of Compound II-1) Tartaric acid 75.05 g (0.5 mol), n-octanol 143
．． 2g (1.1 mol), para-toluenesulfonic acid 4.3
g. Put 100 ml of toluene into a 500 ml three-necked flask and reflux while stirring, and remove the generated water from the system. The reaction became a homogeneous solution in about 30 minutes, and the theoretical amount of water was produced in about 3 hours (about 18.0 ml). Stirring was continued for an additional hour. After cooling, add ethyl acetate to dissolve Na
It was neutralized by stirring with OH water, and the washing with water was repeated. The ethyl acetate layer was taken out and evaporated under reduced pressure to obtain a waxy solid. This product was tartaric acid di-octyl ester, and the purity was 96% by gas chromatography. Further recrystallization resulted in a purity of 99%.

Next, tartrate dioctyl ester 37.4
5g (0.1 mol), 500ml of toluene 100ml
8.8 g of 60% sodium hydride (
0.22 mol) little by little. After stirring at the same temperature for about 30 minutes, 29.9 g (0.2
2 mol) was added dropwise. After the dropwise addition was completed, the mixture was further stirred at 70°C for 2 hours. 500 ml of methanol and 500 ml of ethanol are added to the reaction mixture and dissolved by heating, and insoluble materials are removed by filtration. After the solvent was distilled off and concentrated, the residue was poured into 800 ml of acetonitrile and crystallized to obtain 59.4 g (yield: 87%) of the desired product. Transparently dissolved in water, surface tension (1% aqueous solution) is 28 dyne
/cm. Although the compound represented by the general formula (II) used in the present invention can be synthesized as a single substance by the above-mentioned synthesis method, it is not necessarily necessary to obtain it as a single substance, and even as a mixture, there is no practical problem and, in fact, there is a characteristic of improving performance. Sometimes it happens.

Next, the compound of general formula (III) of the present invention will be explained in detail. R1 in general formula (III)
, R2, R3 are preferable examples, R1, R2
are both alkyl groups having 8 to 16 carbon atoms, and R3 is a hydrogen atom or -(CH2)aSO3M, or R3 is a hydrogen atom or -(CH2)aSO3M, or
1 is a branched alkyl group having 8 to 36 carbon atoms, R2, R
3 is a hydrogen atom or -(CH2)aSO3M. Particularly preferably R3 is -(CH2)aSO3M. A preferred example of the branched alkyl group is a 2-ethylhexyl group or one represented by the following general formula (A).

[0040]

[Chemical formula 19]

Next, general formula (III) used in the present invention
Preferred specific examples of the compounds represented by are shown below, but the present invention is not limited thereto.

[0042]

[C20]

[0043]

[C21]

These compounds used in the present invention are synthesized by reacting an alkyl ether or fatty acid ester produced by the reaction between pentaerythritol and an alkyl halide or by reacting pentaerythritol and a fatty acid with sulfamic acid, and then reacting with sulfamic acid. By treatment, an alkyl sulfonate, alkyl pentaerythritol ether sodium, can be obtained by reacting alkyl pentaerythritol ether sodium sulfate with sultone under base catalysis. Next, a synthesis example will be shown.

Synthesis Example 3 (Synthesis of Compound Example III-1)
27.2g (0.2mol) of pentaerythritol and t-
Pour 500 ml of butyl alcohol into a 1 liter three-necked flask and heat to dissolve. Potassium-t-
After adding and stirring 24.7 g (0.22 mol) of butoxide, 54.8 g (0.22 mol) of dodecyl bromide was added dropwise. After the dropwise addition, the mixture was heated under reflux for 24 hours, and then cooled and the resulting precipitate was filtered. After distilling off the solvent under reduced pressure, the residue was separated into monoalkyl, dialkyl, and trialkyl components using a silica gel column.

30.4 g (0.1 mol) of the obtained mono-dodecyl pentaerythritol ether, 10.7 g (0.11 mol) of sulfamic acid and 200 ml of DMF were mixed into 5
The mixture was placed in a 00ml three-necked flask and reacted at 50°C for 3 hours under a nitrogen stream. After reaction 2N NaOH water 110
ml and stirred to obtain Na salt. After distilling off the solvent under reduced pressure, it was recrystallized from isopropyl alcohol. (Amount obtained, 24
．． 4g (60% yield)).

Synthesis Example 4 (Synthesis of Compound Example III-4)
9.44 g (20 mmol) of di-dodecylpentaerythritol ether synthesized and separated in Synthesis Example 1
, 1.76 g (44 mmol) of NaOH, and 10 ml of toluene were placed in a 100 ml three-necked flask, and the
After stirring at 0°C for 1 hour, 6 g of butane sultone (
44 mmol) is added. 1 hour at 70℃, 1 hour at 80℃
Continue stirring for an hour. Next, 150 ml of methanol and 50 ml of ethanol were added and dissolved by heating, and the insoluble matter was filtered off. After the solvent was distilled off and concentrated, 200 ml of acetonitrile was added to cause crystallization to obtain 11.0 g (yield: 70%) of the target product.

The compound represented by the general formula (I) used in the present invention can be synthesized as a single substance by the above-mentioned synthesis method, but it is not necessarily necessary to obtain it as a single substance, and there is no practical problem in using a mixture, and the performance may be improved. characteristics may be obtained.

The surfactant containing at least one of a polyoxyethylene group, a polyglycerol group, and a polyhydric alcohol residue in the molecule used in the present invention is one that is substantially soluble in water, that is, a hydrophilic interface. It is an activator, and its structure does not matter.

Next, specific examples of the surfactant used in the present invention will be given, but the present invention is not limited thereto.

[0051]

[C22]

[0052]

[C23]

[0053]

[C24]

[0054]

[C25]

In the present invention, hydrophobic photographically useful compounds, that is, hydrophobic organic compounds, include couplers, filter dyes, ultraviolet absorbers, stain inhibitors, dye image stabilizers, antifoggants, stabilizers, etc. These compounds are already known and have been published in Research Disclosure No.
．． 17643, No. 18716, No. 307105
It is stated in the number. Preferred compounds among these compounds are those having a solubility in neutral water of 0.5 or less, and these compounds are referred to as hydrophobic organic compounds in this application.

Particularly preferred compounds among the compounds of the present invention are couplers, specific examples of which are described in Research Disclosure (RD) No. 1, cited above. 17643, VII-C
It is described in the patents listed in ~G.

Examples of yellow couplers include US Pat. No. 3,933,501, US Pat. No. 4,022,620, US Pat.
No. 4,248,961, Special Publication No. 58-1073
9, British Patent No. 1,425,020, British Patent No. 1,47
6,760, US Pat. No. 3,973,968, US Pat. No. 4,314,023, US Pat. No. 4,511,649, European Patent No. 249,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and are described in US Pat. No. 4,310,619, US Pat. No. 3,061,
No. 432, No. 3,725,067, Research Disclosure No. 24220 (June 1984),
Japanese Patent Publication No. 60-33552, Research Disclosure No. 24230 (June 1984), Japanese Patent Application Publication No. 1986
-43659, 61-72238, 60-35
No. 730, No. 55-118034, No. 60-1859
No. 51, U.S. Patent No. 4,500,630, U.S. Patent No. 4,5
Particularly preferred are those described in No. 40,654, No. 4,556,630, International Publication No. WO88/04795, and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2
, No. 369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308 ,
4,334,011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 1
No. 21,365A, No. 249,453A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,999,
Same No. 4,775,616, Same No. 4,451,559, Same No. 4,427,767, Same No. 4,690,889
No. 4,254,212, No. 4,296,19
No. 9, JP-A No. 61-42658, etc. are preferred. Furthermore, JP-A-64-553, JP-A No. 64-554
No. 64-555, No. 64-556, and U.S. Patent No. 4,818,6
The imidazole couplers described in No. 72 can also be used.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820;
, No. 211, No. 4,367,282, No. 4,40
No. 9,320, No. 4,576,910, British Patent 2
, No. 102,137, European Patent No. 341,188A, etc.

Examples of couplers in which coloring dyes have appropriate diffusivity include US Pat. , 234,533 is preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No.
．． Section VII-G of 17643, No. 307105
Section VII-G of U.S. Patent No. 4,163,670;
Special Publication No. 57-39413, U.S. Patent No. 4,004,9
No. 29, No. 4,138,258, British Patent No. 1,1
46,368 is preferred. In addition, couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774,181 and reacting with developing agents as described in U.S. Pat. No. 4,777,120 are also available. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds which release photographically useful residues upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the RD1 described above.
7643, Section VII-F and No. 307105,
Patent listed in Section VII-F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4,248,962, U.S. Patent No. 4,782,01
The one described in No. 2 is preferred.

RD No. 11449, 24241, JP-A-61-201247, etc., the bleach accelerator-releasing couplers described in JP-A No. 61-201247 are effective for shortening the time of the processing step with bleaching ability, and are particularly effective for reducing the time required for processing steps with bleaching ability, and are particularly effective for reducing the time required for the treatment process with bleaching ability. The effect is great when it is added to a photosensitive material that uses .

As a coupler that releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,097
, No. 140, No. 2,131,188, JP-A-59-
Those described in No. 157638 and No. 59-170840 are preferred. Also, JP-A-60-107029, JP-A No. 60-107029,
No. 0-252340, Japanese Patent Application Publication No. 1-44940, 1-
Compounds that release fogging agents, development accelerators, silver halide solvents, etc. through redox reactions with oxidized developing agents described in No. 45687 are also preferred.

Other compounds that can be used in the photosensitive material of the present invention include US Pat. No. 4,130,427.
Competitive coupler described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
Multi-equivalent coupler described in No. 618 etc., JP-A-60-18
DI described in No. 5950, JP-A No. 62-24252, etc.
R redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers that release dyes that recolor after separation as described in EP 173,302A and EP 313,308A. , U.S. Patent No. 4
, 555, 477, etc.;
Couplers that emit leuco dyes as described in JP-A-63-75747, couplers that emit fluorescent dyes as described in U.S. Pat. No. 4,774,181, and the like.

In the present invention, there are a number of methods for preparing the aqueous dispersion of the hydrophobic photographically useful compound, ie, the hydrophobic organic compound. That is, the known methods (1) to (2) described in the prior art can be applied to the general formulas (I) to (2) of the present invention.
An aqueous dispersion can be prepared by carrying out the reaction in the presence of at least one of the compounds (III).

When preparing an aqueous dispersion, a method that does not use a polymeric protective colloid is preferred, and a more preferred method is a method that does not use both a polymeric protective colloid and a high-boiling point organic solvent.

[0069] 1 of the preferred methods for making the aqueous dispersion of the present invention
For example, a hydrophobic organic compound is dissolved in an organic solvent that is miscible with water, and this organic solvent solution and the general formulas (I) to (
This is a method of mixing the compound III) with an aqueous solution of the compound. At this time, it is effective to add an aqueous solution of a compound of general formulas (I) to (III) to the organic solvent solution;
The reverse addition method may be used depending on how the compounds I) to (III) and the hydrophobic organic compound are selected. The rate of addition of the aqueous solution when adding the aqueous solution to the organic solvent liquid is preferably from 1/100 to 1/100 of the total amount of the organic solvent liquid per minute. In the case of the reverse addition method, the addition rate of the organic solvent liquid is preferably 1/50 to 2 of the total amount of the organic solvent liquid per minute.

The compounds of general formulas (I) to (III) may be used by being dissolved in an organic solvent together with a hydrophobic organic compound instead of being made into an aqueous solution, or may be used by partially dissolving them in an organic solvent. Good too.

The hydrophobic organic compound used in preparing the photographic hydrophilic colloid composition of the present invention and the general formulas (I) to (
The ratio of compounds of general formulas (I) to (III)
) The amount of the hydrophobic organic compound is 0.01 to 100, preferably 0.1 to 40, per 1.0 of the weight of the compound. The concentration of the hydrophobic organic compound is in a weight ratio of 0.1 to 20, preferably 0.5 to 10, relative to the hydrophilic colloid composition.

[0072] As the organic solvent for dissolving the hydrophobic organic solvent, any organic solvent that is miscible with water can be used. Specific examples include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, dimethylformamide, dioxane, tetrahydrofuran,
Acetone, diacetone alcohol, acetonitrile, N
-Methyl-2-pyrrolidone, ethylene glycol, ethylene glycol monobutyl ether, etc. Excess organic solvent can be removed from the hydrophilic colloid composition of the present invention by a known method. The methods used are all known, such as methods using anti-permeable membranes or reverse osmosis membranes;
Examples include methods using reduced pressure and heating.

When the aqueous dispersion described above is mixed with a dispersion solution containing a hydrophilic colloid such as gelatin having a function as a binder or a hydrophilic colloid such as a silver halide emulsion, it is necessary to incorporate polyamide into the molecules of the present invention. Hydrophilic colloid compositions of hydrophobic photographically useful compounds can be prepared by using surfactants containing at least one of oxyethylene groups, polyglycerol groups, and polyhydric alcohol residues.

These surfactants prevent the stability of the aqueous dispersion from being impaired or a significant increase in viscosity occurring when the aqueous dispersion is mixed with a hydrophilic colloid solution such as gelatin. It was found that it can be prevented.

[0075] These molecules contain polyoxyethylene groups,
The surfactant containing at least one of a polyglycerol group and a polyhydric alcohol residue may be added to the aqueous dispersion described above, or may be added to other hydrophilic colloids to be mixed with the aqueous dispersion. . It may also be added independently as an aqueous solution. The amount of these surfactants used is 0.001 to 10, preferably 0.0 in weight ratio to the hydrophobic organic compound.
1-1. For example, it is advantageous to use gelatin as the polymeric protective colloid that functions as a binder, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives. ; Various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc.; can be used.

In addition to lime-processed gelatin, acid-processed gelatin, the Journal of the Photographic Society, Japan (Bull
．． Soc. Sci. Photo. Japan)
No. 16, p. 30 (1966) may be used, and hydrolyzed gelatin and oxygen-decomposed products of gelatin may also be used. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. The amount of water as a dispersion medium in the photographic hydrophilic colloid composition of the present invention is not particularly different from the usual amount. The photographically useful compound can be used in an amount of 0.2 to 20% by weight based on water.

The hydrophilic colloid composition of the present invention is preferably used in photographic materials. The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layer. Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

[0079] The intermediate layer includes JP-A-61-43748, JP-A-59-113438, JP-A-59-113440,
It may contain couplers, DIR compounds, etc. as described in JP 61-20037 and JP 61-20038, and may also contain a commonly used color mixing inhibitor.

The plurality of halogen silver emulsion layers constituting each unit photosensitive layer are a high-speed emulsion layer and a low-speed emulsion layer, as described in German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration of layers can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
As described in JP-A Nos. 57-112751, 62-200350, 62-206541, and 62-206543, there is a low-sensitivity emulsion layer on the side away from the support, and a side close to the support. A high-sensitivity emulsion layer may be provided.

As a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL)/high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL
)/High-sensitivity red-sensitive layer (RH)/Low-sensitivity red-sensitive layer (R
L) or BH/BL/GL/GH/RH/RL
or in the order of BH/BL/GH/GL/RL/RH.

Alternatively, as described in Japanese Patent Publication No. 55-34932, the layers may be arranged in the order of blue-sensitive layer/GH/RH/GL/RL from the side farthest from the support. Also, JP-A-56-25738 and JP-A No. 62-6393
As described in No. 6, the layers may be arranged in the order of blue-sensitive layer/GL/RL/GH/RH from the side farthest from the support.

Further, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer with a lower sensitivity than the middle layer. In addition, a silver halide emulsion layer having a lower photosensitivity is arranged, and the photosensitivity is successively lowered toward the support. Even in a case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, medium-sensitivity emulsion is added from the side remote from the support in the same color-sensitive layer. The layers may be arranged in the following order: layer/high-speed emulsion layer/low-speed emulsion layer. In addition, they may be arranged in the following order: high-sensitivity emulsion layer/low-sensitivity emulsion layer/medium-sensitivity emulsion layer or low-sensitivity emulsion layer/middle-sensitivity emulsion layer/high-sensitivity emulsion layer. Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat.
, No. 663,271, No. 4,705,744, No. 4,707,436, JP-A-62-160448,
BL, GL, as described in the specification of No. 63-89580,
It is preferable that a multilayer effect donor layer (CL) having a different spectral sensitivity distribution from the main photosensitive layer such as RL is arranged adjacent to or close to the main photosensitive layer. As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred amount of silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides: Particularly preferred is about 2 mol%.
silver iodobromide or silver iodochlorobromide containing up to about 10 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubic, octahedral, and tetradecahedral, those with irregular crystal shapes such as spherical and plate shapes, and those with irregular crystal shapes such as spherical and plate shapes. It may be one having crystal defects such as crystal planes, 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 with a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) No.
．． 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types)” and the same No. 187
16 (November 1979), page 648, same No. 307
105 (November 1989), pp. 863-865, “Physics and Chemistry of Photography” by Grafkide, published by Paul Montell (
P. Glafkides, Chemie et Ph
isique Photographique, Pa
ul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.F.D.
uffin, Photographic Emuls
ion Chemistry (Focal Press
, 1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V. L. Zeli).
kman et al. , Making and C
oating Photographic Emuls
ion, Focal Press, 1964).

[0088] US Patent No. 3,574,628, US Patent No. 3,
Also preferred are monodisperse emulsions such as those described in No. 655,394 and British Patent No. 1,413,748. Tabular grains having aspect ratios of about 3 or greater can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering by Guto
ff, Photographic Science
and Engineering), Volume 14, 248
~257 pages (1970); U.S. Patent No. 4,434,2
No. 26, No. 4,414,310, No. 4,433,04
No. 8, No. 4,439,520 and British Patent No. 2,11
It can be easily prepared by the method described in, for example, No. 2,157.

The crystal structure may be uniform, the inside and outside may have different halide compositions, it may be a layered structure, or silver halides of different compositions may be bonded by epitaxial bonding. You can also
Further, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used.

The above-mentioned emulsion may be of a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grains, or a type in which a latent image is formed both on the surface and inside the grains. type emulsion. Among the internal latent image types, the core/
It may also be a shell-type internal latent image type emulsion. The method for preparing this core/shell type internal latent image type emulsion was disclosed in Japanese Patent Application Laid-Open No. 59-13
It is described in No. 3542. The thickness of the shell of this emulsion varies depending on the development process, etc., but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are listed in the aforementioned Research Disclosure No. 17643, same No. 18716 and the same No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two types of light-sensitive silver halide emulsions having different characteristics in at least one of grain size, grain size distribution, halogen composition, grain shape, and sensitivity are mixed in the same layer. can be used.

Silver halide grains covered with grain surfaces as described in US Pat. No. 4,082,553, US Pat.
, 626,498, and JP-A-59-214852, silver halide grains whose interiors are covered with colloidal silver are coated with a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid. It can be preferably used for layers. Silver halide grains whose interior or surface is covered are silver halide grains that can be developed uniformly (in a non-imagewise manner) regardless of whether the exposed or unexposed areas of the photosensitive material are exposed. . A method for preparing silver halide grains in which the inside or surface of the grains is covered is described in U.S. Pat. No. 4,626,498 and JP-A-59
-214852.

The silver halides forming the inner core of the core/shell type silver halide grains whose interiors are fogged may have the same halogen composition or may have different halogen compositions. As the silver halide coated inside or on the surface of the grain, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.7.
5 μm, especially 0.05 to 0.6 μm is preferred. Also,
There are no particular limitations on the grain shape; regular grains may be used, or polydisperse emulsions may be used; however, monodisperse grains (at least 95% of the weight or number of silver halide grains are within ±40% of the average grain size) It is preferable that the particles have a particle size of .

[0094] In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is a silver halide fine grain that is not exposed to light during imagewise exposure to obtain a dye image and is not substantially developed during the development process, and is preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains is
There is no need for optical sensitization and no spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or zinc compound. This layer containing fine silver halide grains can preferably contain colloidal silver. The coating silver amount of the photosensitive material of the present invention is preferably 6.0 g/m2 or less, and 4.5 g/m2 or less.
g/m2 or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below. Additive type 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 23-24 Page 648 Right column
Pages 866-868 Supersensitizer
~ Page 649 Right column 4 Brightener Page 24
Page 647 right column 86
Page 8 5 Antifoggant, pages 24-25
Page 649 Right column Pages 868-870 Stabilizer 6 Light absorber, Pages 25-26
Page 649 right column to page 873
filter dye,
Page 650 left column Ultraviolet absorber 7 Stain inhibitor Page 25 right column
Page 650 left column Page 872

~Right column 8 Dye image stabilizer Page 25 Page 650 Left column
Page 872 9 Hardener
Page 26 Page 651 Left column
Pages 874-875 10 Binder
Page 26 Same as above
873-874 pages 11 plasticizer,
Lubricant Page 27 Page 650 Right column Page 876 12 Coating aid,
Pages 26-27 Page 650 Right column
Pages 875-876 Surfactant 13 Static prevention Page 27
Page 650 Right column Pages 876-877 Stopping agent 14 Matting agent
878
~ page 879

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 411,987 and No. 4,435,503. The photosensitive material of the present invention is disclosed in U.S. Pat. Nos. 4,740,454 and 4,7.
No. 88,132, JP-A-62-18539, JP-A-1
It is preferable to contain the mercapto compound described in No.-283551.

The photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-open No. 1-1060.
It is preferable to contain a compound described in No. 52 that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof regardless of the amount of developed silver produced by the development process. International Publication WO88
/04794, dyes dispersed by the method described in Japanese Patent Application Publication No. 1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259
It is preferable to contain the dye described in No. 358.

The coupler used in the present invention can be introduced into a photosensitive material in combination with a dispersion coupler obtained by various known dispersion methods other than the method of the present invention. Examples of high boiling point solvents used in the oil-in-water dispersion method are U.S. Pat.
It is described in No. 027, etc. Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, (2,4-
Di-t-amylphenyl) phthalate, bis(2,4-
di-t-amylphenyl)isophthalate, bis(1,
(1-diethylpropyl) phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy ethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (
2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide,
N,N-diethyl laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2
-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-t-octylaniline, etc.), hydrocarbons (Paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

[0100] The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Patent Application (OLS) No. 2,541,274 and OLS No. 2,541,230. The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned RD. No. 17643, page 28, No.
18716, page 647 right column to page 648 left column, and the same N
o. 307105, page 897. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and 28 μm or less.
The thickness is more preferably 3 μm or less, even more preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr. Sci., Eng.) by A. Green et al.
, Vol. 19, No. 2, pp. 124-129.
T1/2 is defined as the time required to reach 1/2 of the saturated film thickness, with 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30° C. for 3 minutes and 15 seconds as the saturated film thickness.

The membrane swelling rate T1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula: (
It can be calculated according to the formula: maximum swelling film thickness - film thickness)/film thickness. The photosensitive material of the present invention has a hydrophilic colloid layer (with a total dry film thickness of 2 μm to 20 μm) on the side opposite to the side having the emulsion layer.
It is preferable to provide a back layer (referred to as a back layer). This back layer contains the aforementioned light absorbers, filter dyes, ultraviolet absorbers, anti-static agents, hardeners, binders, plasticizers,
It is preferable to contain a lubricant, a coating aid, a surface active agent, etc. The swelling ratio of this back layer is preferably 150 to 500%.

[0104] The color photographic material according to the present invention has the above-mentioned RD. No. 17643, pages 28-29, No.
651 left column to right column of 18716, and the same No. 3071
Development processing can be carried out by the usual method described on pages 880 to 881 of 05.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and a representative example thereof is 3-methyl-4-amino-N
, N-diethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts,
It is common to include development inhibitors or antifoggants such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxy Ethyliminodiacetic acid, 1-hydroxyethylidene-1,1
-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine-di(o-hydroxyphenylacetic acid) and their salts as representative examples. can be mentioned.

When performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination. The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but is generally less than 3 liters per square meter of light-sensitive material, and can be reduced to less than 500 ml by reducing the bromide ion concentration in the replenisher. You can also. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

[0108] The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. In other words, aperture ratio = [contact area between processing liquid and air (cm2)
]÷[Capacity of processing liquid (cm3)] The above aperture ratio is 0.
．． It is preferably 1 or less, more preferably 0.0
01 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, methods using a movable lid described in JP-A No. 1-82033, Examples include the slit development method described in No. 63-216050. Reducing the aperture ratio is important not only for both color development and black-and-white development, but also for subsequent steps, such as bleaching,
It is preferable to apply it to all steps such as bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for color development processing is usually 2 to 5 minutes.
The processing time can be further shortened by setting a high temperature, high pH, and using a high concentration of a color developing agent.

The photographic emulsion layer after color development is usually bleached. Bleaching treatment may be performed simultaneously with fixing treatment (
Bleach-fixing treatment) may be carried out separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment. Furthermore, treatment in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents include organic complex salts of iron (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid,
Aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid, complex salts such as citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts, including ethylenediaminetetraacetate iron(III) complex salts and 1,3-diaminopropanetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. . Additionally, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of bleaching solutions or bleach-fixing solutions using these iron(III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but in order to speed up the processing, the pH can be lowered. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-baths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Compounds having a mercapto group or disulfide group as described in JP-A No. 17129 (July 1978); thiazolidine derivatives as described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832, 53-32735, U.S. Patent No. 3,706,56
Thiourea derivatives described in No. 1; West German Patent No. 1,127,
No. 715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-40943, 49-59644, 53-94
No. 927, No. 54-35727, No. 55-26506
Compounds described in No. 58-163940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and in particular, compounds described in U.S. Pat. Compounds are preferred. Additionally, U.S. Patent No. 4,55
Also preferred are the compounds described in No. 2,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

[0111] In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stains. Particularly preferred organic acids have an acid dissociation constant (
pka) of 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid, etc. are preferred.

[0112] Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates are common, with ammonium thiosulfate being the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2. - It is preferable to add imidazoles such as methylimidazole from 0.1 to 10 mol/liter.

[0114] The total time of the desilvering step is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes.
minutes, more preferably 1 to 2 minutes. Further, the treatment temperature is 25°C to 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and stain generation after treatment is effectively prevented.

[0115] In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening the stirring include a method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material as described in JP-A-62-183460, and a method of stirring using a rotating means as described in JP-A-62-183461. A method to improve the stirring effect, a method to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade installed in the solution, and creating turbulence on the emulsion surface, and circulation of the entire processing solution. One method is to increase the flow rate. Such agitation improvement means include bleaching solutions, bleach-fixing solutions,
It is effective for any fixer. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. In addition, the above-mentioned agitation improvement means are more effective when a bleach accelerator is used,
It is possible to significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by bleach accelerators.

[0116] The automatic developing machine used for the photosensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-60-19125.
It is preferable to have a photosensitive material conveying means described in No. 8 and No. 60-191259. The above-mentioned JP-A-60-1
As described in No. 91257, such a conveyance means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing performance deterioration of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society
y of Motion Picture and T
elevision Engineers Volume 64,
p. 248-253 (May 1955 issue).

According to the multistage countercurrent system described in the above-mentioned document,
Although the amount of water used for washing can be significantly reduced, the increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-
Isothiazolone compounds and thiabendazoles described in No. 8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi.
"Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Technology Association "Sterilization, Disinfection, and Antifungal Technology of Microorganisms" (1982)
“Encyclopedia of Antibacterial and Antifungal Agents” edited by the Society of Industrial Engineers and the Japan Society of Antibacterial and Antifungal Agents (
It is also possible to use the fungicides described in (1986).

[0119] The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but are generally selected in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. be done. Furthermore, in the photosensitive material of the present invention, instead of the above-mentioned washing with water,
It is also possible to work directly with a stabilizing solution. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 57-8543
All known methods described in No. 8-14834 and No. 60-220345 can be used.

[0120]Furthermore, following the water washing treatment, a further stabilization treatment may be carried out, for example, a stabilization treatment containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. You can mention bathing. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

[0121] The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the desilvering process. When each of the above processing solutions becomes concentrated due to evaporation during processing using an automatic processor, etc.,
It is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No.
Indoaniline compounds described in No. 342,597, Research Disclosure No. 3,342,599; 14850 and the same No. The Schiff base type compound described in No. 15159, the Schiff base type compound described in No. Examples include aldol compounds described in No. 13924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.

The silver halide color photosensitive material of the present invention is
If necessary, various types of 1-
Phenyl-3-pyrazolidones may also be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
No. 4547, No. 58-115438, etc.

[0124] Various processing solutions in the present invention can be used at temperatures ranging from 10°C to 50°C.
Used at ℃. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

[0125] The silver halide photosensitive material of the present invention is also disclosed in US Pat.
No. 49, No. 59-218443, No. 61-23805
The present invention can also be applied to heat-developable photosensitive materials such as those described in European Patent No. 6 and European Patent No. 210,660A2.

[0126]

[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 2.5 g of the surfactant listed in Table 1 was dissolved in 50 cc of water. In addition, the yellow coupler YCP-A with the following structure
2.5 g was dissolved in 12.5 cc of n-propanol at 50°C. This n-propanol solution was gradually added to an aqueous surfactant solution to prepare a dispersion. At this time, the n-propanol solution was added in about 1 minute, and the aqueous solution was stirred at about 600 RPM. This dispersion was immersed in a constant temperature layer at 50°C for 24 hours,
Thereafter, it was filtered through a 1 micron filter and the stability of the dispersion was examined.

[0128]

[C26]

[0129]

[Table 1]

From the results in Table 1, compounds (I) of the present invention ~
(III) was found to produce stable aqueous dispersions. It has also been found that the compounds I-1, I-2, and I-8 of the present invention give transparent dispersions, and the compounds having the structure of general formula (I) are advantageous for obtaining fine dispersions.

Next, experiment No. The aqueous dispersions of Nos. 4, 7, and 9 and 25 g of a 10 wt % gelatin solution were mixed, and the mixture was kept at 50° C. for 24 hours and filtered in the same manner as before to examine stability. At this time, 0.125 g of a surfactant of Compound IV of the present invention shown in Table 2 was added to the aqueous dispersion.

[0132]

[Table 2]

From the results shown in Table 2, it was found that the hydrophilic colloid composition of the present invention was stable.

Example 2 2.5 g of the yellow coupler YCP-A of Example 1 was dissolved in 4 cc of ethyl acetate, and this solution was mixed with 10 wt.
% gelatin aqueous solution to prepare a dispersion A. Dispersions B and C were prepared in the same manner as Dispersion A except that the concentration of the aqueous gelatin solution was changed to 5 wt% and 2.5 wt%.

Experiment No. 1 of Example 1. The hydrophilic colloid composition of No. 12 was designated as dispersion D, and the concentration of the gelatin aqueous solution was 5w.
Dispersions E and F were prepared in the same manner as Dispersion D except that the amounts were changed to t% and 2.5wt%. Dispersions A and D, B and E, C
The amount of gelatin contained in and F is the same. Dispersion A~
When D was held at 50° C. for 24 hours, coupler precipitation was observed in dispersion C. The total amount of dispersions A to F was mixed with 40 g of silver chlorobromide emulsion (73 g of silver/kg emulsion, 90 g of gelatin).
g/kg emulsion, silver bromide 80 mol%) and held at 50°C for 24 hours with stirring. When this solution was filtered with a 3μ filter under pressure, an increase in filtration pressure and precipitation of dispersions B and C were observed. On the other hand, a slight increase in filtration pressure was observed in dispersion A, and no increase in filtration pressure or precipitation was observed in dispersions D, E, and F. This shows that the hydrophilic colloid composition of the present invention is suitable for reducing gelatin.

Example 3 On a subbed cellulose triacetate film support,
Sample 301, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below. (Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount in units of g/m2, and for silver halide, the coating amount in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver
Silver
0.18 Gelatin

1.40

Second layer (middle layer) 2,5-di-t-pentadecylhydroquinone
0.18 EX-1

0
．． 070 EX-3

0.020 EX-12

2.0×10-3
U-1

0.060 U-2

0.080
U-3

0.10 HBS-1

0.10 HBS-2

0.
020 Gelatin

1.04

Third layer (first red-sensitive emulsion layer) Emulsion A

Silver 0.25 Emulsion B

Silver 0.25 Sensitizing dye I
6.9×
10-5 Sensitizing dye II

1.8×10-5 Sensitizing dye III

3.1×10-4
EX-2

0.34 EX-10

0.020 U-1


0.070 U-2

0.050 U-3


0.070 HBS-1

0.060 Gelatin

0.87

Fourth layer (second red-sensitive emulsion layer) Emulsion G

Silver 1.00 Sensitizing dye I

5.1×10-5 Sensitizing dye II
1.4×
10-5 Sensitizing dye III

2.3×10-4 EX-2

0.40
EX-3

0.050 EX-10

0.015 U-1


0.070 U-2

0.050 U-3


0.070 Gelatin

1.30

Fifth layer (third red-sensitive emulsion layer) Emulsion D

Silver 1.60 Sensitizing dye I

5.4×10-5 Sensitizing dye II
1.4×
10-5 Sensitizing dye III

2.4×10-4 EX-2

0.097
EX-3

0.010 EX-4

0.080H
BS-1

0.22 HBS-2

0.10 Gelatin

1.63

6th layer (middle layer) EX-5

0.040 HBS-1

0.020 Gelatin

0.80

Seventh layer (first green-sensitive emulsion layer) Emulsion A

Silver 0.15 Emulsion B

Silver 0.15 Sensitizing dye IV
3.0
×10-5 Sensitizing dye V

1.0×10-4 Sensitizing dye VI

3.8×10-4
EX-1

0.021 EX-6

0.26 EX-
7

0.030 EX-8

0.025 HBS-1

0.1
0 HBS-3

0.010 Gelatin

0.63

014
4] 8th layer (second green-sensitive emulsion layer) Emulsion C

Silver 0.45 Sensitizing dye IV

2.1×10-5 Sensitizing dye V
7.0×
10-5 Sensitizing dye VI

2.6×10-4 EX-6

0.094
EX-7

0.026 EX-8

0.018H
BS-1

0.16 HBS-3

8.0×10-3 gelatin

0.50

9th layer (third green-sensitive emulsion layer) Emulsion E

Silver 1.20 Sensitizing dye IV

3.5×10-5 Sensitizing dye V
8.0×
10-5 Sensitizing dye VI

3.0×10-4 EX-1

0.025
EX-11

0.10 EX-13

0.015 HBS-
1
0
．． 25 HBS-2

0.10 Gelatin

1.54

01
46] 10th layer (yellow filter layer) yellow colloidal silver
Silver
0.050 EX-5

0.080 HBS-1

0.
030 Gelatin

0.95

11th layer (first blue-sensitive emulsion layer) Emulsion A

Silver 0.080 Emulsion B

Silver 0.070 Emulsion F
Silver
0.070 Sensitizing dye VII

3.5×10-4 EX-8

0
．． 042 EX-9

0.72 HBS-1

0.28
gelatin

1.10

12th layer (second blue-sensitive emulsion layer) Emulsion G

Silver 0.45 Sensitizing dye VII

2.1×10-4 EX-
9

0.15 EX-10

7.0×10-3 HBS-1

0.050
gelatin

0.78

13th layer (third blue-sensitive emulsion layer) Emulsion H

Silver 0.77 Sensitizing dye VII

2.2×10-4 EX-
9

0.20 HBS-1

0.070 Gelatin

0.69

14th layer (first protective layer) Emulsion I

Silver 0.20 U-4

0.11 U-
5

0.17 HBS-1

5.0×10-2 gelatin

1.0
0

15th layer (second protective layer) H-1

0.40 B-1 (diameter 1.7 μm)

5.0×10-2 B-2 (diameter 1.
7μm)
0.10 B-3

0
．． 10 S-1

0.20 Gelatin

1.20

[
[0152] Furthermore, all layers have good storage stability, processability, pressure resistance,
In order to improve anti-fungal and anti-bacterial properties, anti-static properties and applicability, W-1, W-2, W-3, B-4, B-5, F-1,
F-2, F-3, F-4, F-5, F-6, F-7, F
-8, F-9, F-10, F-11, F-12, F-1
3, and contains iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

[0153] 11th layer HBS-1 0.28 g/m
Sample 302 was prepared in exactly the same manner as 301, except that Sample 2 was removed, the amount of EX-8 added was reduced to 0.021 g/m2, and the amount of gelatin was further reduced to 0.7 g/m2. At this time E
W-3 was used at 0.08 g/m2 as a surfactant for dispersing X-8 and EX-9. Sample 303 was prepared in the same manner as Sample 302 except that 0.24 g/m<2 >of Compound I-8 of the present invention was used in place of W-3 in Sample 302. Sample 304 was prepared in the same manner as Sample 303 except that 0.02 g/m2 of IV-5 was used in addition to I-8.

[0154]

[Table 3]

[0155]

[C27]

[0156]

[C28]

[0157]

[C29]

[0158]

[C30]

[0159]

[Chemical formula 31]

[0160]

[C32]

[0161]

[Chemical formula 33]

[0162]

[C34]

[0163]

[C35]

[0164]

[C36]

[0165]

[C37]

[0166]

[C38]

[0167]

[C39]

[0168] For sample 303, the viscosity of the coating liquid increased during sample preparation, and a uniform sample could not be obtained. Sample 301, 3
After image exposure on 02/304, it was subjected to the processing described below. Samples 301, 302, and 304 all gave almost similar images. This treated sample was heated at 80℃ and 70%R.
When stored for 3 days under H conditions, yellow oily seepage was observed on the surface only in sample 302. Sample 301,
In No. 304, this yellow oil was not observed. From this, thinning of the layer (reduction of gelatin and HBS-1) as seen in sample 302 is accompanied by deterioration of film quality, whereas when the compound of the present invention is used, even if the layer is made thinner, it is accompanied by deterioration of film quality. It turns out that there is nothing wrong with that. In addition, in sample 302, W-
Even if the usage amount of No. 3 was changed to 0.24 g/m2, which is the same as No. 304, the above-mentioned seepage of the oily substance was not improved.

[0169] The sample prepared as described above was
It was cut into widths, subjected to imagewise exposure, and processed using an automatic processor. The treatment was carried out continuously for 500 m on a 35 mm wide sample. The treatment steps and treatment liquid composition are shown below.

[0170]
Processing method Process Processing time
Processing temperature Refill amount* Tank capacity Color development 3 minutes 05 seconds 3
8.0℃ 600ml
5 liter bleach
50 seconds 38.0℃
140ml 3 liters
Bleach fixing 50 seconds 38
．． 0 ℃ -
3 liter fixation
50 seconds 38.0℃ 42
0ml 3 liters
Wash with water 30 seconds 38
．． 0℃ 980ml
2 liters stable (1)
20 seconds 38.0℃
- 2 liters
Stable (2) 20 seconds 38
．． 0℃ 560ml
2 liters dry 1 minute
60℃

*The amount of replenishment is per 1 m2 of photosensitive material.

[
[0171] The washing water flowed in a countercurrent manner from (2) to (1), and all the overflow liquid of the washing water was introduced into the fixing bath. The bleach-fixing bath can be refilled by connecting the top of the automatic processor's bleach tank and the bottom of the bleach-fixing tank, and the top of the fixing tank and the bottom of the bleach-fixing tank with pipes, and supplying replenisher to the bleach tank and fixing tank. All of the overflow liquid generated was allowed to flow into the bleach-fix bath. The amount of developer brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the washing process are each 65 m2 per 1 m2 of photosensitive material.
1, 50ml, 50ml, 50ml. Further, the crossover time is 5 seconds in each case, and this time is included in the processing time for the previous step.

The composition of the treatment liquid is shown below. (color developer)
Mother liquor (g)
Replenisher (g) Diethylenetriaminepentaacetic acid
2.0
2.2 1-hydroxyethylidene-1,1
−
diphosphonic acid
3.
3 3.3 Sodium sulfite

3.9 5.2 Potassium carbonate
37.5 39.0 Potassium bromide
1.4
0.7 Potassium iodide
1.3mg
hydroxylamine sulfate
2.4 3.
3 2-Methyl-4-[N-ethyl-N-
(β-hydroxyethyl)amino]

Aniline sulfate
4.5
6.0 Add water
1.0 liter 1.
0 liter pH
10.
05 10.15

(Bleach solution)
Mother liquor (g)
Replenisher (g) 1,3-propylenediaminetetraacetic acid
Ferric ammonium monohydrate 14
4.0 206.6 Ammonium Bromide

84.0 120.0 Ammonium nitrate

17.5 25.0 Hydroxyacetic acid

63.0 90.0 Acetic acid

54.2 80.
0 Add water
1.0 liter 1.0 liter pH [adjusted with ammonia water]
3.80 3.6
0

(Bleach-fixing solution mother liquor) A 15:85 mixture of the above bleaching solution mother liquor and the following fixing solution mother liquor.

(Fixer)
Mother liquor (g)
Replenisher (g) Ammonium sulfite
19.
0 57.0 Ammonium thiosulfate aqueous solution (700g/liter)
280ml 840ml
imidazole
28.5
85.5 Ethylenediaminetetraacetic acid
12.5
37.5 Add water
1.0 liter 1.
0 liter pH [adjusted with aqueous ammonia and acetic acid]
7.40 7.4
5

(Water wash solution) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IRA-120B manufactured by Rohm and Haas). 400)
Water is passed through a mixed-bed column packed with water to reduce the concentration of calcium and magnesium ions to 3 mg/liter or less,
Subsequently, 20 mg/liter of sodium isocyanurate dichloride and 150 mg/liter of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stable solution) Common to mother solution and replenisher solution
(Unit: g)
Formalin (37%)

2.0ml Sodium p-toluenesulfinate
0.
3 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10)

0.2 Ethylenediaminetetraacetic acid disodium salt 0
．． 05 Add water

1.0 liter pH

7.2

01
78]

EFFECTS OF THE INVENTION The photographic hydrophilic colloid composition of the present invention provides a stable dispersion of hydrophobic photographically useful compounds without the use of a polymeric protective colloid or even with a small amount thereof. Therefore, by using this hydrophilic colloid composition, it is possible to design a light-sensitive material with excellent photographic properties, sharpness, and the like.

Claims (2)

[Claims] [Claim 1] The following general formula (I), (II) or (I
II) A dispersion of a hydrophobic photographically useful compound prepared in the presence of at least one of the compounds represented by: containing at least one of a polyoxyethylene group, a polyglycerol group, or a polyhydric alcohol residue in the molecule. A hydrophilic colloid composition for photography, characterized in that it is mixed with a hydrophilic colloid dispersion in the presence of a surfactant. General formula (I) [Formula 1] General formula (II) [Formula 2] General formula (III) [Formula 3] 2. A silver halide photographic material comprising the photographic hydrophilic colloid composition according to claim 1.