JPS63307451A - Silver halide color photographic sensitive material with improved graininess - Google Patents

Abstract

PURPOSE:To improve the graininess of the obtd. color image by incorporating a specified aqueous coupler in the titled material. CONSTITUTION:The aqueous coupler (A) capable of subjecting a coupling reaction with the oxidant of a color developing main agent is incorporated in the titled material. Said coupler (A) is exemplified by preferably a compd. having a structure shown by formula I or II wherein X is hydrogen atom. or alkyl group, etc., A1 and B1 are each -N= or =C= group, Z is an atomic group necessary for forming a ring together with A1-C(X)=B1, A2 and B2 are each -C(=O)-R or -CN group, etc., R is hydrogen atom. or a monovalent org. group. As the coupler (A), and the reaction product of the coupler (A) and said oxidant are fluxed during developing and a following processing, said coupler and the reaction product many be incorporated in a hydrophilic layer which swells with a development processing solution, in excess.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved graininess.

[Background of the invention]

In recent years, silver halide photographic materials, especially color photographic materials for photography, have become more sensitive to small formats, and higher image quality is required than ever before, and there is a strong need to improve graininess in particular. desired.

Factors that influence graininess include the density of silver halide in the photographic constituent layers, the grain size of silver halide, and the size and shape of the formed dye cloud.

In addition, a decrease in the number of color points due to oxidation of photosensitive nuclei caused by excessive oxidized color developing agent, so-called latent image bleaching, is another possible phenomenon that deteriorates graininess.

On the other hand, there is a conventionally known technique for improving graininess by consuming the acid form of the developing agent.
So-called colorless couplers, which react with oxidized color developing agents competitively with image-forming couplers, and U.S. Pat.
No. 290, No. 2,336,327, No. 2, 403
.

No. 721, No. 2,701,197, No. 2,728,6
Color developing agent oxidized product scavengers such as hydroquinone derivatives and aminophenol derivatives described in JP-A-52-28318 and JP-A-52-28318 and JP-A-57-
No. 111537, No. 57-138636, No. 61-1
Examples include couplers that release a compound that captures the oxidized form of the color-forming ring 1 principal agent from the coupling position of the coupler, as described in No. 02846 and the like.

However, the graininess improvement effect of these techniques is small;
Further improvements are desired. Furthermore, as described in, for example, U.S. Pat. No. 2,889,793, silver halide photographic materials containing diffusion-resistant couplers,
Processed in a color developing bath containing a water-soluble coupler that reacts with an oxidized color developing agent called a combining coupler to form a colorless compound, or is washed out from the light-sensitive material even if a dye is formed. There is a way. However, such a method has the disadvantage that sensitivity and color density are greatly reduced.

As described above, it cannot be said that sufficient development has been made to date of techniques for significantly improving graininess without adversely affecting photographic properties.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic material in which the graininess of the obtained dye image is significantly improved.

[Structure of the invention]

The above objects of the present invention have been achieved by a silver halide color photographic material containing a water-soluble curler capable of coupling reaction with an oxidized color developing agent.

The water-soluble coupler of the present invention is not particularly limited as long as it is water-soluble, but water-soluble couplers having a structure represented by the following general formula (1) or [■] are highly effective in improving graininess. It is something that

General formula [1] General formula [11) -z-' In the formula, X represents a hydrogen atom, an alkyl group, or a group that can be separated by reaction with an oxidized product of a color developing agent, and Z represents A
, -C=represents an atomic group necessary to form a ring in cooperation with B+.

A2 and B2 are - and -R, -CN, respectively.

-sow-R or an aryl group.

R,, R' and R'' each represent a hydrogen atom or a monovalent organic group, and A2 and B may be combined with each other to form a ring.

Here, we will speculate as to why the silver halide color photographic light-sensitive material containing the water-soluble coupler of the present invention has the effect of significantly improving graininess without adversely affecting photographic properties, but this is just speculation and is not a fact. is not clear.

First, if we focus on latent image bleaching, which is thought to reduce the number of color spots and deteriorate the graininess mentioned above, it can be seen that in the early stages of color development, when the concentration of the color developing agent that diffuses into the silver halide emulsion layer is low, It seems that the area around the latent image nucleus in the layer is likely to become an oxidizing atmosphere, and latent image bleaching is likely to occur. Furthermore, since the diffusion of developer components into the photographic constituent layers does not seem to occur completely uniformly, especially in the early stages of development,
A situation where slight variations in development occur, and as development progresses, some reinforced latent image nuclei and weak latent image nuclei remain undeveloped, and the weak latent image nuclei are easily bleached by the generated oxidized product of the color developing agent. It is also possible that it will become. Furthermore, such a phenomenon is considered to be more likely to occur in a multilayer color photographic light-sensitive material consisting of a plurality of photographic constituent layers.

Considering this situation, the conventional graininess improvement techniques mentioned above, such as colorless couplers, color developing agent oxidized product scavengers, and couplers that release a compound that captures color developing agent oxidized products from the coupling position of the coupler, etc. are all hydrophobic compounds, and exist in the oil phase emulsified and dispersed in the form of minute oil droplets in the photographic constituent layer.What is the gelatin medium phase (hydrophilic phase) in which the oxidized product of the color developing agent is produced? Different phases. For this reason, especially in the early stages of color development, it is thought that it is difficult to exhibit the effect of quickly consuming the oxidized color developing agent generated in the gelatin medium phase.

On the other hand, since the water-soluble coupler of the present invention exists in the gelatin medium phase, it can quickly consume the oxidized color developing agent generated during the initial stage of color development, thereby effectively preventing latent image bleaching. However, it is thought that graininess can be improved.

In addition, when the compound that consumes the oxidized color developing agent is a hydrophobic compound, or when the color developing bath contains a water-soluble compound that consumes the oxidized color developing agent, such as the above-mentioned competing coupler, the color forming During development, the oxidized color developing agent is constantly consumed, so the oxidized color developing agent useful for forming dye images is also consumed, which inevitably causes negative effects on photographic performance such as a decrease in sensitivity and color density. It seems to be.

On the other hand, since the water-soluble coupler of the present invention flows out of the photographic constituent layers after the initial stage of color development, the consumption of the oxidized color developing agent, which is useful for dye image formation, is minimized, resulting in photographic performance. It is thought that the negative impact on

[Specific structure of the invention]

The "water-soluble coupler" used in the present invention is defined as follows.

"An aqueous solution (p
H10,0, prepared with a small amount of sulfuric acid and potassium hydroxide) A coupler that dissolves at least 1 mmol in H11 at 25°C Preferred are water-soluble couplers having a solubility of .

The water-soluble coupler of the present invention preferably has at least one of the groups shown below in the molecule in order to improve water solubility.

SOJ, C00II, Oll, N112.
Among these groups, one 5O311, C00II, -011
is an alkali metal salt (e.g., sodium, potassium salt)
; Salts such as ammonium salts and organic ammonium salts (eg, pyridinium, piperidinium, triethylammonium, triethanolamine salts) may be formed.

-NH2 is any inorganic acid, organic acid, such as hydrochloric acid, sulfuric acid,
It may form a salt with sub[M, carboxylic acids, phosphoric acids, 9-)luenesulfonic acid, etc.

The water-soluble couplers of the present invention do not form dye images.11 The water-soluble couplers of the present invention and the reaction products of the water-soluble couplers of the present invention and the oxidized color developing agent flow out during development and subsequent processing. It is preferable to do so.

Therefore, the reaction product of the water-soluble coupler of the present invention and the oxidized color developing agent may have any spectral absorption and may be colorless.

The water-soluble coupler of the present invention is a hydrophobic compound phase (dispersed fine oil droplet phase) consisting of a diffusion-resistant coupler, a high-boiling organic solvent, a color antifoggant, an image stabilizer, etc. that forms a dye image in a photographic constituent layer. ), but it is preferable that the gelatin medium phase (hydrophilic phase), which is swollen by the processing solution during color development, contains the gelatin medium in a larger amount.

The molecular weight of the water-soluble coupler of the present invention is preferably 1000.
It is less than 500, more preferably less than 500.

Next, the water-soluble coupler represented by the general formula (1) or [■] will be described in detail.

In general formulas CI) and CI[), the alkyl group represented by X preferably has 1 to 10 carbon atoms, may be linear or branched, and may have a substituent.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine, bromine, fluorine atoms, etc.), alkoxy, aryloxy, heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy. , aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclicthio, alkyloxythio, carbonylthio, acylamino, sulfonamide,
Nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, ゝ-Z-'(A+','B+' and Z' are each the above A +
, B + and Z, and R and R' each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Preferably X is a hydrogen atom.

-a formula CI), A, and I3. are each -N
= or =C〈, specifically the following general formula ([
-1) to (1-6).

General formula (1-1) General formula (1-2) General formula (
1-3) General formula (1-4) General formula (1-5)
In the general formula ([-6), X and Z are respectively synonymous with X and Z in the general formula (l), and R+
*Rz*R3+R1 and R1 each represent a hydrogen atom or a monovalent organic group, R+, R2, R3
, R4 and R1 are not particularly limited, but include, for example, halogen atoms, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocycle, acyl, sulfonyl, sulfinyl, phosphonyl. , carbamoyl, sulfamoyl, cyano, spiro compound residue, bridged hydrocarbon compound residue, alkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, acylamino, sulfonamide, imide, ureido, sulfamoyl Amino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl,
Examples include aryloxycarbonyl, alkylthio, arylthio, heterocyclic thio, sulfo, nitro, carboxy, and hydroxy groups.

R6 and R6 represent a divalent organic group having one loss through an oxygen atom, a sulfur atom, a carbon atom, or a nitrogen atom,
Additionally, in general formulas (1-1) to (1-6), the structures represented by general formulas (1-2), (1-3), and (1-5) may be in a conjugate relationship with each other. , general formula Cl-4
) and [:l-6).

In general formulas (1-1) to (1-6), Z represents an atomic group necessary to form a ring in cooperation with, and preferably,
It is an atomic group consisting of carbon atoms, hydrogen atoms, oxygen atoms, and nitrogen atoms. The ring formed is preferably a 5- to 6-membered ring, and may have a substituent, 1! As a substituent, the above-mentioned R+
, R2, R3, R4 and R7. Further, Z may cooperate with R1-R1 to form a ring.

In the general formula [■], X has the same meaning as or in the general formula CI].

-fi In the formula [■], A2 and B2 represent an aryl group, among which A2 and B2 are T, H,
James: The Theory of the Photographic Process
acti described in thePhotographic Process) 3rd edition, page 388, figure 17.6
Combinations that result in ve couplers are preferred.

R, R' and R'' represent a hydrogen atom or a monovalent organic group;
and a group represented by R7.

Further, R and R' may be combined with each other to form a ring, A
2 and 82 may be combined with each other to form a ring, and the ring formed is preferably a 5- to 6-membered ring.

In the compound represented by the -ffm formula [11], when A and 82 combine with each other to form a ring, the compound may be in a conjugate relationship with the structure represented by the -1R formula (1).

Among the water-soluble curlers of the present invention, more preferred ones are represented by the following general formulas CII [) to [edited].

General formula (I[[) General formula [■] General formula [
V] General formula (Vl) General formula [■]
General formula [■] In the above general formulas (III) to [revised], X has the same meaning as X in the above -m formula (1').

R6-R22 and R2 represent a hydrogen atom or a monovalent organic group, and as the monovalent organic group, the above R1゜R2, R
Examples include groups represented by 3, R< and Rt.

Here, R, R', R'' have the same meanings as the above R, R', R'', and R and R' may be combined with each other to form a ring, n
represents an integer of O to 4, and when n is 2 or more, R may be the same or different.

One of Za and zb represents -N=, and the other represents a hydrogen atom or a monovalent organic group.

l represents an integer from O to 2, when l is 2, R12 may be the same or different; Good too.

In general formula (II), R1 and R, and/or R
3° and R1 may be bonded to each other to form a ring.

In general formula (III), Rs, Re, Rt. or R1
In the group represented by 1, in the general formula [■], in the group represented by R11, in the general formula [■], in the group represented by R13 or R1, -m in the formula (Vl), Rts Or in the group represented by R3, in the m formula [■], in the group represented by R17 or R11 -
In formula m [■], in the group represented by R1 or R2゜-ff1 In the group represented by R21 or R22 in formula CI -in formula (X), R2 is represented General formula (X
In I), -SO,
It is preferable that at least one of H, -COOH, -OH, and -Nff2 is included.

Among the water-soluble couplers represented by general formulas (Ill) to (XI), particularly preferred are formulas -m [:II[), [l
V:] and (V) are water-soluble couplers.

The most preferred water-soluble couplers of the present invention are represented by the following general formulas [X■] and (XII[).

General formula (Xn) 0M ^ General formula (Xlll) Rho 1 In the general formula (Xll) and (Xt[[), X has the same meaning as X in the general formula [1].

R2? , R2@ and R2, represent monovalent organic groups, p
represents an integer of 0 to 2, Q represents an integer of 0 to 4, and r represents an integer of 0 to 2.

Any one of them is −N=, and the other three squirrels.

Examples of the monovalent organic groups represented by R29,12a, n21 and R2° include the groups represented by R+, R2, R3, R4 and R1.

When p, q and " are each 2 or more, R21゜l(
2 and 1121 may be the same or different.

The water solubility represented by the general formula [X■] is R
In the group represented by zt or R21, -So, 11°-C
OO11, -OH, -Ni1. It is preferable to have at least one of the following.

In the general formula (Xlll), Zl is -N-, and the water-soluble coupler represented by the general formula (XI[i) has -SOJ in the group represented by R2 or R5゜.
, at least one of -COO11, -011, -812
It is preferable to have one.

Next, specific examples of water-soluble couplers used in the present invention will be given, but these are merely examples for explaining the present invention, and the present invention is not limited thereto.

しυU+t ti8 119NCC1l
zCON(CHs)z NCCH2CN
t52 1531(i
5 166167
゛ 168υ The water-soluble couplers of the present invention are already known compounds, and some are commercially available.
No. 34,272, No. 2,474,293, No. 2,52
1.908, JP-A-48-59838, JP-A No. 51-2
No. 8034, U.S. Patent No. 2,875,057, U.S. Patent No. 3,2
No. 65,506, West German Patent No. 1,547°868, West German Application Publication v! No. 42,219,917, British Patent No. 1,42
No. 5.020, JP-A-51-10783, U.S. Patent No. 2
, No. 600,788, No. 2,983,608, West German Patent No. 1,810,464, West German Patent Application (OL S)
No. 2,408,665, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1973, Journal of the Chemical Industry. Perkin Transactions I
(J,Chem,Soc,,Perkin
Trar+s, I ), (19fufu).

2047-2052, U.S. Patent No. 3,725,067,
Those skilled in the art can easily synthesize it by referring to the methods described in JP-A Nos. 59-99437, 80-172982, and 60-190779.

The water-soluble coupler of the present invention is used in an amount of o,oot to 1 mol, preferably 0.005 to 0.5 mol, per mol of photosensitive silver halide in the photographic light-sensitive material.

Two or more types of water-soluble couplers of the present invention may be used in combination.

In order to incorporate the water-soluble coupler of the present invention into a photographic light-sensitive material, the water-soluble coupler of the present invention may be mixed with water or an alkaline aqueous solution, and if necessary, a water-soluble organic solvent (e.g., methanol, ethanol, acetone, etc.). and dissolve it.
It can be added to a coating solution during the production of photographic materials. In addition, a homogeneous solution in which the water-soluble coupler of the present invention is dissolved (
The water-soluble coupler may be incorporated into the photographic material by immersing the coated photographic material in an aqueous solution, an alkaline aqueous solution, an aqueous solution containing a water-soluble organic solvent, etc.).

In the present invention, a "photographic light-sensitive material" refers to a material prior to color development processing. Therefore, in the present invention, a silver halide color photographic light-sensitive material after photographing or exposure is treated as described above immediately before color development processing. A water-soluble coupler may be added by immersing the sample in a homogeneous solution containing a water-soluble compound. In this case, drying may or may not be performed after 1 m of color development.

The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., but the effects of the present invention are particularly effective when applied to color negative film used for photography. is effectively demonstrated.

The silver halide photographic materials of the present invention, including this color negative film, may be for monochromatic or multicolor use. In the case of multicolor silver halide photographic materials, subtractive color reproduction is used. For this purpose, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as diffusion-resistant couplers for image formation and a light-insensitive layer are usually deposited on a support in an appropriate number and layer order. Although it has a layered structure, the number of layers and the order of the layers may be changed as appropriate depending on the important performance and purpose of use.

As the yellow coupler, benzoylacetanilide and pivaloylacetanilide compounds can be used.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

Examples of magenta couplers include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indacylon-based compounds.

Furthermore, by coupling with a colored coupler having a color correction effect and an oxidized form of a developing agent, a developer, a development inhibitor, a silver halide solvent, a toning agent, a hardening agent, a caprylic agent, an antifoggant, Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers, and desensitizers can be used.

Hydrophobic compounds such as couplers can be prepared by solid dispersion method,
Hydrophobic additives such as couplers can be added to silver halide photographic materials using various methods such as latex dispersion and oil-in-water emulsion dispersion. is usually dissolved in a high boiling point organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low boiling point and/or water-soluble organic solvent, and emulsified in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. After being dispersed, it may be added to the desired hydrophilic colloid layer.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in emulsions can be used.

Silver halide emulsions are chemically sensitized by a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method, or the like. Furthermore, in the photographic industry, dyes known as sensitizing dyes can be used to optically sensitize to a desired wavelength range.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

The photosensitive materials include color antifoggants, hardeners, plasticizers, polymer latex, ultraviolet absorbers, formalin scavenger-1 mordants, development accelerators, development retardants, bleaching accelerators,
Optical brighteners, matting agents, lubricants, stabilizers, antistatic agents, surfactants, etc. can be used as desired.

The silver halide photographic material of the present invention can form images by performing various color development treatments.

[Specific effects of the invention]

By containing the water-soluble coupler of the present invention, the silver halide color photographic light-sensitive material of the present invention was able to significantly improve graininess without adversely affecting photographic properties.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example-1 11.6 g of the following magenta coupler M-1 was dissolved in ethyl acetate 5
After mixing this with 6% gelatin aqueous solution 350 mt' and 5% sodium dodecylbenzenesulfonate aqueous solution Soml, the emulsion obtained by ultrasonic dispersion was iodine. It was added to IKg of silver bromide emulsion (containing 70 g of silver), a hardener and a coating aid were added, and coated on a subbed cellulose triacetate film to a coated silver amount of 1.4 g/m''. This was designated as sample 1.

Next, add the table below to the 6% gelatin aqueous solution used when preparing sample 1.
Sample 2 was prepared in the same manner as Sample 1 except that 3 x 10-2 mol of the water-soluble coupler of the present invention shown in Sample 1 was dissolved and added.
~9 was created. In addition, it was completely the same as Sample 1 except that Comparative Compound ■ (colorless coupler 1 described in British Patent No. 1,284,649) IXIO'' mol was dissolved and added in ethyl acetate and tricresyl phosphate together with magenta coupler M-1. Sample 10 was prepared.

Each sample was exposed to wedge light and subjected to the following treatment steps, followed by sensitometry and maximum color density (D
IIIIX) was calculated. Furthermore, the granularity (RMS) at an image density of Kabrido 0.3 was measured. The results are also shown in Table-1.

Comparative compound 1 Processing step (38°C) Color development during processing
Bleach for 3 minutes and 15 seconds
Wash with water for 1 minute and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
3 minutes and 15 seconds Stabilization bath 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step was as follows.

[Color developer composition] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4,75.

Anhydrous WR sodium nitrite 4.25.

Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid 3 sl
・Lium salt (l water salt) 2.5.

Potassium hydroxide 1.0g Add water to make 11, and adjust to p) 110.0 using potassium hydroxide.

[Bleach solution composition] Iron ethylenediaminetetraacetate Ammonium salt too. o.

Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10.0z1 water to make 11,
p) (adjust to 6.0 using aqueous ammonia.

[Fixer composition] Ammonium thiosulfate (50% water soluble!> 162+sl
Add 12.4 g of anhydrous sodium sulfite water to make up to 1 liter, and adjust the pH to 6.5 using acetic acid.

[Stabilizing liquid composition] Formalin (37% aqueous solution) 5. Oa1 Konidax (Konishi Roku Photo Industry Co., Ltd.) F. hα Add water to make 11.・-The following margin ゛＼-Table-1 *Represented as a relative value with the sensitivity of sample 1 as 100.

As shown in Table 1, sample 10 using comparative compounds
Although graininess was improved, significant desensitization and a decrease in maximum color density were observed. On the other hand, Samples 2 to 9 containing the water-soluble coupler of the present invention showed a significant improvement in graininess without decreasing sensitivity or maximum color density.

Example 2 Each of the following R1 was sequentially placed on a subbed transparent polyester base from the support side to create each sample shown in Table 2 below.

I 1; Antihalation layer A gelatin aqueous solution containing black colloidal silver was added at 0.5H/m
It was applied to a dry film thickness of 3.0 μm at a ratio of 3.0 μm.

Layer 2: Intermediate layer An aqueous gelatin solution was applied to a dry film thickness of 1.0 μm.

Scrap 3: Red-sensitive, low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (
A silver iodobromide emulsion containing 4 mol% of silver iodide with an average grain size of 0.6 μm and a silver iodobromide emulsion containing 4 mol% of silver iodide with an average grain size of 0.3 μm in a ratio of 2:1. ) was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-
Ethyl-3,3'-di(3-sulfopropyl)-4,
5゜4',5'-dibenzothiacarbocyanine hydroxide (SD-1), anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfobutyl)thiacarbocyanine hydroxide (SD -2) and anhydrous 2-(2-
1(5-chloro-3-ethyl-2(3H)-penzothiazoliden)methyl)-1-butenyl]-5-chloro-3
After adding -(4-sulfobutyl)benzoxacilium hydroxide (SD-3), 4-hydroxy-6-
Methyl-1,3,3a,7-chitrazaindene 1.0g
, 1-phenyl-5-mercaptotetrazole 20.0
mg was added to obtain a red-sensitive low-sensitivity emulsion.

Next, as a cyan coupler, 2-(2,4-di-t-pentylphenoxy]-echloro-N-(4-([[[
4-cyanophenylaminocopower! levonyl]amino]-
10 mol% of 3-hydroxyphenyl]hexanamide (C-1) per mol of silver (all mol% hereinafter refers to silver 1).
(on moles), N-(3-carboxypropyl)-1-hydroxy-4-(1-(4-nitrophenyl)-3-undecyl-4-[(1-phenyl-IH-tetrazole- 5-ylcothiomethyl l[:
IH-pyrazol-5yl]oxy]-2-naphthalenecarboxamide (D-1) 065 mol%, 5-(acetylamide)-3-([
4-([:3-CCC4-(2,4-di-t-pentylphenoxy]butyramido]carbonyl]-4-hydroxy-1-naphthalenyl]oxy]phenyl]azo)
0.01 mol% of sodium -4-hydroxy-2,7-naphthalene disulfonate (CC-1) and tricresyl phosphate were added to 150 mf of ethyl acetate and dissolved by heating. The 6 dispersion was added to 550 ml of a 5% gelatin aqueous solution and emulsified and dispersed in a colloid mill. After heating and removing ethyl acetate, the above red-sensitive low-sensitivity emulsion was added to give silver 1.5 ν/-2. I applied it to make it look like this.

Layer 4: Red-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (
(average grain size 1.2 μm, containing 7 mol% silver iodide) was chemically sensitized with gold and sulfur sensitizers, and 5D-1, 5D-2 and 5D-3 were added as red-sensitive sensitizing dyes. After adding 4
-Hydroxy-6-methyl-1,3,3a,7-tetrazaindene 1,Q[l,l-phenyl-5-mercaptotetrazole 10. OB was added to obtain a red-sensitive emulsion. Furthermore, 1.8 mol% of C-1 as a cyan coupler, D
N -(4-(2,4-di-t-pentylphenoxy)butyl]-1-hydroxy-4-C(
1 phenyl-IH-tetrazol-5-yl)thio-2-naphthalenecarboxamide (D-2>0.4 mol%,
Add tricresyl phosphate to 60 ml of ethyl acetate, dissolve by heating, and prepare 7.5% gelatin aqueous solution 3 containing 1.5 g of sodium triisopropylnaphthalene sulfonate.
The above-mentioned red-sensitive high-sensitivity emulsion was added to the dispersion which was added to 0al and emulsified and dispersed in a colloid mill, and then coated at a silver concentration of 1.2 g/2.

Layer 5m The same material as intermediate layer 12 was applied. - N6; Green-sensitive, low-sensitivity silver halide emulsion layer average grain size 0.6
Silver iodobromide emulsion containing 4 mol% of silver iodide and an average grain size of 0
．． A silver iodobromide emulsion with a diameter of 3 μm and containing 7 mol % of silver iodide was chemically sensitized with gold and sulfur sensitizers, respectively, and anhydrous 5,5'-dichloro-9-ethyl- 3
, 3'-di(3-sulfobutyl)oxacarbocyanine hydroxide (SD-4>, anhydrous 3,3'-diphenyl-9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide ( SD-5) and anhydrous 9-ethyl-3,3'-di(3-sulfopropyl)
-5,6,5',6'-dibenzoxacarbocyanine hydroxide (SD-6>) was added, then 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene 1.0 g, 1-phenyl -5-mercaptothi 1-razole ZO,O+ur was added and produced in a conventional manner.

Two types of silver halide emulsions obtained in this way were mixed into 1
:1 ratio to obtain a green-sensitive, low-sensitivity silver halide emulsion.

Furthermore, as a magenta coupler, 3-[((2,4-G L
-pentylphenoxy]acetyl]amino]-N-[4
, 10.0 mol% of DIR compound 5-((3- Octadecyl-2,4-dioxo)-pyrrolidin-1-yl 12-((1-phenyl-IH-tetrazol-5-yl)thio-2-1-indasilone (D
-3) 0.5 mol%, colored magenta coupler 3-[
:[(2,4-di-t-pentylphenoxy]acetyl]amino)-N-[:4.5-dihydro-4-[(methoxyphenyl)azo]-5-oxo-1-(2,4,6
0.8 mol% of -trichlorophenyl)-1H-pyrazol-3-ylcubenzamide (CM-1) and a high boiling point solvent were added to 240 ml of ethyl acetate, dissolved by heating, and sodium l-liisobrobynaphthalenesulfonate was added. The above-mentioned recording-sensitive low-frequency emulsion was added to a dispersion that was added to a 7.5% gelatin aqueous solution containing 7.5% aqueous gelatin and emulsified and dispersed in a colloid mill, and coated at a silver concentration of 1.0 g/w''.

N7; Green-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (
average particle size 1.2 μm, containing 17 mol% iodide) was chemically sensitized with gold and sulfur sensitizers, and 5D-4, 5D-5 and 5D-6 were added as green-sensitive sensitizing dyes. and then 4-hydroxy-6-methyl-1,3,3m,7-
A green-sensitive, high-sensitivity silver halide emulsion layer is obtained by adding citrazaindene 1, o, , 1-phenyl-5-mercaptothiol, and rasol 10.0 ezH.

Furthermore, as a magenta coupler, 2-C2,4-di-t-
pentylphenoxy)-N-(4-[3-(7-chloro-6-methyl-11-pyrazolo[5,1-c]-1,
2,4-triazol-3-yl]propyl]phenyl]butanamide (M-3) 1.9 mol%, DIR compound (D-3) 0.03 mol%, colored magenta coupler (CM-1) 0 Add .3 mol% and a high boiling point solvent to ethyl acetate 200+*1, heat and dissolve to form 7.5 containing sodium triisopropylnaphthalene sulfonate.
76 into an aqueous gelatin solution and emulsified and dispersed in a colloid mill, the above green-sensitive high-sensitivity emulsion was added to obtain silver 1.
It was coated at a weight of 0.06 g/m2.

1 communication 8; middle class Same as 712.

2. Layer 9m yellow filter 1 layer C color in gelatin aqueous solution in which colloidal silver is dispersed.
3 g of 3-di-t-octylhydroquinone and 1.5 g of di-2-ethylhexyl phthalate were dissolved in 10-1 ethyl acetate.
A dispersion of gelatin dissolved in an aqueous gelatin solution containing 0.3 g of sodium triisopropylnaphthalene sulfonate was added, and this was added to gelatin at 0.91 r/m', 2,
5-di-t-octylhydroquinone 0.11g/m”
It was applied at a ratio of 92fi to a thickness of 1.2μ.

Layer 10: Blue-sensitive silver halide emulsion layer A silver iodobromide emulsion (average grain size 0.6μ, containing 6 mol% silver iodide) was chemically sensitized with gold and sulfur sensitizers, and further sensitizing dye as anhydrous 5,5'-dimethoxy-3,3'-di(3-sulfopropyl)thiacyanine hydroxide (S
D-7) and then 4-hydroxy-6-methyl-
20.0 mg of 1,3,3m,7-titrazainden t,og,1-phenyl-5-mercaptotetrazole was added and adjusted in a conventional manner to prepare a blue-sensitive, low-sensitivity silver halide emulsion.

Furthermore, as a yellow coupler, N -(5-((4-[
2,4-di-L-pentylphenoxy]-1-oxobutyl]amino]-2-chlorophenyl]-α-(2゜2
-dimethyl)-1-oxopropyl)-3,5-dioxo-1-phenyl-2-phenylmethyl-1,2゜4-
Add 30 mol% of triacylidine-4-acetamide (Y-1) and a high boiling point solvent into 300 ml of ethyl acetate,
The above blue-sensitive low-sensitivity emulsion was added to a dispersion that was dissolved by heating, added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate, and emulsified and dispersed in a colloid mill to obtain a lio, 5 g/m''. Apply as shown.

Layer 11: Blue-sensitive high-sensitivity silver halide emulsion layer A silver iodobromide emulsion (containing 7% converted silver with an average grain size of 1.2 μm) was sensitized with gold and sulfur sensitizers, and further As a sensitizing dye, 5
Add D-7, then 4-hydroxy-6-methyl-1
,3,3a,7-chitrazaindene1. Add 10.0 mg of Og, 1-phenyl-5-mercaptotetrazole and adjust in the usual manner to prepare a blue-sensitive, high-sensitivity silver halide emulsion.

Furthermore, 11 mol% of the yellow coupler (Y-1,) and a high boiling point solvent were added to 240 mZ of ethyl acetate, dissolved by heating, and added to a 7.5% gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate, and placed in a colloid mill. The above-mentioned blue-sensitive high-sensitivity emulsion was added to the emulsified dispersion and coated at a silver weight of 0.35 g/-2.

Layer 12: Intermediate layer 2-[2-hydroxy-3,5-di-t-pentylphenyl]benzotriazole as a high-boiling solvent and ultraviolet absorber was added to 4 ml of ethyl acetate, and sodium triisopropylnaphthalene sulfonate was added.7. It was added to a 5% aqueous gelatin solution and emulsified and dispersed using a colloid mill. To this, add gelatin at a rate of 1.0 g/m'' to a dry film thickness of 1.0 μ-
It was applied so that

Layer 13: 4 g of gelatin, 0.2-bisvinifresulfonylethane per 100 mN of protective layer. Sample 11 was prepared by applying an aqueous gelatin solution containing gelatin at a rate of 1.3 g/m'' to a dry film thickness of 1.2 μm.

Next, add Table 2 to the gelatin aqueous solution used when preparing sample 11.
Samples 12 to 39 were prepared in the same manner as Sample 11, except that the water-soluble coupler of the present invention shown in 1 was added in an amount of 5 mol % based on the photosensitive silver halide in the sample.

Each sample was wedge-exposed and treated in the same manner as in Example-1, followed by sensitometry, and the sensitivity and maximum color density (D Furthermore, the graininess (wax) at an image density of fog + 0.3 was determined for each photosensitive layer.
RMS) was measured. The results are shown in Table-2.

Margins below *In each photosensitive layer, relative values are shown when the sensitivity of sample 1 is set as 100.

As can be seen from 'l<2, samples 12 to 39 of the present invention containing the water-soluble couplers of the present invention all exhibit a significant improvement in graininess without decreasing the sensitivity or maximum color density. In particular, the general formulas [11], [■] and [
Samples 12-2 containing a water-soluble coupler represented by
Sample No. 8 was excellent in graininess improvement. Moreover, it can be seen that Samples 16 to 26 containing the water-soluble couplers represented by the general formulas [X[] and [X t[[] have even greater graininess improvement effects and are more excellent.

As described above, it can be seen that the present invention is very effective in improving graininess even in multilayer multilayer color photographic materials.

Example 3 After wedge exposure, sample 11 prepared in Example 2 was immersed in a prebath (described below) containing the water-soluble coupler of the present invention immediately before development, and was sufficiently swollen to form the water-soluble coupler of the present invention. was incorporated into the sample, and then the same treatments and measurements as in Example-2 were performed. As a comparison, when a pre-bath was not used and a water-soluble coupler of the present invention was contained in the developer as shown in Table 3 (Experiments 2 to 5),
Although the graininess is improved, the sensitivity and maximum color density are greatly reduced.On the other hand, in the case of the present invention, which contains a water-soluble coupler by immersing the sample in a pre-bath containing the water-soluble coupler, It can be seen that in all of Experiments 3 to 17, graininess was significantly improved without decreasing sensitivity or maximum color density.

Claims (2)

[Claims] (1) A silver halide color photographic material characterized by containing a water-soluble coupler capable of a coupling reaction with an oxidized form of a color developing agent. (2) The silver halide color photographic light-sensitive material according to claim 1, wherein the water-soluble coupler has a structure represented by the following general formula [I] or [II]. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Represents a group that can be separated by reaction. A_1 and B_1 each represent -N= or =C<, and Z is ▲
There are mathematical formulas, chemical formulas, tables, etc. Together with ▼, it represents the atomic group necessary to form a ring. A_2 and B_2 each have ▲mathematical formulas, chemical formulas, tables, etc.▼, -CN, ▲have mathematical formulas, chemical formulas, tables, etc.▼
, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, -NO_2, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -SO_2-R or represents an aryl group. R, R' and R'' each represent a hydrogen atom or a monovalent organic group. Also, A_2 and B_2 may be bonded to each other to form a ring.]