JPS62250433A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable the rapid processing, to increase the sensitivity and to reduce the fog and color turbidity by incorporating a specified hydroquinone compound which inactivates the oxidized product of a color developing agent into a photographic constituent layer in >=0.02 weight ratio to all of couplers. CONSTITUTION:A hydroquinone compound which inactivates the oxidized product of a color developing agent is incorporated into a photographic constituent layer of a silver halide color photographic sensitive material in >=0.02 weight ratio to all of couplers in the layer. The hydroquinone compound used is represented by formula I (where R1 is optionally substituted alkyl, n=1, 2 or 3, the total number of C atoms in R1 is >=8, in case of n>=2, groups R1 may be different from each other, R2 is halogen, hydroxyl, sulfo or carboxyl, m=0, 1, 2 or 3, in case of m>=2, groups R2 may be different from each other and n+m<=4). The sensitive material is composed of two or more photosensitive silver halide emulsion layers and one of the layers is a silver halide emulsion layer contg. silver halide particles having >=80mol% silver chloride content. A hydroquinone compound represented by formula II (where each of J and J' is alkylene, each of R3 and R3' is alkyl or the like and the total number of C atoms in J', R3 and R3' is >=6) may be used. The compound gives high sensitivity and reduces color turbidity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic material having a silver halide emulsion layer containing silver halide grains containing 80 mol% or more of silver chloride. The present invention relates to a silver halide color photographic light-sensitive material that can be rapidly processed, has high sensitivity, has low fog, has little color turbidity, and has excellent color reproducibility.

[Prior art and its problems]

In recent years, there has been a demand in the industry for silver halide color photographic materials that can be rapidly processed.

In other words, silver halide color photographic light-sensitive materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that processing is received. In recent years, it has become necessary to process and return the material to the user within a few hours of receipt, and there is an urgent need to develop silver halide color photographic materials that can be processed even more rapidly. It's broken.

As one of the technologies to meet such demands for speeding up, Japanese Patent Application Laid-open No. 58-184142 and Japanese Patent Publication No. 56-189
A technique for reducing silver bromide of silver halide as described in No. 39 is known. Furthermore, high chloride silver halide emulsion (8
It means silver halide containing 0 mol% or more of silver chloride. ) is known to be able to be processed significantly faster. There may be many reasons for this, but one of the reasons may be that it is highly soluble. In conventional silver halide photographic materials, especially color photographic papers, a blue-sensitive emulsion layer using silver halide grains with a large grain size is located at the bottom layer, which makes it difficult to develop the blue-sensitive emulsion layer. The problem was a decline in sexuality. However, by using a high chloride silver halide emulsion, not only these problems are solved, but also a significant reduction in the processing time is achieved. In particular, high chloride silver halide emulsions have a remarkable effect of accelerating development when they do not contain bromide ions, which are commonly used in color developing solutions.

Furthermore, since silver chloride hardly absorbs visible light, when it is used in silver halide color photographic light-sensitive materials, the blue sensitivity of green-sensitive emulsions and red-sensitive emulsions and blue-sensitive emulsions are higher than that of conventional emulsions. It is known that color reproducibility is improved in that the difference between blue sensitivity and blue sensitivity is expanded.

However, although high chloride silver halide emulsions are known to have these advantages, they have low sensitivity because they hardly absorb visible light, and are particularly disadvantageous when used as blue-sensitive emulsions.

In addition, fogging tends to occur, and when trying to obtain the sensitivity and maximum density required for photographic performance, fog increases, making it impossible to obtain satisfactory photographic performance. It is known that development processing is performed in the presence of a development inhibitor such as potassium bromide, azoles, and azaindenes in order to suppress fog to a low level. However, the use of these development inhibitors has an undesirable effect from the viewpoint of speeding up development, since the area to be developed also receives a certain degree of development inhibition effect at the same time.

Furthermore, when a silver halide color photographic light-sensitive material having a high chloride silver halide emulsion layer is rapidly subjected to color development processing,
Since the oxidized product of the color developing agent produced in excess diffuses into other silver halide emulsion layers other than the white layer, color turbidity tends to occur and color reproducibility tends to deteriorate.

In particular, when a silver halide color photographic light-sensitive material having a high chloride silver halide emulsion layer is subjected to ultra-quick color development processing using a color developing solution that does not contain bromide ions, fog,
Also, there is a problem that color turbidity tends to increase significantly.

[Purpose of the invention]

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to enable significantly rapid processing, obtain high sensitivity, reduce fogging, reduce color turbidity, and improve color reproducibility. An object of the present invention is to provide a silver halide color photographic light-sensitive material with excellent properties.

[Structure of the invention]

As a result of intensive research by the present inventors, the object of the present invention is to provide a silver halide color having at least one silver halide emulsion layer containing silver halide grains having 80 mol% or more of silver chloride on a support. In a photographic light-sensitive material, a hydroquinone compound that deactivates the oxidized form of a color developing agent represented by the following general formula [I] is added in the photographic constituent layer in a weight ratio to all the couplers in the photographic constituent layer. This was achieved using a silver halide color photographic material characterized by containing 0.02 or more.

General formula [■] H tI [In the formula, R is a substituted or unsubstituted alkyl group, and n represents an integer from 1 to 3, provided that the total number of carbon atoms in R1 is 8 or more, and n is In the case of 2 or more, R1 may be the same or different. R2 represents a halogen atom, a hydroxyl group, a sulfo group, or a carboxyl group. m is O
represents an integer from 3 to 3, and when m is 2 or more, R2 may be the same or different. Further, the sum of n and m is 4 or less. ] The hydroquinone compound of the present invention has the following general formula (I
This includes compounds represented by I). Among the hydroquinone compounds of the present invention, the compound represented by the general formula (II) is excellent because it provides high sensitivity and has remarkable improvement effects such as suppressing color turbidity to a low level.

General formula (II) H [In the formula, J and J' represent an alkylene group, and R3 and R1' represent a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, or aryol group. J.

J'+Rff+R: The total number of carbon atoms in l' is 6 or more. ] It is a surprising fact that the present invention not only enables rapid color development processing and improves color reproducibility such as reducing fog and color turbidity, but also provides high sensitivity. This was something that no one expected.

[Specific structure of the invention]

Hereinafter, the configuration of the present invention will be explained in more detail.

The light-sensitive silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention is a silver halide emulsion containing silver halide grains containing 80 mol % or more of silver chloride. The emulsion preferably has a silver chloride content of 95 mol% or more, particularly preferably 100 mol%.

This silver halide emulsion may contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride. In this case, silver bromide is contained in an amount of 20 mol% or less, preferably 5 mol% or less. When silver iodide is present, it is usually 1 mol% or less, preferably 0.5 mol% or less, and most preferably 0%. Such silver halide grains having 80 mol% or more of silver chloride according to the present invention account for 80% or more by weight of all the silver halide grains in the silver halide emulsion layer containing the silver halide grains. It is preferably contained, and more preferably 100%.

The silver halide color photographic light-sensitive material of the present invention can be composed of two or more light-sensitive silver halide emulsion layers. At least one of these two or more photosensitive silver halide emulsion layers must be a silver halide emulsion layer containing silver halide grains containing 80 mol % or more of silver chloride. There are no particular restrictions on the composition of silver halide in other photosensitive silver halide emulsion layers, but at least
It is preferable to contain silver chlorobromide grains or silver chloroiodide grains containing 0 mol % of silver chloride. The amount of silver bromide and silver iodide in the silver halide color photographic material of the present invention is preferably about 30 mol% or less, more preferably about 10 mol% or less, based on the total silver halide emulsion. It is.

These silver halides may be produced by an ammonia method, a neutral method, an acidic method, etc., or by a simultaneous mixing method, forward mixing method, back mixing method, conversion method, etc. It may be something like that.

The crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure in which the inside and outside are different. Further, the silver halide may be a surface latent image type that forms a latent image mainly on the surface, or an internal latent image type that forms a latent image mainly inside the grain.

In addition, the silver halide emulsion of the present invention includes salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum, and gold (for example, ammonium chloroparadate, potassium chloroparadate, potassium chloroparadite, potassium chloroaurate, etc.). Noble metal sensitization with active gelatin, sulfur sensitization with unstable sulfur (e.g. sodium thiosulfate, etc.), selenium sensitization with selenium compounds, stannous salts,
Reductive enhancement with polyamines, thiourea dioxide, etc. and low pAg can be performed.

Further, these silver halide emulsions can be optically sensitized using various aggravating dyes in order to impart photosensitivity in a desired wavelength range. Preferred exacerbating pigments include:
For example, U.S. Patent No. 1.939.201, U.S. Patent No. 2.07
No. 2,908, No. 2.739.149, No. 2, 2
No. 13.995, No. 2.493.748, No. 2.
519.001, West German Patent No. 929.080,
The cyanine dyes, merocyanine dyes, or composite cyanine dyes described in the specifications of British Patent No. 505.979 can be used alone or in combination of two or more.

These various optical sensitizing dyes are used for purposes other than their original purpose, such as preventing capri, preventing deterioration of photographic performance due to storage of silver chloride color photographic materials, and adjusting development (for example, gradation control, etc.) It can also be used for other purposes.

Next, the hydroquinone compound of the present invention will be explained in more detail.

First, the compound that deactivates the oxidized form of the color developing agent is a compound that reacts with the oxidized form of the color developing agent, deactivates it, and prevents the oxidized form of the color developing agent from reacting with the coupler.

In the above general formula [I], the alkyl group represented by R1 is preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, ethyl group, propyl group, t-
Examples include butyl group, n-octyl group, and -dodecyl group. Substituents that RI has include sulfo groups, carboxyl groups, cyano groups, hydroxyl groups, halogen atoms (e.g., fluorine atoms, chlorine atoms, bromine atoms, etc.),
-COOR,.

Examples include C0R5, OR&, 5OJt, -NH3O□R6, and the like. Here R4, Rs, Ri, Rt, Rs
represents an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group.

Further, the alkyl group represented by R4 to R6 is preferably a straight chain or branched alkyl group having 1 to 1 carbon atoms,
For example, methyl group, ethyl group, propyl group, butyl group, hexyl group, isobutyl group, etc.; cycloalkyl group includes, for example, cyclopentyl group, cyclohexyl group, etc., and alkenyl group includes those having 2 to 18 carbon atoms. are preferable, such as allyl group, octenyl group, octadecenyl group, etc., and examples of the aryl group include phenyl group, naphthyl group, etc. Also, R4, Rs, Ri, Rt
, Ra may further have a substituent.

-a R2 in formula (1) represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a hydroxyl group, a sulfo group, or a carboxyl group, and a sulfo group or a carboxyl group is preferable. n is preferably 1 or 2, and m is preferably 0 or l.

The alkylene group represented by J and J' in general formula (n) is
Straight chain and branched alkylene groups with 1 to 1 carbon atoms
An 8-branched alkylene group is preferred.

The alkyl group represented by R,, R,' in the general formula (It) is preferably a straight chain or branched one having 1 to 18 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group. cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, etc., and alkenyl groups preferably have 2 to 18 carbon atoms, such as allyl groups, octenyl groups, octadecenyl groups, etc. Examples of the group include a phenyl group and a naphthyl group. Also, R3+R
, / may further have a substituent, and examples of the substituent include the same substituents as those of R1 described above.

The hydroquinone compounds of the present invention can be used alone or in combination of two or more. The hydroquinone compound of the present invention can be added to any layer among the photographic constituent layers, but is preferably added to a light-sensitive silver halide emulsion layer or between two light-sensitive silver halide emulsion layers. added to the intermediate layer. More preferably, it is added to a silver halide emulsion layer containing silver halide grains having 80 mol % or more of silver chloride or a layer adjacent thereto. Additionally, along with the hydroquinone compound of the present invention,
It is also possible to add a quinone compound which is an oxidized product of the hydroquinone compound.

The hydroquinone compound of the present invention needs to be contained in a weight ratio of 0.02 or more to all the couplers in the photographic constituent layers, preferably 0.02 to 1, more preferably 0.02 to 1. Contains 0.2. Further, in a photosensitive silver halide emulsion layer containing a coupler, the weight ratio of the coupler to the coupler contained in the layer is 0.01 to 1, preferably 0.01 to 0.1. The amount to be added is defined by the total amount when two or more hydroquinone compounds of the present invention are used in combination.

In order to add the hydroquinone compound used in the present invention to the photographic constituent layer, it can be added as is in the coating solution to form the layer, or in a solvent that does not have an adverse effect on the photosensitive material.
For example, it can be added after being dissolved in water, alcohol, etc. to an appropriate concentration.

Preferably, the hydroquinone compound is dissolved in a high boiling point solvent and/or a low boiling point organic solvent, and then added after being emulsified and dispersed in an aqueous solution.

Examples of high boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Examples of high boiling point organic solvents that can be used in the present invention include U.S. Pat.
No. 4, No. 2,835,579, No. 3,287.134
No. 2,353.262, No. 2,852,383, No. 3,554,755, No. 3,676, 137,
3,676.142, 3,700.454, 3,748.141, 3,779,765, 3
, No. 837.863, British Patent No. 958.441, L.
222,753, 0LS2.538.889, JP-A-47-1031, JP-A-49-90523, JP-A-50-2
No. 3823, No. 51-26037, No. 51-2792
No. 1, No. 51-27922, No. 51-26035,
No. 51-26036, No. 50-62632, No. 53
-1520, 53-1521, 53-1512
No. 7, No. 54-119921, No. 54-119922
No. 55-25057, No. 55-36869, No. 56-19049, No. 56-81836, Special Publication No. 4
Examples include those described in No. 8-29060.

Low-boiling or water-soluble organic solvents that can be used with or in place of high-boiling solvents are described in U.S. Patent No. 2,801.171;
Examples include those described in No. 2,949,360 and the like. Organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and water-soluble organic solvents include acetone, Examples include methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol, and the like.

The hydroquinone compound of the present invention may be added at any time during the manufacturing process, but it is preferable to add it immediately before coating.

Typical specific examples of the hydroquinone compound of the present invention will be described below, but the present invention is not limited thereto.

HQ-1 *-CIItCHzCIItCIlzCOOCHtCH
CHtClltCIIoC11ffllCH3 しH3 * CHtClltCHtCOOCHtCHtOCH
zCllzCHtCHsIA-(CHt)scOO-C
HtCII(C1,)4CH31tcos *-(CIl ri 4COO-(CIt) go (
CI ri *C1l sC1+.

*-(Cut) *COO-(CHgC00-(CHs
CLHQ-13 HQ-14 H υn HQ-15 0■ HQ-16 H υh HQ-17 0M υ■ HQ-18 CI υH HQ-19 H CI.

C.I.

HQ-28 0H H HQ-29 H HQ-32 0■ υh HQ-34 II υH HQ-35 HQ-36 H υH HQ-37 Curve υ■ HQ-33 0M The dye image-forming coupler used in the present invention is particularly limited. Although various couplers can be used, the compounds described in the following patents are included as representative examples.

Examples of yellow dye image-forming couplers include 4-equivalent or 2-equivalent acylacetamide type and benzoylmethane type couplers.
equivalent couplers, these are described, for example, in US Pat.
No. 778.658, No. 2.875.057, No. 2
．． 908.573, 2,908,513, 3.227°155, 3,227.550, 3.253.924, 3,265.506,
3,277.155, 3.341.331, 3.369.895, 3.384.657
No. 3゜408, 194, No. 3.415.65
No. 2, No. 3,447.928, No. 3.551.1
55, German Patent No. 3,582.322, German Patent No. 3.725°072, German Patent No. 1.547.868, German Patent No. 2
．． 057.941, 2,162.899, 2.163.812, 2.213.461, 2,219,917, 2,261.361,
Japanese Patent Publication No. 2.263.875, Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 48-29432, Japanese Patent Publication No. 48-66834,
No. 49-10736, No. 49-122335, No. 5
No. 0-28834, No. 50-132926, No. 55-
It is described in each specification of No. 144240 and No. 56-87041.

The magenta dye image-forming couplers include 4-equivalent or 2-equivalent magenta dye image-forming couplers of the 5-virazolone type, pyrazoloazole type, pyrazolinobenzimidazole type, indasilone type, and cyanoacetyl type, and these are, for example, Patent No. 2,600,788, Patent No. 3,061,432, Patent No. 3,062.653, Patent No. 3,127,269, Patent No. 3.311.476,
Same No. 3.152.896, No. 3,419.391, No. 3,519゜429, No. 3,558.318
No. 3.684.514, No. 3.705,89
No. 6, No. 3,888.680, No. 3.907.5
No. 71, No. 3,928,044, No. 3.930,
No. 861, No. 3, No. 930.816, No. 3,933
．． No. 500, JP-A-49-29639, JP-A No. 49-11
No. 1631, No. 49-129538, No. 51-112
No. 341, No. 52-58922, No. 55-62454
No. 55-118034, No. 56-38643,
No. 56-135841, Special Publication No. 46-60479,
No. 52-34937, No. 55-29421, No. 55
-35696, British Patent No. 1.247.493, Belgian Patent No. 792.525, West German Patent No. 2.1
No. 56.111.

Examples of cyan dye image-forming couplers include 4-equivalent or 2-equivalent cyan dye image-forming couplers of phenol type and naphthol type, and these are described, for example, in U.S. Pat. No. 730, No. 2,434,272, No. 2,474,293
No. 2. '698,794, same No. 2,706,6
No. 84, No. 2,772゜162, No. 2,801.
No. 171, No. 2.895.826, No. 2,908
．． No. 573, No. 3,034,892, No. 3,04
No. 6,129, No. 3,227,550, No. 3,2
No. 53,294, No. 3.311,476, No. 3.
386.301, 3.419.390, 3
, No. 458,315, No. 3.476.563, No. 3.516.831, No. 3.560,212, No. 3.582,322, No. 3.583,971. ,
Same No. 3,59L383, Same No. 3,619゜196,
No. 3,632,347, No. 3,652,286, No. 3.737,326, No. 3.758.308
No. 3,779,768, No. 3,839,04
4, West German Patent No. 2,163,811, West German Patent No. 2.
No. 207.468, Special Publication No. 39-27563, No. 45
-28836, JP-A No. 47-37425, JP-A No. 50-
No. 10135, No. 50-25228, No. 50-112
No. 038, No. 50-117422, No. 50-1304
No. 41, No. 53-109630, No. 55-32071
No. 55-163537, No. 56-1938, No. 56-13643, No. 56-29235, No. 56-
No. 65134, No. 56-104333, and Research Disclosure (Research Disclosure).
osure) 1976, 14853, etc.

In the present invention, it is advantageous to use gelatin as the hydrophilic colloid for dispersing silver halide, but other hydrophilic colloids can also be used.

Examples of preferable hydrophilic colloids include gelatin such as alkali-treated seratin or acid-treated gelatin, but a portion of this gelatin may be substituted with derivative gelatin such as phthalated gelatin, phenylcarbamoyl gelatin, albumin, or agar. , gum arabic, alginic acid, partially hydrolyzed cellulose derivative, partially hydrolyzed polyvinyl acetate 1
．． Mention may be made of polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone and copolymers of these vinyl compounds.

The silver halide color photographic material of the present invention may contain various known photographic additives. Such examples include, for example, ultraviolet absorbers (such as benzophenone compounds and benzotriazole compounds);
Dye image stabilizers (for example, phenolic compounds, bisphenol compounds, hydroxychroman compounds, bispirochroman compounds, hydantoin compounds, dialkoxybenzene compounds, etc.), stain inhibitors other than the hydroquinone compounds of the present invention, Surfactants (e.g., sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkylsuccinate ester sulfonate, polyalkylene glycol, etc.), water-soluble anti-irradiation dyes (e.g., azo compounds, styryl compounds, triphenylmethane) hardening agents (e.g. halogen s-triazine compounds, vinyl sulfone compounds, acryloyl compounds, ethyleneimino compounds, N-methylol compounds, epoxy compounds, etc.) (aluminum salts, etc.), film property improvers (e.g. glycerin, aliphatic polyhydric alcohols, polymer dispersions (latex), solid/liquid paraffin, colloidal silica, etc.), fluorescent whitening agents ( Examples include diaminostilbene compounds) and various oil-soluble paints.

The photographic layers constituting the silver halide color photographic light-sensitive material of the present invention include, in addition to the red-sensitive emulsion layer, green-sensitive emulsion layer, and blue-sensitive emulsion layer, a subbing layer, an intermediate layer, and a yellow-sensitive emulsion layer. Each layer such as a filter layer, an ultraviolet absorbing layer, a protective layer, and an antihalation layer can be provided as necessary.

The support for the silver halide color photographic light-sensitive material of the present invention includes supports such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, and polystyrene, or, for example, paper and polyolefin (
For example, a laminate of two or more substrates, such as a laminate with polyethylene, polypropylene, etc., can be used as appropriate depending on the purpose.

This support is subjected to various surface treatments on -C in order to improve its adhesion to the silver halide emulsion layer, such as roughening the surface mechanically or with an appropriate organic solvent, and electron impact treatment. Alternatively, a surface treatment such as flame treatment, or a subbing treatment to provide a subbing layer can also be used.

The silver chloride coupler photographic light-sensitive material of the present invention includes all kinds of silver halide color photographic light-sensitive materials such as color negative films, color positive films, color reversal films, and color papers, but is particularly preferably used in color papers.

As the color developing agent used in the color developing solution for color development processing of the silver halide color photographic light-sensitive material of the present invention, aromatic primary amine compounds, particularly P-phenylenediamine compounds, are representative. As a preferable example, N
, N-diethyl-P-phenylenediamine hydrochloride, N-
Ethyl-P-phenylenediamine hydrochloride, N,N-dimethyl-P-phenylenediamine hydrochloride, 2-amino-5
-(N-ethyl-N-dodecylamino)-toluene, N
-Ethyl-N-(β-methanesulfonamidoethyl)-
3-Methyl-4-aminoaniline sulfate, N-ethyl-
N-β-hydroxyethylaminoaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-P-)luenesulfonate, N,N-diethyl-3-methyl-4-amino Aniline, N-ethyl-N-(β-hydroxyethyl)-3-methyl-4-aminoaniline, and the like can be mentioned. These color developing agents may be used alone or in combination of two or more, and one or more of these color developing agents and other black and white developing agents such as hydroquinone, 1-phenyl-
It may be used in combination with 3-pyrazolidone and N-methyl-P-aminophenols. This color developing agent may be included in the silver chloride color photographic light-sensitive material of the present invention. In this case, the amount of this color developing agent added is usually 0.000000000000000000 ml per mole of silver halide contained in the color photographic light-sensitive material. The amount ranges from 2 mol to 2 mol, preferably from 0.4 mol to 0.7 mol.

In addition to the above-mentioned color developing solution, the color developing solution includes, for example, alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, tribasic sodium phosphate, potassium carbonate, potassium hydrogen carbonate, and N,N-diethylhydroxylamine. , preservatives such as sodium sulfite, potassium sulfite, and glucose, organic solvents such as methanol, ethanol, butanol, benzyl alcohol, ethylene glycol, and diethylene glycol, development regulators and fluorescent brighteners such as citrazic acid and polyethylene glycol, and heavy metals. Various photographic additives known in the photographic field, such as ion hiding agents and development accelerators, can be contained as necessary.

The color photographic light-sensitive material of the present invention is developed with a color developing solution that does not contain any water-soluble bromide or contains a very small amount of water-soluble bromide. When an excessive amount of water-soluble bromide is contained, the development speed of the color photographic material is drastically reduced, making it impossible to achieve the object of the present invention. The bromide ion concentration in the color developer is calculated in terms of potassium bromide.
Usually about 0.1g or less, preferably 0.05g per serving
It is as follows.

Development control agents (fog control) contained in the color developing solution include chlorides such as sodium chloride and potassium chloride, or chlorides such as adenine, guanine, etc.
A compound described in Japanese Patent No. 5345 that has an acid dissociation constant of 10-B or less and a solubility product with silver ions of 10-'' or less is used.

The pH of the color developing solution used in the present invention is generally 9.0 to 9.0.
12.0, preferably between 9.5 and 11.0.

The color photographic material of the present invention is color developed by a conventionally known method. That is, the imagewise exposed silver chloride color photographic material is color developed with the color developing solution of the present invention to form a dye image and a silver image. Thereafter, in order to leave only the dye image, a negative-positive method can be used in which the silver salt is oxidized to silver salt in a bleaching bath, and then the remaining silver halide and other silver salts are dissolved and removed in a fixing bath. Also,
A negative silver image is created by developing with a developer containing a black and white developing agent, followed by at least one full exposure or fog treatment with a suitable fogging agent, followed by color development, bleaching and fixing. A color inversion method can be used to form a .

The bleaching and fixing treatments performed to leave a dye image may be performed in separate steps, but from the standpoint of rapid processing, it is preferable to perform the bleaching treatment and the fixing treatment at the same time.

The bleaching agent for individual bleaching treatment is iron (I).
II), cobalt (I [I), chromium (Vl), copper (I
Compounds of polyvalent metals such as I), peracids, quinones, nitroso compounds, etc. can be used. Specifically, ferricyanide, dichromate, organic acid salts of iron (I) or cobalt (I), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanol tetra Aminopolycarboxylate salts such as acetic acid or complex salts of organic acids such as citric acid, tartaric acid, malic acid; persulfates, permanganates; nitrosophenols, etc. can be used.

Examples of fixing agents include thiosulfates (for example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, etc.), thiocyanates (for example, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, etc.), 3,6 -Thioether compounds such as 1,8-octanediol can be mentioned.

The processing temperature of various processing steps such as color development, bleach-fixing, washing with water (or stabilization as an alternative to washing), and drying of the color photographic material of the present invention is set at 30°C or higher from the viewpoint of rapid processing. Preferably, this is done.

〔Example〕

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

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare 11 ml of silver halide color photographic light-sensitive material samples.

N1...1.2g/rrr gelatin, 0.32g
A blue-sensitive silver halide emulsion (silver chloride content: 50 mol %) of 0.50 g/m2 was dissolved in 0.50 g/m of dioctyl phthalate. , so g/m of yellow coupler (Y-1).

Layer 2...0.70 g/trr gelatin, 8m
g/bo irradiation dye (AI-1) and 4 mg
An intermediate layer consisting of (A I -2) of /m'.

Layer 3 = 1.25 g/rd gelatin, 0.2
0 g/m green-sensitive silver halide emulsion (silver chloride content 50 mol%), 0.62 g/n? dissolved in 0.30 g/nl dioctyl phthalate. Magenta coupler (M-1) layer 4...intermediate layer consisting of 1.2 g/rd gelatin.

Layer 5 - 1.40 g/rrr gelatin, 0.2
Red-sensitive silver halide emulsion (silver chloride content 50 mol%) of 0 g/n (containing 0.45 g/m cyan coupler (C-1) dissolved in 0.20 g/m dioctyl phthalate) layer.

Layer 6 - 1.0 g/rri of gelatin and 0.20 g/m
to dioctyl phthalate? 0.30 g dissolved /
A layer containing an ultraviolet absorber (UV-1) of m.

Layer 7: A layer containing 0.5 g/m of gelatin.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-3-triazine sodium was added in layers 2.4 and 7.
Each was added in an amount of 0.017 g per 1 g of gelatin.

In addition, the halogen composition of the silver halide in layers 1, 3, and 5 was changed as shown in Table 1, and the hydroquinone compound of the present invention was added as shown in Table 1.
18 was created.

(C-1) CsH++(t) (AI-1) (AI-2) (UV-1) Each of the photosensitive material samples N111 to 18 was exposed through an optical wedge and then processed in the following steps.

Processing process (35℃) Color development 45 seconds and bleach fixing for 1 minute 15 seconds
Stabilization for 45 seconds Drying for 1 minute and 30 seconds 60 to 80°C for 2 minutes The composition of each treatment solution is as follows.

Color developing solution Bleach-fixing solution Stabilizing solution Sensitometry was performed on each sample after the above treatment to determine the sensitivity (S) and capri (Fog) of the blue-sensitive emulsion layer. The results are shown in Table-1.

As is clear from Table 1, Samples 11hl to 11h4, which do not use high chloride silver halide emulsions, are poor in speed, have low sensitivity when processed quickly for 45 seconds, and do not have sufficient photographic performance. Samples 1'h5 and 11h8, which use the high chloride silver halide emulsion of the present invention but contain less than the specified amount of the hydroquinone compound of the present invention, can achieve rapidity but have low sensitivity. , Capri is expensive. In contrast, using the high chloride silver halide emulsion of the present invention,
Sample N16 of the present invention containing the hydroquinone compound of the present invention within the specified amount range of the present invention, Nu? ,
It can be seen that all of llh 9 to 18 are fast, have high sensitivity, and have low capri. Furthermore, samples of the present invention, 11h9~
Among the above, N19. is a sample in which HQ-2 selected from the hydroquinone compounds of the present invention represented by the general formula [■] is used alone or in combination within the more preferable addition amount range of the present invention. It can be seen that N113 has high sensitivity and excellent photographic performance.

Example 2 Each of the photosensitive material samples 1 to 18 was exposed to blue light through an optical wedge (using an interference filter with a center wavelength of 460 nm) and then processed according to the development process described above (only 45 seconds of development). The composition of each treatment liquid is also as described above.

After the above development process, a densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.,
Sakura densitometer PDA-60), the blue light absorption density D'B of the unexposed area, the blue light absorption density DB of the exposed area, the green light absorption density D'G of the unexposed area, and the green light absorption density of the exposed area The absorption concentration DG was determined.

Next, the ratio (Q) between the blue light absorption density excluding the fog density and the green light absorption density was determined according to the following formula.

Optical density (D) Q is the Q value under the condition of DB=1.0.

Let Q2 be the Q value under the condition of DB=2.0.

The results are shown in Table-2.

Table 2 As is clear from Table 2, although high chloride silver halide emulsions were used, samples 5 and 8 contained less than the specified amount of the hydroquinone compound of the present invention.
The value of Q is large (the green turbidity in the blue part is large), and the color turbidity is large, but the sample of the present invention, Magnet 6. Il
h? , Han 9 to Arashi 18 are Q.

゛ is small, and color turbidity is improved. In addition, for sample magnets 1 to 4 with high silver bromide content, Q is small, but due to color turbidity due to blue light absorption of silver bromide, Q, to Q
There is a significant deterioration in color reproducibility to 2.

Here, too, when compared with the same addition amount, it can be seen that color reproducibility is improved more effectively when HQ-2 selected from the general formula (If) is used alone or in combination.

Representative Patent Attorney Toru Takatsuki Procedural Amendment Form) July 16, 1985 Director General of the Patent Office Michibu Uga 1, Indication of the Case 1986 Patent Application No. 093538 3, Person making the amendment Related Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(1'27) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Subject of amendment Written amendment to the specification December 23, 1988 1, Indication of the case 1988 Patent Application No. 093538 2, Title of the invention Silver halide color photographic light-sensitive material 3, relationship with the amended person case Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Subject of amendment In the specification, "Detailed Description of the Invention" column 7, Contents of amendment As shown in the attached sheet 11... jil)
The structural formula of r(AI-2)J on page 44 of the same book is as follows. Correct to.

” that's all Procedural amendment.

Commissioner of the Patent Office Kuro 1) Mr. Yu Akira1, Indication of the case 1986 Patent Application No. 0935382, Name of the invention Silver halide color photographic light-sensitive material 3, Person making the amendment Relationship to the case Patent applicant address Tokyo 1-26-2 Nishi-Shinjuku, Shinjuku-ku Name
(127) Roku Konishi Photo Industry Co., Ltd. Dia Palace Nibancho 506 FAX 03 (2'21) 19245,
Date of amendment order Voluntary 6, Subject of amendment In the description, "Detailed explanation of the invention" column (1) July 16, 1985 r on page 44 in the specification
(AI-2)'' is corrected as follows.

” that's all

Claims (2)

[Claims] (1) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide grains having 80 mol% or more of silver chloride on a support, the photographic constituent layer has the following general formula: A hydroquinone compound that deactivates the oxidized color developing agent represented by [I] is added at a weight ratio of 0 to all the couplers in the photographic constituent layer.
．． A silver halide color photographic light-sensitive material containing 02 or more. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 is a substituted or unsubstituted alkyl group, and n represents an integer from 1 to 3. However, the total number of carbon atoms in R_1 is 8 or more, and when n is 2 or more, R_1 may be the same or different. R_2 represents a halogen atom, a hydroxyl group, a sulfo group, or a carboxyl group. m represents an integer from 0 to 3, and if m is 2 or more, R_
2 may be the same or different. Further, the sum of n and m is 4 or less. ] (2) The silver halide color photographic light-sensitive material according to claim (1), wherein the hydroquinone compound is represented by the following general formula [II]. General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. represent. J, J', R_3,
The total number of carbon atoms in R_3' is 6 or more. ]