JPH0640210B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has excellent processing stability during development and high-quality images with improved sharpness. And a silver halide color photographic light-sensitive material.

BACKGROUND OF THE INVENTION In recent years, there has been an increasing demand for silver halide color photographic light-sensitive materials (hereinafter light-sensitive materials) to have high sensitivity and high image quality (sharpness and granularity). With the increasing demand for smaller formats such as a negative film with a smaller screen size, there is an increasing demand for improved technology for improving the sensitivity and image quality of photosensitive materials. Therefore, in order to satisfy these characteristics, many technical improvements have been made in the production of photosensitive materials to date, and the performance of photosensitive materials is also improving. However,
In general, the sensitivity of a photosensitive material and the image quality are contradictory to each other. For example, when the sensitivity is increased, the quality of the image often deteriorates. There is an urgent need to cultivate the technology for obtaining profits.

In order to improve the sharpness of the light-sensitive material, studies have been made from both aspects of the optical effect and the developing effect. From the viewpoint of optical effects, there is a method of reducing the amount of light (irradiation light) scattered by hitting silver halide grains randomly dispersed in a binder such as gelatin. In this method, a coloring substance such as a dye is added to the silver halide emulsion layer to absorb light scattered by the light-sensitive silver halide grains. However, this method has a problem that it is accompanied by a desensitizing action. As another method, it has been proposed to reduce the thickness of the silver halide emulsion layer to suppress the light scattering path as much as possible. Especially in the case of a silver halide emulsion layer closer to the support,
Since the light scattering path from the surface of the photosensitive material becomes long, thinning the film can be an effective means for improving sharpness. However, in this method, it is necessary to reduce the amount of the binder used, which causes deterioration of film quality in the coupler-embedded multilayer light-sensitive material, so that the amount of the coupler added is naturally limited and it becomes difficult to obtain a good dye image. . Further, from the viewpoint of graininess, it is not preferable to reduce the amount of silver contained in the photographic emulsion layer for thinning.

The inventors of the present invention have found that the combined use of a fine grain silver halide and a non-diffusible dye in a light-sensitive material produces a synergistic effect far superior to those obtained when they are used alone. I have found

[Object of the Invention] It is an object of the present invention to provide a light-sensitive material which is excellent in image quality, particularly in image sharpness, and has improved processing stability during development without impairing sensitivity.

The above object of the present invention and other objects which will become apparent from the following description are as follows. A red-sensitive emulsion layer group comprising at least two layers having substantially the same color sensitivity on a support but different sensitivities, A silver halide color photographic light-sensitive material having a green-sensitive emulsion layer group and a plurality of non-photosensitive hydrophilic colloid layers, wherein at least one of the non-photosensitive hydrophilic colloid layers contains fine grain silver halide and the red-sensitive In the emulsion layer group, at least one of the non-photosensitive hydrophilic colloid layers located farther from the support than the red-sensitive emulsion layer closest to the support contains a non-diffusing red absorbing dye. And / or a non-diffusible green color in at least one of the non-photosensitive hydrophilic colloid layers located farther from the support than the green-sensitive emulsion layer closest to the support in the green-sensitive emulsion layer group. Sucking It found to be achieved by a silver halide color photographic material containing a dye.

[Specific Structure of the Invention] As described above, the light-sensitive material of the present invention comprises a red-sensitive emulsion layer group composed of at least two layers having substantially the same color sensitivity but different sensitivities on a support, and a green-sensitive layer. At least an emulsion layer group and a plurality of non-photosensitive hydrophilic colloid layers are coated. In the red-sensitive emulsion layer group and the green-sensitive emulsion layer group, the plurality of emulsion layers having substantially the same color sensitivity but different sensitivities may be adjacent to each other or may be separated from each other. Good. Examples of the light-sensitive material in the case where a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities are adjacent to each other include a red-sensitive silver halide emulsion layer and a green-sensitive material on a support. -Sensitive silver halide emulsion layers and blue-sensitive silver halide emulsion layers are separated into high-sensitivity silver halide emulsion layers and low-sensitivity silver halide emulsion layers.
And the layer structure that is sequentially applied in the adjacent state (forward layer structure)
Can be mentioned. An example in which the silver halide emulsion layer is separated is described as described in US Pat. No. 3,663,228. Red sensitive silver halide emulsion layers, green sensitive silver halide emulsion layers, and blue sensitive silver halide emulsion layers, each of which has a low sensitivity emulsion layer, are coated in this order from the support side, and the low sensitivity emulsion layer group comprises A two-layer unit structure (reverse layer structure) in which a high-sensitivity emulsion layer group of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer is applied in order from the support side. The light-sensitive material can be mentioned. A part or all of the light-sensitive silver halide emulsion layers having different color sensitivities and between the light-sensitive silver halide emulsion layers having the same color sensitivities but different sensitivities are non-photosensitive hydrophilic. The intermediate layer of the photosensitive colloid layer may be provided, and the uppermost layer may be provided with a protective layer of the non-photosensitive hydrophilic colloid layer.

Further, in the case of the reverse layer constitution, the fine grain silver halide is an optional intermediate layer, preferably an intermediate layer between the low-sensitivity blue-sensitive silver halide emulsion layer and the high-sensitivity red-sensitive silver halide emulsion layer, and the high-sensitivity red. An intermediate layer between the sensitive silver halide emulsion layer and the high-sensitivity green-sensitive silver halide emulsion layer, a high-sensitivity green-sensitive silver halide emulsion layer, and a yellow filter layer between the high-sensitivity blue-sensitive silver halide emulsion layer, It is added to at least one intermediate layer between the high-sensitivity blue-sensitive silver halide emulsion layer and the protective layer.
More preferably, it is added to the intermediate layer between the high-sensitivity blue-sensitive silver halide emulsion layer and the protective layer.

In the normal layer structure and the reverse layer structure, for example, the green-sensitive silver halide emulsion layer has high, medium and low sensitivity.
It may have a layer structure, and the blue-sensitive and red-sensitive silver halide emulsion layers may have the same three-layer structure.

At least one layer of the non-photosensitive hydrophilic colloid layer containing fine grain silver halide may simultaneously contain a red absorbing dye and / or a green absorbing dye, and further, a part or all of these dyes may be different from each other. It may be contained in the layer, and the latter is preferable. The silver halide color photographic light-sensitive material of the present invention can be provided with a blue-sensitive emulsion layer group in addition to the above-mentioned red-sensitive emulsion layer group and green-sensitive emulsion layer group. There may be two or more layers, and in the case of two or more layers, the emulsion layers may be adjacent to each other or may be separated from each other. When the red-sensitive and green-sensitive emulsion layer groups and the blue-sensitive emulsion layer group are composed of two or more silver halide emulsion layers having different sensitivities, each of these layers is preferably a support. In contrast, the most distant silver halide emulsion layer is defined as the layer having the highest sensitivity, and the sensitivity is gradually reduced toward the support, and there is no light-sensing between each silver halide emulsion layer. A functional layer can also be provided.

Here, the fine grain silver halide means a silver halide grain which is not exposed to light during imagewise exposure for obtaining a dye image, is not substantially developed in the developing treatment, and is not pre-coupled.

This fine grain silver halide has a silver bromide content of 0 to 100.
As long as the content is mol% and the silver halide contains silver bromide in such a ratio, it may have various compositions.

Further, it may contain silver chloride and / or silver iodide, if necessary. The fine grain silver halide preferably has an average grain size of 0.01 μm to 0.3 μm, more preferably 0.02 μm.
Those having a size of μm to 0.2 μm are used. The average grain size of such silver halide grains means the average value of the diameters of circles corresponding to the projected areas of the individual silver halide grains, and this measurement is described, for example, in "Basics of photographic engineering-silver salt photography. Ed.- "(edited by the Photographic Society of Japan, issued January 30, 1979) Paragraphs 227 to 228
It can be determined by the method described in the section.

The fine grain silver halide can be obtained in the same manner as in preparing a normal photosensitive silver halide emulsion, or according to the case of preparing a normal photosensitive silver halide emulsion. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However,
Prior to adding the fine silver halide grains to the coating solution, known stabilizers such as triazole compounds, azaindene compounds, benzthiazolium compounds, mercapto compounds and zinc compounds are added in advance. It is preferable.

When two or more non-photosensitive hydrophilic colloid layers having at least one layer are provided in the silver halide color photographic light-sensitive material of the present invention, if fine grain silver halide is added to at least one layer among them. Is enough.

The amount of fine grain silver halide added to the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention depends on several factors, such as the halogen composition of fine grain silver halide, the particle size, the bromine ion concentration in the developer, The amount of silver varies from 0.1 to 50 mg / dm ² , preferably from 1 to 10 mg / dm, depending on the photosensitive emulsion layer.
^{Is 2} . When the addition of fine grain silver halide covers two or more non-photosensitive hydrophilic colloid layers, the total amount may be the above-mentioned addition amount. In this case, it is not necessary to add the same amount of fine grain silver halide to each colloid layer. When the amount of fine grain silver halide added is less than 0.1 mg / dm ² , the developability cannot be sufficiently promoted, and when it exceeds 50 mg / dm ² , the sensitivity is remarkably lowered or the fog density is increased. , Causing a significant inconvenience in photographic performance.

The fine grain silver halide may be contained anywhere in the non-photosensitive hydrophilic colloid layer, but is preferably in the non-photosensitive hydrophilic colloid layer adjacent to the silver halide emulsion layer farthest from the support. Therefore, it is to be added to the non-photosensitive hydrophilic colloid layer on the side far from the support.

The non-diffusible green absorbing dye and / or the non-diffusing red absorbing dye in the present invention are
As long as the above-mentioned dye added during preparation of the non-photosensitive hydrophilic colloid layer is substantially present in the non-photosensitive hydrophilic colloid layer without diffusing into other layers even after the production is completed, any one may be selected. Can be used.

As an example of the non-diffusible dye, for example, a diffusible acid dye and a polymer mordant containing a basic group are allowed to coexist in the same non-photosensitive hydrophilic colloid layer to make the acid dye non-diffuse. be able to.

As the basic mordant used in the present invention, a polymer mordant containing the above basic group, for example, imidazole, pyridine, alkylaminoalkyl (meth) acrylate,
Alternatively, examples thereof include polymers containing quaternary salts thereof, aminoguanidine and the like. These basic polymer mordants preferably used in the present invention are described in detail in the respective U.S. Pat. That is,
2,548,546, 2,675,316, 2,882,156 and
3,706,563 and the like, and among them, particularly preferable basic polymer mordant in the present invention is Patent No. 2,882,156.
And the condensation products of poly (N-oxoalkyl (meth) acrylamide) with aminoguanidine as described in U.S. Pat. No. 3,706,563.

Next, typical examples of the basic polymer mordant preferably used in the present invention will be given.

[Mordant-1] n≈500 [mordanting agent-2] n≈500 [mordanting agent-3] n≈300 [mordanting agent-4] The dye used in combination with the basic polymer mordant may be any acidic dye, but preferably an acidic dye having a sulfo group or a carboxyl group, for example, an azo type or triphenylmethane. Acid dyes such as system dyes, anthraquinone dyes, acetylyl dyes, benzylidene dyes, merocyanine dyes, and oxonol dyes can be used.

Next, typical examples of the acid dye used in the present invention will be given.

[Dye-1] [Dye-2] [Dye-3] [Dye-4] [Dye-5] [Dye-6] [Dye-7] [Dye-8] [Dye-9] The above acid dye and basic polymer mordant can be synthesized by a known method, and can be contained in the non-photosensitive hydrophilic colloid layer by a known method.

Examples of preferred non-diffusible green absorbing dyes for use in the present invention are the reaction products of known magenta couplers with known color developing agents.

Examples of preferable non-diffusible red absorbing dyes include:
There are reaction products of known cyan couplers with known color developing agents.

Specific examples of the magenta coupler include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based couplers. As such a magenta coupler, U.S. Pat.Nos. 2,600,788, 2,983,608, and 3,062,653,
No. 3,127,269, No. 3,311,476, No. 3,419,391
No. 3,519,429, No. 3,558,319, No. 3,582,32
No. 2, No. 3,615,506, No. 3,834,908, No. 3,891,4
45, West German patent 1,810,464, West German patent application (OLS)
2,408,665, 2,417,945, 2,418,959, 2,42
4,467, JP-B-40-6031, JP-A-49-74027, 49-7
No. 4028, No. 49-129538, No. 50-60233, No. 50-159336
No. 51, No. 51-20826, No. 51-26541, No. 52-42121, No. 52
-58922, 53-55122, Japanese Patent Application No. 55-110943 and the like.

Further, examples of the above cyan coupler include phenol or naphthol derivatives, for example, US Pat.
No. 2,423,730, No. 2,474,293, No. 2,801,171, No. 2,895,826, No. 3,476,563, No. 3,737,326,
No. 3,758,308, No. 3,893,044, JP-A-47-3
7425, 50-10135, 50-25228, 50-112038,
The couplers described in JP-A Nos. 50-117422 and 50-130441, and the couplers described in JP-A-58-98731 are preferable.

As the known color developing agent which reacts with the above coupler, aromatic primary amine compounds, especially p-phenylenediamine compounds, are preferable, and 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-toluenesulfonate, N, N-diethyl-3-methyl-
4-aminoaniline, N-ethyl-N- (β-hydroxyethyl) -3-methyl-4-aminoaniline and the like can be mentioned.

Examples of other preferable non-diffusible red absorbing dyes include known colored cyan couplers.

Examples of known colored cyan couplers include U.S. Pat.Nos. 2,521,908, 3,034,892, and British Patent 1,255,11.
Examples thereof include compounds described in JP-A No. 48-22028.

Further, U.S. Pat.No. 3,476,563, JP-A-50-10135, 50-
Colored cyan couplers of the type in which the dye flows out into the processing bath upon reaction with the oxidation product of the color developing agent as described in 123341 can also be used.

Particularly preferred colored cyan couplers are compounds represented by the following general formulas [I] -a and [I] -b.

General formula [I] -a General formula [I] -b In formulas [I] -a and [I] -b, R ₁ and R ₂ are each a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a mono- or bicycloalkyl group (for example, a cyclohexyl group). ), A terpenyl group (for example, a nobornyl group), an aryl group (for example, a phenyl group, a naphthyl group, etc.), a heterocyclic group (for example, a benzimidazolyl group, a benzothiazolyl group, etc.) or a non-ring necessary for forming a heterocycle such as morpholine and pyridine. Represents a metal atom. The above alkyl group, aryl group and heterocyclic group may be substituted, and examples of the substituent include a halogen atom, a nitro group, a hydroxy group and a carboxy group (wherein the coupler has at least 12 carbon atoms at the uncoupling position or a corresponding group). A ballast group), an amino group, an aryl group, a substituted amino group (alkylamino, dialkylamino, anilino, N-alkylanilino, etc.), an albonic acid ester group (carbalkoxy, carboaryloxy, etc.), an amide group ( Acetamide, butylamide, ethylsulfonamide, N-methylbenzamide, N-propylbenzamide, 4-t-butylbenzamide, etc.), carbamyl group (carbamyl, N-octadecylcarbamyl, N, N-).
Dihexylcarbamyl, N-methyl-N-phenylcarbamyl, 3-pentadecylphenylcarbamyl, etc.), sulfamyl group (when the coupler has at least 12 carbon atoms or a corresponding ballast group at the uncoupling position,
N-propylsulfamyl, N-trisulfamyl, etc.), alkoxy group (ethoxy, octadecyloxy, etc.), sulfo group (when the coupler has at least 12 carbon atoms or a corresponding ballast group at the non-coupling position), Examples thereof include substituted sulfonyl groups (methylsulfonyl, octadecylsulfonylethoxyethoxysulfonyl, decyloxysulfonyl, phenylsulfonyl, tolylsulfonyl, phenoxysulfonyl, etc.).

R ₃ is a group represented by —COR ₅ or —COOR ₅ (wherein R ₅ represents an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group), and R ₄ is a hydrogen atom or 1 carbon atom. It represents an alkyl group of -10.

General formula [II] -a General formula [II] -b In the general formulas [II] -a and [II] -b, R ₁₁ is a hydrocarbon residue, R ₁₂ is an amino group, an alkyl group, an acylamino group, a ureido group, an alkoxycarbonyl group and their substitution products, a carboxyl group, etc. Indicates. -L- represents an alkyleneoxy group having 1 to 6 carbon atoms, and m is 0 or 1.
Represents [DD] represents a diffusible dye residue, and azo,
A diffusible dye residue having a known dye moiety such as azomethine, indoaniline, indophenol, and anthraquinone is shown. Preferred [DD] is represented by the following formula.

In the formula, R ₁ represents a hydrocarbon residue, R ₂ represents each group of amino, alkyl, acylamino, ureido, alkoxycarbonyl and their substitution products, carboxyl group, etc., M represents an alkali metal ion, ammonium ion, etc. Represents a cation or a hydrogen atom.

Examples of other preferable non-diffusible dyes used in the present invention include compounds represented by the following general formula [III].

General formula [III] Here, -Ball represents an organic stabilizing group having a molecular size and configuration which renders the compound non-diffusible during development in an alkaline processing composition.

Examples of the above-mentioned organic stable groups include general formulas [IV] to [VI]
The thing represented by is mentioned.

General formula [IV] [IV] In the formula, Z is a benzene ring to which an OY group is bonded,
Saturated carbocycle fused at the 3rd and 6th positions (5 to 7 members)
Represents a group of non-metal atoms necessary for forming Y, and Y represents a hydrogen atom or a group capable of cleaving a bond with an oxygen atom in an alkaline solution.

B represents an organic group which renders the compound represented by the general formula [IV] non-diffusible in the color light-sensitive material, and the organic group is a long-chain alkyl group; or an aromatic group such as a benzene group or a naphthalene group. Or a long-chain alkyl group bonded to one end of an appropriate divalent group or a benzene-based or naphthalene-based aromatic group as a representative one. The long-chain alkyl group or aromatic group may be substituted here, and a suitable divalent group is -O-; -S-; ^{_{-SO 2 -; - SO -;}} - R 2 -; - OR 3 R 4 -; -
CR ³ = CR ⁴ - (here ^{R 2} represents a hydrogen atom, an alkyl group or an aryl group, _{R 3} and _{R 4} are each,
It represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. ); And a substituted or unsubstituted aromatic divalent group,
One selected from the group consisting of a non-aromatic carbocyclic group and a non-aromatic heterocyclic group is used as a constituent element, and one of these is selected or a plurality of these are arbitrarily combined in a linear form. Is a divalent group.

General formula [V] In the formula [V], W represents an organic group which makes the compound represented by the above general formula [IV] non-diffusible in the color light-sensitive material, and is generally an aliphatic group or aromatic group having 8 to 20 carbon atoms. Examples of the organic stabilizing group include a group, an alicyclic group, and a heterocyclic group. In the compound of the present invention, these groups have 5 indole rings.
It is bonded to the 6-position or the 6-position via a nitrogen atom, and as an embodiment via such a nitrogen atom, -NHCO- group,
Examples thereof include those via a group such as NHSO ₂ — group and —NR ₃ — group (R ₃ represents a hydrogen atom or an alkyl group). The above organic stabilizing group is bonded to the 5-position or 6-position of the indole ring, but is preferably bonded to the 5-position.

In the general formula [V], R ₂₁ represents a monovalent organic group, and examples thereof include an alkyl group and an alkoxy group, and an alkyl group and an alkoxy group having 1 to 3 carbon atoms are preferable.

In the general formula [V], R ₂₂ represents a low-molecular group bonded through a carbon atom, and the group has 1 to 10 carbon atoms.
9 substituents are preferred, for example alkyl groups having 1 to 9 carbon atoms, phenyl groups and (R ₂₄ and R _{25 each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₂₄ and R ₂₅ may simultaneously form a ring).

R ₂₂ is more preferably unsubstituted or substituted with a group selected from the group consisting of a halogen atom, an acetylamide group, a methylsulfonamide group, a nitro group, a carboxy group, a sulfo group, a methanesulfone group, an alkyl group and an alkoxy group. Phenyl group.

General formula [VI] In the formula, Respectively directly to the above benzene ring or (R ′ is an alkyl group), an alkylene group (which may be branched), —O—, —S—, —SO ₂ —, a phenylene group (which may be substituted with an alkyl group or the like), or A halogen atom, a sulfo group, a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, which are bonded via a group formed by arbitrarily combining these.
It represents a heterocyclic group such as an amino group, a cyano group, an alkylamino group, an arylamino group, an alkylthio group and a pyridyl group, and may be the same or different.

D represents a group represented by -OR ₁ or -NHR ₂ . Here, R ₁ represents a hydrogen atom or a group in which the bond between R ₁ and O is cleaved under the condition of a hydroxide ion concentration of 10 ⁻⁸ to 2 mol / mol, preferably a hydrogen atom, Is a group represented by. Here, R ₃ is an alkyl group, especially an alkyl group having 1 to 18 carbon atoms.

In general formula [III] Represents a suitable divalent group, and as a suitable divalent group, -O-;-S-; ^{_{-SO 2 -; - SO -;}} - NR 1 CO -; - NR 1 SO
₂ −; −CR ² R ³ −; CR ³ −CR ⁴ − and the like. (Here, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ² and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group.) —Col in the general formula [III] is diffusible. Of magenta or cyan dye components, or precursor components of these dyes.

Such ingredients are well known to those of skill in the art and include azo,
Dyes such as azomethine, azopyrazolone, indoaniline, indophenol, anthraquinone, triarylmethane, alizarin, merocyanine, nitro, quinoline, cyanine, indigoid, phthalocyanine, metal complex forming dyes, as well as leuco dyes, pH value fluctuations,
When a surrounding environment having a different reaction source with the complex-forming substance is applied, the transition occurs in a bathochromic or bathochromic manner.
d) ”dye precursors such as dyes and the like. Further, -Col is a coupler component such as phenol,
Naphthol, indazolone, pyrazolone, U.S. Pat.
The compounds described in No. 756,142 may be used. These components may optionally have a solubilizing group.

In one preferred embodiment of the p-sulfonamidophenol of the present invention, Col represents the preformed dye component. This is because such p-sulfonamidophenol compounds are more applicable for degrading p-sulfonamidophenol and finally adjusting the shade of the dye that is transferred to form the dye image. If so, the color of the degradable diffusing paint component is essentially the same as the color of the original starting compound.

Examples of -Col include those represented by the formulas [VII] to [XII].

[VII] [VIII] [IX] In formulas [VII] to [IX], Q is at the 5-position or 8-position with respect to G, a hydroxyl group or a formula —NHCOR ³ or —N
HSO ₂ R ³ (wherein R ³ is an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, a benzyl group,
A phenyl group or a substituted phenyl group having 6 to 9 carbon atoms), G is a hydroxyl group or a salt thereof, or a formula thereof. Or (In the formula, R ⁴ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group or a substituted phenyl group having 6 to 18 carbon atoms), and represents a hydrolyzable acyloxy group, and r is 1 or 2 Represents an integer, Z is a cyano group, a trifluoromethyl group, a fluorosulfonyl group, a carboxy group, a carboxylic acid ester of the formula —COOR ⁴ (wherein R ⁴ represents the above), and a 2-position to the azo bond. Or 8-position nitro group, fluorine, chlorine or bromine atom, alkyl or substituted alkylsulfonyl group having 1 to 8 carbon atoms, phenyl or substituted phenylsulfonyl group having 6 to 9 carbon atoms, alkyl having 2 to 5 carbon atoms carbonyl group of the formula _-SO 2 ^NR 5 ^{R 6} (wherein ^{R 5} is a hydrogen atom, alkyl or substituted alkyl group having 1 to 8 carbon atoms, ^{R 6} is hydrogen atoms , An alkyl or substituted alkyl group having 1 to 6 carbon atoms, a benzyl group, phenyl, a substituted phenyl group having 6 to 9 carbon atoms, an alkyl or substituted alkylcarbonyl group having 2 to 7 carbon atoms, and 7 to 10 carbon atoms Represents a phenyl or substituted phenylcarbonyl group, an alkyl or substituted alkylsulfonyl group having 1 to 6 carbon atoms, a phenyl or substituted phenylsulfonyl group having 6 to 9 carbon atoms, or R ⁵ and R ⁶ are bonded to each other. Represents a morpholino group or a piperidine group) together with a nitrogen atom thereof, or a formula —CON (R ⁵ ) ₂ (in the formula, R
⁵ are the same or different and each is the same as the above, and represents a carbamoyl group, Z ₃₁ represents hydrogen or Z, R ₃₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. Represents a substituted alkyl group, an alkoxy group having 1 to 4 carbon atoms or a halogen atom, and D is a cyano group, a sulfo group, a fluorosulfonyl group, a halogen atom, -SO ₂ -phenyl group or 6 carbon atoms.
To 9 substituents -SO ₂ - phenyl group, an alkyl or an alkylsulfonyl group having 1 to 8 carbon atoms, carbon atoms 6
To phenyl or substituted phenylsulfonyl group, alkyl or alkylsulfinyl group having 1 to 8 carbon atoms, phenyl or substituted phenylsulfinyl group having 6 to 9 carbon atoms, sulfamoyl group of formula —SO ₂ NR ⁵ R ⁶ , or formula -CON ^(R _{5) 2} (wherein ^{R 5} and ^{R 6}
Each have the same meaning as defined above for Z), but no more than one sulfo group and no more than one carboxy group are present in the compound.

[X] [XI] [XII] In formulas [X] to [XII], Y is a hydrogen atom, Or Represents

Here, R ₄₂ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and R ₄₃ represents an acyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkyleneoxyalkyl group, a carboxyalkyl group, a carboxyphenyl group. , A carboxyalkylphenyl group, a hydroxyalkylphenyl group, an alkoxyphenyl group, or a group having the same meaning as the group represented by R ₄₂ .

W represents —CO— or —SO ₂ —, R ₃₇ represents an alkyl group having 1 to 6 carbon atoms, an aryl group, or Represents (Here, R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group. However, R ₄₄ and R ₄₅ cannot be hydrogen atoms at the same time.) R ₃₈ is a carbon atom It represents an alkyl group having 1 to 6 or an aryl group having 6 to 10 carbon atoms.

R ₃₉ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a dialkylamino group, and R ₄₀ represents an alkyl group, an alkylthio group, an arylthio group, a halogen atom or an acylamino group. Here, n is 0, 1 or 2.

R ₄₁ is an alkyl group or an aromatic group (eg, a phenyl group,
A naphthyl group).

Next, specific representative examples of the non-diffusing green absorbing dye and the non-diffusing red absorbing dye used in the present invention are shown, but the compounds used in the present invention are not limited to these.

A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-41 A-42 A-43 A-44 A-45 A-46 These non-diffusing red and / or green absorbing dyes may be added to any of the non-photosensitive hydrophilic colloid layers, but are preferably added to the protective layer furthest from the support. More preferably, the non-diffusing red absorbing dye is added to the non-photosensitive hydrophilic colloid layer adjacent to the red-sensitive emulsion layer on the side remote from the support, and / or the non-diffusing green absorbing dye is green. It is added to the non-photosensitive hydrophilic colloid layer adjacent to the side facing away from the support with respect to the sensitive emulsion layer.

When the silver halide color photographic light-sensitive material of the present invention has a reverse layer structure, the red absorbing dye and the green absorbing dye are added to at least one of the intermediate layer and the protective layer, preferably the protective layer, and more preferably the protective layer. The non-diffusible red absorbing dye is
In the intermediate layer provided between the low-sensitivity red-sensitive silver halide emulsion layer and the low-sensitivity green-sensitive silver halide emulsion layer and / or the non-diffusible green absorbing dye is the low-sensitivity green-sensitive silver halide emulsion layer. And the low-sensitivity blue-sensitive silver halide emulsion layer.

The amount of non-diffusible dye added is 1 to 200 mg / m ² , preferably 5 to 100 mg / m ² . Further, with respect to the non-photosensitive hydrophilic colloid layer containing fine grain silver halide, it may be added to the non-photosensitive hydrophilic colloid layer at any position, but a preferable positional relationship is that the layer containing the non-diffusible dye is It is on the side closer to the support with respect to the layer containing fine grain silver halide.

In the light-sensitive material of the present invention, other known couplers can be used together with the non-diffusible dye and the non-light-sensitive fine grain silver halide. Such couplers include magenta couplers, yellow couplers and cyan couplers. Specific examples of magenta couplers include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based couplers. Examples of such magenta couplers include U.S. Pat.Nos. 2,600,788, 2,983,608, and 3,062,653.
No. 3, No. 3,127,269, No. 3,311,476, No. 3,419,39
1, No. 3,519,429, No. 3,558,319, No. 3,582,3
No. 22, No. 3,615,506, No. 3,834,908, No. 3,891,
445, West German patent 1,810,464, West German patent application (OLS)
2,408,665, 2,417,945, 2,418,959, 2,42
4,467, JP-B-40-6031, JP-A-49-74027, 49-7
4028, 49-129538, 50-60233, 50-159336, 51-2
0826, 51-26541, 52-42121, 52-58922, 53-551
No. 22, Japanese Patent Application No. 55-110943, and the like.
Among such magenta couplers, as a colored magenta coupler, an arylazo-substituted or heteroarylazo-substituted compound is used at the active site of the colorless magenta coupler, and, for example, U.S. Pat.
No. 2, No. 2,688,539, No. 2,725,292, No. 2,983,60
No. 8, No. 3,005,712, No. 3,519,429, British Patent No. 8
The compounds described in 00,262, 1,044,778, Belgian Patent No. 676,691 and the like can be mentioned. Examples of the yellow couplers include benzoylacetanilide type and pivaloylacetanilide type yellow couplers, and 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction. .

Specific examples of yellow couplers that can be used in the present invention are described in US Pat.
No. 2,875,057, No. 3,265,506, No. 3,408,194, No. 3,551,155, No. 3,582,322, No. 3,725,072,
No. 3,891,445, West German patent 1,547,868, West German application published
2,219,917, 2,261,361, 2,414,006, British Patent 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133.
No. 48-73147, 50-6341, 50-87650, 50-123342
No., 50-130442, 51-21827, 51-102636, 52-82424
No. 52-115219, No. 58-95346, etc.

Further, the cyan coupler includes a phenol or naphthol derivative, and the colored cyan coupler further includes a compound in which an arylazo-substituted phenoxy group is substituted at the coupling position of a colorless cyan coupler through an alkoxy group. Can be mentioned.

Such cyan couplers include, for example, US Pat.
No. 2,423,730, No. 2,474,293, No. 2,801,171, No. 2,895,826, No. 3,476,563, No. 3,737,326,
No. 3,758,308, No. 3,893,044, JP-A-47-3
No. 7425, No. 50-10135, No. 50-25228, No. 50-112038
Nos. 50-117422 and 50-130441, and couplers described in JP-A-58-98731 are preferable. Further, as a colored cyan coupler as a masking coupler, for example, US Pat.
521,908, 3,034,892, British patent 1,255,111
And the compounds described in JP-A-48-22028.

Further, U.S. Pat.No. 3,476,563, JP-A-50-10135, 50-
Colored cyan couplers of the type in which the dye flows out into the processing bath upon reaction with the oxidation product of the color developing agent as described in 123341 can also be used.

The conventionally known magenta couplers, yellow couplers and cyan couplers used in the present invention, when they are contained in the photosensitive layer together with the diffusible and non-diffusible DIR compounds, 0.002 to 0.5 mol per mol of silver halide, It is preferably used in the range of 0.009 mol to 0.35 mol.

The silver halide color photographic light-sensitive material of the present invention comprises a diffusible and non-diffusible DIR compound or its precursor together with
A ureido type phenolic cyan coupler having a phenylureido group, a naphthylureido group or a heterocyclic ureido group at the 5-position and an acylamino group at the 5-position can be used in combination. Such ureido-type phenol-based cyan couplers are disclosed in JP-A-56-65134, JP-A-57-204543, and JP-A-57-204544.
No. 57-204545. The ureido-type phenol-based cyan coupler is used as a diffusible and non-diffusible D
When used in combination with an IR compound, the added layer may be the same as or different from the layer containing the diffusible and non-diffusible DIR compound. When the ureido cyan coupler is used in combination with the diffusible and non-diffusible DIR compound, the complex color defect of the cyan dye, which tends to occur when the bleaching ability during the bleaching process is lowered, is improved, and the dye has a good color balance. Images can be obtained.

Furthermore, in the present invention, in order to improve the graininess of a dye image, the dye formed is slightly mobile when it undergoes a coupling reaction with an oxidant of a color developing agent together with a diffusible and non-diffusible DIR compound. Can be used. Such couplers are described in, for example, JP-A-57-82837, JP-A-58-217932 and JP-A-58-174755, and are non-diffusible in the emulsion.
The coupler can be added in the same layer or in a different layer to which the diffusible and non-diffusible DIR compounds are added, but the halogens having different sensitivities have substantially the same color sensitivity. Of the silver halide emulsion layers, it is preferably contained in the high sensitivity layer. The amount of this coupler added is
The amount is 0.001 to 0.5 g / m ² , preferably 0.005 to 0.5 g / m ² .

As the silver halide emulsion used in the silver halide color photographic light-sensitive material of the present invention, any silver halide emulsion used in the art can be applied. For example, it may contain silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide crystals, or a mixture of these crystals. The silver halide emulsion may be large grains or small grains and may be monodisperse or polydisperse. The silver halide crystal may be any of cubic crystal, octahedron, epitaxial mixed crystal and the like. The emulsion can be a negative emulsion or a direct positive emulsion. They are surface latent image type emulsions which mainly form a latent image on the surface of silver halide grains,
An internal latent image type emulsion forming a latent image inside a silver halide grain or a mixture of a surface latent image type emulsion and an internal latent image type emulsion can be used.

The silver halide emulsion used in the present invention includes various production methods including a production method which is usually carried out, for example, a method as described in JP-B-46-7772, that is, at least a part of which solubility is larger than that of silver bromide. A so-called conversion emulsion is prepared by forming an emulsion of silver salt grains consisting of silver salt, and then converting at least a part of the grains into silver bromide or silver iodide salt, or an average grain size of 0.1 μm or less. It can be prepared by any method such as a method for producing a Lippmann emulsion comprising the finely divided silver halide.

When the silver halide used in the present invention is required to be a high-sensitivity silver halide emulsion in absolute value, as the silver halide, iodobromide containing 1 to 10 mol% of silver iodide is used. It is preferably silver, and the particle size is 0.5 to
It is preferably 3.0 μm. Further, the silver halide used as a low-sensitivity silver halide emulsion in combination with the above-mentioned high-sensitivity emulsion is preferably silver iodobromide containing 1 to 12 mol% of silver iodide, and the grain size is 0.1 to 0.8 μm. Preferably there is.

As the binder of the silver halide emulsion layer according to the present invention, conventionally known binders are used, and examples thereof include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyethyl cellulose derivatives. , Cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole, polyacrylamide, and other single or copolymer synthetic hydrophilic polymers, and the like.

The silver halide photographic emulsion in which the above-mentioned silver halide grains are dispersed in a binder solution can be sensitized with a chemical sensitizer. The chemical sensitizers that can be advantageously used in combination in the present invention are roughly classified into four types, that is, a noble metal sensitizer, a sulfur sensitizer, a selenium sensitizer and a reduction sensitizer.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium and platinum can be used.

When a gold compound is used, ammonium thiocyanate and sodium thiocyanate can be used together.

As the sulfur sensitizer, in addition to active gelatin, a sulfur compound can be used.

As the selenium sensitizer, active and inactive selenium compounds can be used.

Reduction sensitizers include monovalent tin salts, polyamines, bisalkylamino sulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

The emulsion used in the present invention contains 5 × 10 ^{−3 to} 3 × 10 ⁻³ mol of an appropriate sensitizing dye for 1 mol of silver halide in order to impart photosensitivity to a desired wavelength range. It may be optically sensitized. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used. Examples of the sensitizing dye that can be advantageously used in the present invention include the following.

That is, as the sensitizing dye used in the green photosensitive emulsion, for example, U.S. Patent Nos. 1,939,201, 2,072,908 and 2,739,
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in No. 149, No. 2,945,763 and British Patent No. 505,979. Further, as the sensitizing dye used for the red light-sensitive emulsion, for example, U.S. Pat.Nos. 2,269,234 and 2,2
70,378, 2,442,710, 2,454,629, 2,
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes such as those described in No. 766,280. Furthermore, U.S. Pat.
No. 3,995, No. 2,493,748, No. 2,519,001, Cyanine dyes such as those described in West German Patent No. 929,080, merocyanine dyes or complex cyanine dyes can be advantageously used in green or red light-sensitive emulsions. .

These sensitizing dyes may be used alone or in combination. A combination of sensitizing dyes is often used especially for the purpose of supersensitization. A typical example is
U.S. Pat.Nos. 2,688,545, 2,977,229, 3,397,
No. 060, No. 3,522,052, No. 3,527,641, No. 3,67
1,293, 3,628,964, 3,666,480, 3,6
72,898, 3,679,428, 3,703,377, 3,
No. 769,301, No. 3,814,609, No. 3,837,862, No. 3
4,026,707, British Patents 1,344,281, 1,507,803
No. 4, Japanese Patent Publication No. 43-4936, No. 53-12375, JP-A-52-109925
No. 52-110618.

The silver halide used in the silver halide emulsion layer of the present invention preferably has a silver iodide content of 2% to 15 mol%, and particularly preferably a silver iodide content of 4% to 10 mol%. Is preferred.

The silver halide color photographic light-sensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes of preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent Nos. 584,609 and 1,177,429.
No. 48-85130, No. 49-99620, No. 49-114420
No. 52-108115, U.S. Pat.Nos. 2,274,782, 2,53
3,472, 2,956,879, 3,148,187, 3,1
77,078, 3,247,127, 3,540,887, 3,
No. 575,704, No. 3,653,905, No. 3,718,472, No. 3
4,070,352 and 4,071,312.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, brightening agents, color image fading inhibitors, antistatic agents, hardeners, interfaces described in Research Disclosure No. 17643 Activators, plasticizers, wetting agents and the like can be used.

The support of the silver halide color photographic light-sensitive material used in the present invention is preferably, for example, a glass plate, a cellulose acetate, a polyester film such as cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, In addition, a baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a support provided with a reflective layer or a reflector may be used together. These supports are appropriately selected depending on the purpose of use of the light-sensitive material.

Various coating methods such as deep pink coating, air doctor coating, curtain coating, and hopper coating can be used for coating the emulsion layers and other constituent layers used in the present invention. In addition, U.S. Patent Nos. 2,761,791 and 2,941,8
It is also possible to use simultaneous coating of two or more layers according to the method described in No. 98.

Further, in the silver halide color photographic light-sensitive material used in the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and further, a filter layer, an anti-curl layer, a protective layer, an antihalation layer. Various layers such as the above can be appropriately combined and used as the constituent layers. In these constituent layers, a hydrophilic colloid which can be used in the emulsion as described above can be similarly used as a binder, and various kinds thereof can be contained in the emulsion layer as described above. The above photographic additives can be incorporated in the same manner.

The silver halide color photographic light-sensitive material of the present invention includes all kinds of color photographic light-sensitive materials such as a color negative film, a color positive film, a color reversal film and a color paper, and is particularly useful in a color negative film.

As the color developing agent contained in the color developing solution for processing the silver halide color photographic light-sensitive material of the present invention, aromatic first
Preferred are primary amine compounds, especially p-phenylenediamine compounds, such as N, N-diethyl-p-phenylenediamine hydrochloride, N-ethyl-p-phenylenediamine hydrochloride, N, N-dimethyl-phenylenediamine hydrochloride. Two
-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-toluenesulfonate, N, N-diethyl-3-methyl- 4-aminoaniline, 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 kinds.

In addition, L. F. A. "Photographic Processes" by Nason
2 of "sing Chemistry" (published by Focal Press, 1966)
26-229, U.S. Pat. Nos. 2,193,013 and 2,592,3
No. 64, JP-A-48-64933 and the like may be used.

The silver halide photographic light-sensitive material used in the present invention can contain these color developing agents as the color developing agent itself or as a precursor thereof in the hydrophilic colloid layer. The color developing agent precursor is a compound capable of forming a color developing agent under alkaline conditions, and examples thereof include a Schiff base precursor with an aromatic aldehyde compound, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, and a urethane type precursor. To be Precursors for these aromatic primary amine color developing agents are disclosed in US Pat. Nos. 2,507,114 and
2,695,234, 3,342,599, 3,719,492, British Patent 803,783, JP-A-53-185628, 54-79035, Research Disclosure 12146, 13924, 1515.
It is described in 9. The amount of these aromatic primary amine color developing agents or their precursors added is roughly
The amount is in the range of 0.1 to 5 moles, preferably 0.3 to 3 moles, per mole of photosensitive silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate these color developing agents or precursors into the light-sensitive material, they can be dissolved in an appropriate solvent such as water, methanol, ethanol or acetone and added, or dibutyl phthalate, dioctyl phthalate, tricresyl phosphate and the like. It may be added as an emulsified dispersion using the high boiling point organic solvent, or may be added by impregnating it with a latex polymer as described in Research Disclosure 14850.

The color developing solution of the present invention is, for example, an alkali agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, and tribasic sodium phosphate, and development inhibition of sodium bromide, potassium bromide and the like. Agents, various organic solvents such as methanol, ethanol, acetone, butanol, benzyl alcohol, phenoxybutanol, diethylene glycol, ethylene glycol, N, N-dimethylformamide, hydroxylamine, preservatives such as sodium sulfite, citrazinic acid, polyethylene glycol , Development modifiers such as polyvinylpyrrolidone, water-soluble fluorescent whitening agents such as diaminostilbene compounds, heavy metal ion concealing agents such as ethylenediaminetetraacetic acid and alkyliminodiacetic acid, and various known additives such as development accelerators. If necessary Can.

The pH value of this color developing solution is usually 7 or higher, most commonly about 9.5-12. The higher the pH, the faster the developing speed and the shorter the time required for the color developing step, but the stability of the processing solution is deteriorated, and therefore it is generally not preferable to set the pH to 11 or more.

Regarding the temperature, the higher the temperature, the shorter the processing time of the color developing step, but if the processing temperature is too high, problems such as increased fog and decreased stability of the processing liquid may occur. Not preferable.

The processing time in the color developing step of the present invention is 45 seconds to 5 minutes, preferably 60 seconds to 4 minutes.

The silver halide photographic color true light-sensitive material of the present invention, because of its rapid processing, does not cause defective recolorability even when subjected to the one-solution bleach-fixing process, and has improved graininess and visual color reproducibility. It is preferred that the silver halide color photographic light-sensitive material of the present invention is subjected to one-solution bleach-fixing treatment.

The silver halide color photographic light-sensitive material of the present invention may be processed separately from the bleaching step and the constant fixing step.

Further, other photographic processing steps other than the bleach-fixing processing step of the present invention may be carried out in the same manner as ordinary processing steps.

As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones and nitroso compounds are used. For example, ferricyanide, dichromate, organic complex salts of iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates; nitrosophenol and the like can be used.

As the bleaching agent in the bleach-fixing process of the present invention, metal complex salts of organic acids are particularly preferable among the above.

The metal complex salt of an organic acid has an action of oxidizing metal silver produced by development to convert it to silver halide, and its structure is an organic acid such as aminopolycarboxylic acid or oxalic acid, citric acid, and iron, cobalt, It is coordinated with a metal ion such as copper. The most preferred organic acid used for forming such a metal complex salt of an organic acid is, for example, aminopolycarboxylic acid.

These aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. The following may be mentioned as typical examples of the aminopolycarboxylic acid.

Ethylenediaminetetraacetic acid Ethylenediamine-N- (β-hydroxyethyl)-
N, N, N'-Triacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Cyclohexanediaminetetraacetic acid Iminodiacetic acid Methyliminodiacetic acid Ethyliminodiacetic acid Hydroxyethyliminodiacetic acid propyliminodiacetic acid butyliminodiacetic acid Dihydroxyethylglycine Ethyletherdiaminetetraacetic acid glycoletherdiaminetetraacetic acid Ethylenediamine Tetrapropionic acid Phenylenediamine tetraacetic acid Ethylenediaminetetraacetic acid disodium salt Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriamine pentaacetic acid pentasodium salt Ethylenediamine-N- (β-hydroxyethyl)-
N, N, N'-triacetic acid sodium salt Propylenediaminetetraacetic acid sodium salt Nitrilotriacetic acid sodium salt Dichlorohexanediaminetetraacetic acid sodium salt The metal in the metal complex salt of the organic acid used in the present invention can coordinate with the organic acid. Metals such as chromium, manganese, iron, cobalt, nickel and copper,
Particularly preferred for the present invention is iron.

The metal complex salt of an organic acid in the present invention can be any combination of the above-mentioned organic acid and metal, but particularly preferred are ferric salts of ethylenediaminetetraacetic acid, for example, sodium iron (III) diaminetetraacetic acid (III), ethylenediaminetetraacetic acid. It is iron (III) acetate. Further, metal complex salts of two or more kinds of organic acids having different structures may be used in combination. The specific amount used is about 5 per processing solution.
It is preferably used in an amount of about 400 to 400 g, particularly about 10 to 200 g per processing solution.

The bleach-fixing solution used in the present invention contains, as a bleaching agent, a metal complex salt of an organic acid as described above (for example, an iron complex salt), and a silver halide fixing agent such as thiosulfates, thiocyanates and thioureas. A liquid having a composition containing is applied. Further, from a bleach-fixing solution comprising a composition containing a small amount of a halogen compound such as potassium bromide in addition to a bleaching agent and the above-mentioned silver halide fixing agent, or conversely, comprising a composition containing a large amount of a halogen compound such as potassium bromide. It is also possible to use a bleach-fixing solution containing a bleach-fixing solution, and a special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide.

[Specific effects of the present invention] The silver halide color photographic light-sensitive material of the present invention is characterized in that fine grain silver halide and a non-diffusing red and / or green absorbing dye are used in combination. Compared with a photosensitive material, it shows various characteristics superior to those of the photosensitive materials used alone, and the sharpness is greatly improved while maintaining high sensitivity, and the processing stability of the photosensitive material is also improved as a side effect. That was unexpected.

[Specific Examples of the Present Invention] Examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 Sample-1 was prepared by successively coating the following layers from the support side on a support made of a cellulose triacetate film subjected to an undercoating process.

First layer: antihalation layer containing black colloidal silver (dry film thickness 2.5 μm) Second layer: intermediate layer made of gelatin (dry film thickness 1.0 μm) Third layer: red-sensitive low-sensitivity silver halide emulsion layer 6 mol % Silver iodobromide emulsion (average grain size
0.5 μm, 0.25 mol of silver halide emulsion per 500 g of emulsion,
Gelatin (containing 15 g) was prepared by a conventional method, and 500 g of this emulsion was chemically sensitized with gold and sulfur sensitizers, and a red-sensitizing sensitizing dye was further added to perform spectral sensitization by a conventional method. Next, 420 g of the following dispersion (C-1) was added to 500 g of this emulsion to prepare a coating, which was coated so that the dry film thickness would be 3.0 μm.

Fourth layer: Red sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion containing 7 mol% of silver iodide (average grain size
0.6 μm, containing 0.25 mole of silver halide and 15 g of gelatin per 500 g of emulsion) were chemically and spectrally sensitized in the same manner as in the above emulsion, and further 500 g of the following dispersion (C-1) 185 m Was added to prepare an emulsion, and the emulsion was coated so that the dry film thickness was 1.5 μm.

Fifth layer: an intermediate layer made of gelatin containing 2,5-di-tert-octylhydroquinone (dry film thickness 0.8 μm) Sixth layer: green sensitive low-sensitivity silver halide emulsion layer containing 6 mol% of silver iodide Silver iodobromide emulsion (average grain size
0.5 μm, containing 0.25 mol of silver halide and 20 g of gelatin per 500 g of emulsion) were prepared by an ordinary method.
0 g was chemically sensitized with gold and sulfur sensitizers, and a green sensitizing dye was further added to carry out spectral sensitization by a usual method. Next, 380 m of the following dispersion (M-1) was added to 500 g of this emulsion to prepare a coating, and the coating was applied so that the dry film thickness was 3.7 μm.

Seventh layer: green sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion containing 7 mol% of silver iodide (average grain size
0.6 μm, containing 0.25 mol of silver halide and 20 g of gelatin per 500 g of emulsion) were prepared and sensitized by the same method as the above (sixth layer). The following dispersion (M-1) 8 was added to 500 g of this emulsion.
It was prepared by adding 5 m and coated so that the dry film thickness was 1.5 μm.

Eighth layer: gelatin layer containing yellow colloidal silver and 2,5-di-tert-octylhydroquinone (dry film thickness: 1.0 μm
m) Ninth layer: Blue-sensitive low-sensitivity silver halide emulsion layer Silver iodobromide emulsion containing 6 mol% of silver iodide (average grain size
0.5 μm, containing 0.25 mol of silver halide and 40 g of gelatin per 500 g of emulsion) were prepared by an ordinary method.
0 g was chemically sensitized with gold and sulfur sensitizers. Next, 1350 m of the following dispersion (Y-1) was added to 500 g of this emulsion to prepare a coating, and the coating was applied so that the dry film thickness was 3.0 μm.

Layer 10: Blue sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion containing 7 mol% of silver iodide (average grain size
0.8 μm, containing 0.25 mol of silver halide per 500 g of emulsion and containing 40 g of gelatin) were prepared and sensitized in the same manner as in the above (the ninth layer). The following dispersion (Y-1) 550 was added to 500 g of this emulsion.
m to prepare a coating film, and the coating was applied so that the dry film thickness was 2.0 μm.

11th layer: an intermediate layer made of gelatin containing a UV absorber (dry film thickness 1.2 μm) 12th layer: a protective layer made of gelatin containing a matting agent (dry film thickness 0.7 μm) Dispersion (C-1) 30 g of coupler (1) and 3.0 of the following coupler (2)
g was dissolved in a mixture of 33 g of tricresyl phosphate (TCP) and 198 g of ethyl acetate (EA), and 2.0 g of sodium triisopropylnaphthalenesulfonate (SUR-1) was added.
Was added to 440 m of a 10% gelatin aqueous solution containing and was emulsified and dispersed by a colloid mill to prepare 1000 m.

-Dispersion (M-1) It prepared by the same operation as the dispersion (C-1).

Coupler (3) 40.0 g Coupler (4) 8.0 g TCP 48 g EA 145 g 10% Gel 400 m SUR-1 4.5 g Prepared to 1000 m Dispersion (Y-1) Same as dispersion (C-1) Prepared by operation.

Coupler (5) 50.0 g TCP 5.0 g EA 165 g 10% Gel 370 m SUR-1 4.0 g 1000 m Prepared as described above, Sample 1 was prepared, and as shown in Table 1 below, it was non-diffusible. Samples 1 to 11 were prepared by adding a dye and fine grain silver halide.

-Dispersion (C-2) The dispersion was prepared in the same manner as the dispersion (C-1) except that 1.4 g of the following DIR compound was added.

-Dispersion (M-2) The dispersion was prepared in the same manner as the dispersion (M-2) except that 1.7 g of the following DIR compound was added.

Dispersion (Dye-1) 30 g of the non-diffusible dye (A-17) was dissolved in a mixture of 15 g of tricresyl phosphate (TCP) and 90 g of ethyl acetate (EA), and sodium triisopropylnaphthalenesulfonate (SUR-1) was added. ) Add to 450m of 10% gelatin aqueous solution containing 5.0g, emulsify and disperse with colloid mill 1
It was adjusted to 000 m.

-Dispersion (Dye-2) The non-diffusible dye (A-17) of the dispersion (Dye-1) was added to (A
Dispersion / Preparation was carried out in the same manner as Dispersion (Dye-1) except that -13) was used instead.

[Compound used to prepare Samples 1 to 11] Coupler (1) Coupler (2) Coupler (3) Coupler (4) Coupler (5) DIR compound (1) Each of these samples was exposed to white light through a wedge and then processed according to the following processing steps.

Development process (38 ℃) Processing time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Used in each processing step The composition of the treated liquid is as follows.

Color developer composition: Bleach solution composition: Fixer composition: Stabilizer composition: Then, the sensitivity, sharpness, and development stability of the color images formed on the above samples were measured. The results are shown in Table 2.

Here, the sensitivity indicates a relative value with the sensitivity value of the cyan and magenta images of Sample-1 which was exposed to white being taken as 100. The sharpness of the image is evaluated by MTF (= Modulation Trausf
er function) to determine the spatial frequencies of MTF 90% and 50%. Low frequency region (MTF 90% resolution) and high frequency region (MTF50
The higher the spatial frequency, the better the sharpness.

Further, the evaluation of the development stability was carried out by the ratio γa / γo × gamma value (γo) under the above-mentioned developing conditions and the gamma value (γa) at a developing time shorter than that by 20 seconds (2 minutes 55 seconds).
It was measured by measuring 100 (%). That is, the ratio is 100 (%)
The closer to, the better the development stability.

As is clear from Table 2, the present invention (Samples 6 to 11) has a remarkable effect of improving the image sharpness in both the low frequency region and the high frequency region. At the same time, it is clear that the development stability is also excellent.

In addition, in the comparison in the present invention, the addition position of the non-diffusible dye is more than that of the protective layer (the twelfth layer), and the red-sensitive non-diffusible dye is the non-photosensitive hydrophilic colloid layer adjacent to the red-sensitive emulsion layer group ( It can be seen that the green-sensitive non-diffusible dye is added to the non-photosensitive hydrophilic colloid layer (8th layer) adjacent to the green-sensitive emulsion layer group in the fifth layer) to have a larger improvement effect.

Example 2 Sample-12 was prepared by sequentially coating the following layers from the support side on a support made of a cellulose triacetate film subjected to an undercoating process.

First layer: antihalation layer containing black colloidal silver (dry film thickness 2.5 μm) Second layer: intermediate layer made of gelatin (dry film thickness 1.0 μm) Third layer: red-sensitive low-sensitivity silver halide emulsion layer 6 mol % Silver iodobromide emulsion (average grain size
0.5 μm, 0.25 mol of silver halide emulsion per 500 g of emulsion,
Gelatin (containing 15 g) was prepared by a conventional method, and 500 g of this emulsion was chemically sensitized with gold and sulfur sensitizers, and a red-sensitizing sensitizing dye was further added to perform spectral sensitization by a conventional method. Next, 420 m of the following dispersion (C-1) was added to 500 g of this emulsion to prepare a coating, and the coating was applied so that the dry film thickness was 2.7 μm.

Fourth layer: intermediate layer made of gelatin containing 2,5-di-tert-octylhydroquinone (dry film thickness: 0.7 μm) Fifth layer: green-sensitive low-sensitivity silver halide emulsion layer: 6 mol% of silver iodide Silver iodobromide emulsion (average grain size
0.5 μm, containing 0.25 mol of silver halide and 20 g of gelatin per 500 g of emulsion) were prepared by an ordinary method.
0 g was chemically sensitized with gold and sulfur sensitizers. Further, a green-sensitizing sensitizing dye was added to carry out spectral sensitization by a usual method. Next, 380 m of the following dispersion (M-1) was added to 500 g of this emulsion to prepare a dry film thickness of 3.5 μm.

Sixth layer: Middle layer made of gelatin containing 2,5-di-tert-octylhydroquinone (dry film thickness: 0.7 μm) Seventh layer: Blue-sensitive low-sensitivity silver halide emulsion layer Containing 6 mol% of silver iodide Silver iodobromide emulsion (average grain size
0.5 μm, containing 0.25 mol of silver halide and 40 g of gelatin per 500 g of emulsion) were prepared by an ordinary method.
0 g was chemically sensitized with gold and sulfur sensitizers. Then, 1350 m of the following Dispersion (Y-1) was added to 500 g of this emulsion to prepare a dry film thickness of 2.8 μm.

Eighth layer: Middle layer made of gelatin containing 2,5-di-tert-octylhydroquinone (dry film thickness: 0.7 μm) Ninth layer: Red-sensitive high-sensitivity silver halide emulsion layer Containing 7 mol% of silver iodide Silver iodobromide emulsion (average grain size
0.6 µm, containing 0.25 mol of silver halide and 15 g of gelatin per 500 g of emulsion) were chemically and spectrally sensitized in the same manner as in the above emulsion. Prepared by adding
It was applied so that it would be m.

Tenth layer: an intermediate layer made of gelatin containing 2,5-di-tert-octylhydroquinone (dry film thickness: 0.7 μm) Eleventh layer: green sensitive high-sensitivity silver halide emulsion layer: 7 mol% of silver iodide is contained. Silver iodobromide emulsion (average grain size
0.6 μm, containing 0.25 mol of silver halide and 20 g of gelatin per 500 g of emulsion) were prepared and sensitized by the same method as the above (sixth layer). The following dispersion (M-1) was added to 500 g of this emulsion.
It was prepared by adding 85 m, and applied so that the dry film thickness was 1.5 μm.

12th layer: gelatin layer containing yellow colloidal silver and 2,5-di-tert-octylhydroquinone (dry film thickness 1.0 μm
m) Thirteenth layer: Blue sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion containing 7 mol% of silver iodide (average grain size
0.8 μm, containing 0.25 mol of silver halide per 500 g of emulsion and containing 40 g of gelatin) were prepared and sensitized in the same manner as in the above (the ninth layer). The following dispersion (Y-1) 550 was added to 500 g of this emulsion.
m to prepare a coating film, and the coating was applied so that the dry film thickness was 2.0 μm.

14th layer: Middle layer made of gelatin containing UV absorber (dry film thickness 1.2 μm) 15th layer: Protective layer made of gelatin containing matting agent (dry film thickness 0.7 μm) Dispersion (C-1) , (M-1) and (Y-1) are dispersions (C-1), (M-1) and (Y-1) of the examples.
The same one was used.

In Sample 12, the red dye (Dye-1) of the present invention was added to the fourth or fifteenth layer, and the green dye (Dye-) of the present invention was added.
2) was added to the 6th or 15th layer.

The grain size of fine grain silver halide and the amount of halogen composition added were the same as in Example 1, and this fine grain silver halide was added to the 14th layer.

When the sensitivity, sharpness and development stability of the color image obtained by processing the sample prepared as described above in the same manner as in Example 1 were examined, almost the same results as in Example 1 were obtained. It can be seen that the present invention is effective in both the forward layer structure and the reverse layer structure.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-60-128441 (JP, A) JP-A-53-58236 (JP, A) JP-A-55-161235 (JP, A) JP-A-57- 158639 (JP, A) JP 59-170838 (JP, A) JP 52-20830 (JP, A) JP-B-6-21937 (JP, B2)

Claims (1)

[Claims] 1. A red-sensitive emulsion layer group, a green-sensitive emulsion layer group, and a plurality of non-photosensitive hydrophilic groups which are composed of at least two layers having substantially the same color sensitivity on a support but different sensitivities. A silver halide color photographic light-sensitive material having a photosensitive colloid layer, at least one of the non-photosensitive hydrophilic colloid layers contains fine grain silver halide, and the red-sensitive emulsion closest to the support in the red-sensitive emulsion layer group. At least one of the non-photosensitive hydrophilic colloid layers located farther from the support than the emulsion layer contains a non-diffusible red absorbing dye and / or is the most support of the green-sensitive emulsion layer group. A silver halide color photographic light-sensitive material, characterized in that at least one of the non-photosensitive hydrophilic colloid layers located farther from the support than the green-sensitive emulsion layer closer to Material .