JPH01233452A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To make it possible to form an image in the presence of a yellow coupler, and to improve the sharpness and the sensitivity of the title material by incorporating a specified color forming coupler in at least one layer mounted on a supporting body. CONSTITUTION:The color forming coupler shown by formula I is incorporated in at least one layer mounted on the supporting body. In formula I, R1 is an atomic group necessary for forming a 5-membered nitrogen contg. unsatd. heterocyclic ring, R2 is an aromatic group, B1 and B2 are each a ballast group, X1 is a group which is capable of being released by allowing it to react with the oxidant of an aromatic primary amine color developing main agent and does not show a photographic availability, (n) and (m) are each 0 or 1. The compd. shown by formula I is applied to a multilayer and multicolor photographic material having at least 3 different spectral sensitivities and mounted on the supporting body. Thus, the yellow coupler having a sufficient coupling activity of the sensitive material is obtd. in a development processing system which uses a color developer not contg. benzyl alcohol.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic material containing a novel yellow dye-forming coupler (hereinafter referred to as yellow coupler). The present invention relates to a color photographic light-sensitive material that achieves particularly improved sharpness and high sensitivity by forming images in the presence of a novel yellow coupler that has a high formation rate and high color density.

(Prior Art) As is well known, subtractive color photography uses oxidation products of a color developer produced by reducing exposed silver halide grains with an aromatic primary amine color developer and yellow,
Color images are formed by oxidative coupling in silver halide emulsions with couplers that form cyan and magenta dyes.

In such cases, a compound having an active methylene group is generally used as a yellow coupler to form a yellow pigment, and a pyrazolone, pyrazolobenzimidazole, or indacylon coupler is used as a magenta coupler to form a magenta dye. Phenol-based and naphthol-based compounds having hydroxyl groups are used as cyan couplers to form cyan dyes.

Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent;
Alternatively, it is dissolved in the silver halide emulsion using an auxiliary solvent if necessary, or added to the emulsion as an aqueous alkaline solution. Generally, the former is superior to the latter in terms of light resistance, moisture resistance, heat resistance, graininess, color sharpness, and the like.

The basic properties required of each coupler are not only to form a dye, but also to have high solubility in high-boiling organic solvents or alkalis, good dispersibility and stability in silver halide photographic emulsions, and formation. The resulting dyes are fast to light, heat, and moisture, have excellent spectral absorption characteristics, have good transparency, provide clear images, and more importantly, have high color density and It is desired to have various properties such as a high rate of pigment formation.

Furthermore, in order to reduce the cost of waste liquid treatment, it has become necessary to remove benzyl alcohol added during color development processing. However, the current situation is that when a color development processing solution to which benzyl alcohol is not added is generally used, the color development properties of the coupler added to the silver halide photographic emulsion, that is, the rate of dye formation and the maximum color development density are reduced. Therefore, it is desired that yellow couplers have color development properties that do not depend on benzyl alcohol and that the storage stability of the above-mentioned images is improved.

Furthermore, many studies have been conducted with the aim of improving the sharpness by 1 g and increasing the sensitivity of color photographic materials.

One technique is to improve the coupler. In other words, a coupler having a high color density per unit weight is advantageous in making the layer thinner because the amount of the coupler added to the light-sensitive material layer can be reduced accordingly.

This reduces scattering of light incident on the photosensitive layer and improves sharpness. Further, the higher the reactivity of the coupler with respect to the oxidized developing agent, the more efficiently the oxidized developing agent can be utilized, which is advantageous for increasing the sensitivity of the photosensitive material.

On the other hand, it is known that when the amount of high boiling point organic solvent used is reduced, the coloring properties of yellow couplers are reduced. However, in order to reduce the film thickness of the photosensitive emulsion layer, it is preferable to reduce the amount of high boiling point organic solvent used.
A yellow coupler is desired that exhibits sufficient color development even when the amount of high-boiling organic solvent used is reduced.

The skeleton structures of yellow couplers include pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, malonester monoamide type, benzothiazolylacetate type, benzoxacylylacetate type, and benzothiazolylacetate type. Imidazolylacetamide-type or benzimidazolylacetate-type couplers are known.

Specific examples of these yellow couplers are given in U.S. Pat.
No. 75,057, No. 3,265,506, No. 3,40
No. 8,194, No. 3,551,155, No. 3,582
, No. 322, No. 3,725.072, No. 4,356,
No. 258, No. 3゜891.445, West German Patent No. 1,54
No. 7,868, West German Application No. 2,219,917, West German Application No. 2,261.361, West German Application No. 2,414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. No. 47-26133, No. 48-73147,
No. 51-102636, No. 50-6341, No. 50
-123342, 50-130442, 51-
No. 21827, No. 50-87650, No. 52-824
No. 24, No. 52-115219, etc.

However, these known yellow couplers cannot be said to fully satisfy the above conditions.
For this reason, attempts have been made to modify the structure of the acyl group of acylacetanilide.For example, U.S. Pat. Couplers having a -1,1-dioxide nucleus are disclosed.

The couplers described herein had low color density and did not exhibit a yellow hue, so they were not sufficiently practical.

Moreover, JP-A-52-82423 only discloses a DIR coupler.

(Problem M to be Solved by the Invention) The first object of the present invention is to improve sharpness and increase sensitivity by forming images in the presence of a new yellow coupler that has a high dye formation rate and high color density. The object of the present invention is to provide a glass photographic material that can achieve the desired effect.

A second object of the present invention is to provide a novel yellow coupler that has sufficient coupling activity in a development processing system using a color developer to which no benzyl alcohol is added, and a method for forming a yellow dye image using the same.

A third object of the present invention is to provide a novel yellow coupler which is excellent in solubility in alkali or high-boiling organic solvents, dispersibility in silver halide color photographic emulsions, and stability.

A fourth object of the present invention is to provide a novel yellow coupler that exhibits little deterioration in color development even when the amount of high-boiling organic solvent used is reduced, and that allows the thickness of the photosensitive layer to be reduced.

(Means for Solving the Problems) That is, the present invention provides a silver halide color photographic material characterized by containing a dye-forming coupler represented by the following formula (I) in at least one layer on a support. It is something to do.

General formula: Person 1 represents the atomic group necessary to form a nitrogen-unsaturated heterocycle, R2 represents an aromatic group, B1. B2 represents a ballast group, Xl represents a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent and has no photographic utility; n and m each represent 0 or 1; where n+m=1. ) The compound represented by general formula (I) will be explained in detail below.

Man! The atomic groups necessary to form an elementary unsaturated heterocycle are: In a heterocycle, one nitrogen atom and the other three ring-forming atoms are all carbon atoms, or two carbon atoms and one nitrogen atom. consisting of atoms, oxygen atoms or sulfur atoms. This heterocycle may be substituted and may have other fused rings, these fused rings furthermore! i#! ! Specific examples of substituents on the above heterocycles and condensed rings which may be
butyl), aryl groups (eg phenyl), halogen atoms (eg industrial atoms, fluorine atoms, bromine atoms), alkoxy groups (eg methoxy, ethoxy), acylamino groups (eg acetamide).

Alkoxycarbonyl group (e.g. methoxycarbonyl)
, a sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), an acyl group (eg, acetyl), a sulfonamide group (eg, methanesulfonamide), a sulfamoyl group (eg, methylsulfonyl), and the like. Examples of the aromatic group represented by R2 include a phenyl group, a naphthyl group, a phenylene group, and these groups may have a substituent. Examples include substituents. B1 and B2 represent a ballast group, and a ballast group is a group that increases the molecular weight sufficiently so that it becomes immobilized in a photographic layer to which a coupler is added, and is a group containing a total number of carbon atoms of 8 or more. be.

Specifically, a ballast group commonly used in dye-forming pullers can be used.

Xl represents a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent and does not exhibit photographic utility. is the group represented.

- Formula (A) Crystal, 11-z "Zl represents a group of nonmetallic atoms necessary to form a 5- or 6-membered ring together with the nitrogen atom bonded to the active site." Specific examples include the following skeletons.

In addition, the nitrogen atom and carbon atom of the heterocycle may have a substituent that can be substituted. Specific examples thereof include an alkyl group (e.g., methyl, ethyl, ethoxyethyl), an aryl group (e.g., phenyl, -chlorophenyl), aralkyl groups (e.g. benzyl), alkoxy groups (e.g. methoxy).

ethoxy), halogen atoms (e.g. chlorine atoms).

fluorine atom), acylamino group (e.g. acetamide)
, a sulfonamide group (e.g. methanesulfonamide),
Examples include a sulfonyl group, a sulfamoyl group, a carbamoyl group, a carboxy group, an alkoxycarbonyl group, a hydroxyl group, a nitro group, a cyano group, and an alkenyl group (eg, vinylmethyl).

General Formula (B) Here, R3 represents an aryl group. Specific examples of the aryl group are phenyl group and naphthyl group, which may have a substituent. Specific examples of substituents include, for example, halogen atoms (e.g., chlorine atoms, etc.), alkyl groups (e.g., methyl), alkoxy groups (e.g., methoxy), acylamide (e.g., acetamide), sulfonamide groups (e.g., methanesulfonamide), sulfonyl groups ( For example, methylsulfonyl, 4
-hydroxyphenylsulfonyl), sulfamoyl group, carbamoyl group, carboxy group, alkoxycarbonyl group, hydroxyl group, cyano group, nitro group, and the like. n and m represent 1 or O''t'n+m=1, which means that the numbers are included.

A more preferable coupler used in the present invention is represented by the following formula (II).

- Formula (II) Qo represents a hydrogen atom or a monovalent group. ), Z2 is 1
．． X1B2 representing a 2-phenylene, vinylene or dimethylene group (which may have a substituent) has the same meaning as in general formula (I).

Preferred ones are the following general formulas (I) (IV) (V)
Indicated by (M).

l! (I[) (R') (V)
(VI) where 23 is substituted or unsubstituted 1
, two condensed benzene rings, and examples of the substituent include the above-mentioned substituents. Q represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and preferred groups of the ballast group represented by B2 are 10R4 group, -COR4 group, -3R4 group
Examples include groups. Here, R4 represents an alkyl group, R5 and R6 represent a hydrogen atom or an alkyl group, the above group may have a substituent, and the total number of carbon atoms in the above ballast group is 8 to 32. Particularly preferably 8 to 24.

Particularly preferred Xl is represented by the following general formulas (C) and (D).

General formula (C) Here, 24 represents a group of nonmetallic atoms forming a 5-membered heterocycle.

General formula (D) 7 where R7 is an arylsulfonyl group, an alkylsulfonyl group, an alkoxycarbonyl group, a cyano group, an acyl group,
It represents an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, a carboxy group, or an alkylcarbamoyl group, and the number of carbon atoms thereof is preferably in the range of 1 to 10. R8 is a hydrogen atom, a halogen atom, an alkyl group (1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms),
Represents a hydroxyl group, acylamino group, cyano group, or alkylsulfonamide group.

The compounds of general formula (I) according to the invention can be applied in multilayer, multicolor photographic materials having at least three different spectral sensitivities on the support. A multilayer natural/natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a θ-blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Furthermore, the compound of the present invention represented by general formula (I) can be used in any layer such as a high-speed layer or a medium-speed layer, and can also be used in a light-sensitive silver halide emulsion layer or a layer adjacent thereto. .

The amount of the compound of the present invention represented by general formula (I) varies depending on the structure and use of the compound, but is preferably lXl0-7 to 1 mol per mol of silver present in the same layer or an adjacent layer, particularly preferably 1xlO ' to 0.5 mole.

The compound of the present invention represented by general formula (I) may be used alone in a certain layer, or may be used in combination with a known coupler in any ratio.

Next, typical examples of couplers used in the present invention will be listed, but the couplers used in the present invention are not limited to these.

Photo ζ (C'J's
Dimension QtoCo (Fl
() Bukou Q Konohe no Sa
Synthesis Example (Synthesis of Exemplary Coupler (1)) Exemplary coupler (1) can be synthesized by the following route.

Synthesis of 3. 22 g and 2.40 g of orthoaminophenol were suspended in 300 ml of benzene and reacted at 30-40°C for 2 hours with stirring. 0 As the reaction progressed, the suspension became almost homogeneous. After the reaction, the mixture was poured into ice water,
The precipitated oily substance was extracted with 400 ml of ethyl acetate.

The organic layer was washed with water and then dried over magnesium sulfate. Next, the solvent was distilled off under reduced pressure to obtain 40 g of an oil. Fast atom impact ionization mass spectrometry, Po5iti
This was confirmed by observing (M+H)'' = 206 using the ve detection method.

Synthesis of No. 5 3.31.0 g and 4.42.4 g were stirred and heated at 140° C. to react. Ethanol produced during the reaction was distilled out of the system under reduced pressure. After reacting at 140"C for 3 hours, it was cooled to 50"C. Ethyl acetate 100111 was added to the mixture, and the mixture was cooled to 15° C. with stirring, and the precipitated crystals were collected by filtration. Yield: 43g, melting point: 11
The temperature ranged from 1 to 112°C. Similar to 3, mass spectrometry (M+H
)” = 584 was observed, confirming that it was 5.

Synthesis of Exemplary Coupler (1) 5.17.5 g was dissolved in DO form 150111J, and 2.9 g of sulfuryl chloride was added dropwise at 5-15° C. with stirring. After reacting at the same temperature for 2 hours, ice water was poured. Sodium bicarbonate was added portionwise to the reaction mixture to neutralize the reaction solution. The organic layer was washed with water and then dried over magnesium sulfate.

Next, chloroform was distilled off under reduced pressure to obtain 17 g of oil. On the other hand, add 6.21 g to 200 g of dimethylformamide
d, and 12.5 d of triethylamine was added dropwise thereto while stirring at 20°C. To this mixture, a solution of 17 g of the previously obtained oil dissolved in 35711i of dimethylformamide (35711i) was added dropwise while stirring at 30 to 40°C. After reacting at the same temperature for 3 hours, 300ml of ethyl acetate and 200ml of water were added. After washing the a-layer with water, it was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain an oily substance 3.
8g was obtained. The obtained oily substance was subjected to silica gel chromatography, and the portion containing the target compound was concentrated under reduced pressure to a powder state, thereby obtaining 9.8 g of exemplified coupler (1). The structure was confirmed by the observation of (M+H)'' = 816 in the mass spectrometry.

Other couplers of the invention can also be synthesized by substituting appropriate compounds for 1.4.6.

The light-sensitive material of the present invention may be provided with at least IM of silver halide emulsion layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. There are no particular restrictions on the number or order of layers and non-photosensitive layers.A typical example is to prepare a plurality of silver halide emulsions with substantially the same color sensitivity but different photosensitivity on a support. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a layer, the light-sensitive layer being a unit light-sensitive layer having sensitivity to any of blue light, green light, and red light; In multilayer silver halide color photographic materials,
Generally, there is an arrangement of unit photosensitive layers, or a red-sensitive layer and a green-sensitive layer in order from the support side.

The blue sensitive layer is installed in this order. However, depending on the purpose, the stirrup arrangement order may be reversed, or the arrangement order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1,121,470 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, the layers are arranged so that the sensitivity decreases toward the support. Preferably, a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 462-200350, No. 62-2
As described in No. 06541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or BH/BL/GL/GH/RH/RL, or BH/BL/GH/GL/RL/RH They can be installed in the following order:

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer that is more sensitive than the middle layer. An example is an arrangement consisting of three layers having different photosensitivity, in which a silver halide emulsion layer with a low density is arranged, and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention are:

For example, Research Disclosure (RD), No.
17643 (December 1978), pp. 22-23,”
1. Emulsion preparation
onand types)”, and No. 18 of the same
716 (November 1979), 64B pages, graphic "Physics and Chemistry of Photography", published by Paul Montell (P.

Glafkides, Chemie et Ph1s
ique PhotographiquePaul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin
.

Photographic Emulsion C
hemistry (Focal Press.

1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelik
manet al-Making and (:oat
ing Photographic Emulsion,
Focal Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are.

Written by Gatsuto, Photographic Science and
Engineering (Gutoff Photography
hicScience and Engineering
g), Vol. 14, pp. 248-257 (1970)
: U.S. Patent No. 4,434.226, U.S. Patent No. 4,414,3
No. 10, No. 4゜433.048, No. 4,439,52
0 and British Patent No. 2,112,157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a single layer structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening 3 and spectral sensitization. The additives used in such a process are described in the aforementioned Research Disclosure No. 17643 and Research Disclosure No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures listed above, and are listed in the Table below. The location is shown.

Additive type RD 17643 RD 1137
161 Chemical sensitizers Page 23 Page 548 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, Pages 23-24 Page 648 Right column - Super sensitizers
Page 649, right column 4 Brightener
Page 24 5 Antifouling agent Pages 24-25 Page 649 Right column ~
and Stabilizer 6 Light absorber, pages 25-26, page 549, right column ~
Filter dye, page 650, left column, ultraviolet absorber 7, stain inhibitor, page 5, right G, page 650, left to right column 8, dye image stabilizer, page 25, 9 hardener, page 26, page 651, left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column 12 Coating aid, pages 26-27 Same as above Surface active agent 1 Costatic prevention Page 27 Same as above Stop agent Also prevents deterioration of photographic performance due to formaldehyde gas Therefore, it is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde, as described in U.S. Pat.

Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) No. 17643. (2) It is described in the patents listed in C to G.

As a yellow coupler, for example, 3.93 per U.S. patent
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401.752, Special Publication No. 5
B-10739, British Patent Section 1,425,020;
No. 1,476°760, U.S. Patent No. 3,973,9
No. 68, No. 4,314,023, No. 4.511,
Preferred are those described in No. 649, European Patent No. f5249,473A, and the like.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
0,619, European Patent No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3,061,432, European Patent No. 3,725,067, Research Disclosure No. 24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure No. 2
4230 (June 1984), JP-A-60-4365
No. 9, No. 61-72238, No. 60-35730,
No. 55-118034, No. 60-185951, U.S. Patent No. 4,500,630, No. 4,540,65
Particularly preferred are those described in No. 4, No. 4,556,630, and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4,296,200, No. 2,369,9
No. 29, No. 2,801.171, No. 2,772,
No. 162, No. 2,895,826, No. 3,772
, No. 002, No. 3,758,308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121.365
No. A, No. 249,453A, U.S. Patent No. 3,446
, No. 622, No. 4,333.999, No. 4,45
No. 1,559, No. 4,427,767, No. 4,6
No. 90,889, No. 4,254,212, No. 4,
296.199, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No. 17643.
Paragraph ■-G, U.S. Pat.
The one described in No. 368 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent Section 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576.910, British Patent Section 2,102
, No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
■-Patent listed in Section F, JP-A-57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Patent No. 4,248,962.

Couplers that imagewise release a nucleating agent or a development accelerator upon development include British Patent Section 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. .

Multi-equivalent couplers described in 4,310,618 etc.
JP-A-60-185950, JP-A-62-24252
DIR redox compound-releasing couplers or DIR coupler-releasing couplers or DIR coupler-releasing redox compounds or DIR redox compound-releasing redoxes described in European Patent No. 173,302A, couplers that release dyes that recolor after separation, R ,D.

No. 11449, 24241, JP-A-61-201
Examples thereof include bleach accelerator-releasing couplers described in US Pat. No. 247 and the like, and ligand-releasing couplers described in US Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of highly sensitive solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027 and the like.

The temperature at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high-elevation point organic solvents include phthalate esters (dibutyl phthalate).

Dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t
-amylphenyl)phthalate, bis(2,4-di-t)
-amyl phenyl) isophthalate, bis(1,l-diethylpropyl) phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, Tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate,
-ethylhexyl-p-hydroxybenshade, etc.)
, amides (N,N-diethyldodecanamide, N,N
-diethyl laurylamide.

N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-
di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N -dibutyl-2-butoxy-5-t-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the temperature is about 30°C or higher, preferably 50°C or higher and about 160°C.
Organic solvents of C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

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

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, and same No. 187
16, pages 64 and 7, right column to page 648, left column.

The color photographic material according to the present invention includes the above-mentioned RD, N
o, 17643, pages 28-29, and same No. 187
16, No. 651, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, and P-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, hydrazine sulfites, phenyl semicarbalads, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2°2.2]octane) Various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, sodium boron hydrite, etc. fogging agents, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids,
Various chelating agents such as phosphoric acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-
1,l-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',
Representative examples include N''-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone.

Known black and white developing agents such as 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 3 m2 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 m1.
You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be carried out simultaneously with the fixing process, or may be carried out separately (bleach-fixing process) 1. Furthermore, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process.
Depending on the purpose, it is also possible to carry out treatment in two sequential bleach-fixing baths, to carry out fixing treatment before bleach-fixing treatment, or to carry out bleaching treatment after bleach-fixing treatment. As bleaching agents, 1. For example, polyvalent compounds such as iron (■), cobalt (■), chromium (■), copper (II), peracids, quinones, nitro compounds, etc. are used.0 Typical bleaching agents As an agent, ferricyanide; dichromate: iron (m)
Or organic complex salts of cobalt (m), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-
Aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.: PerT & acid salts: Bromates: Permanganates: Nitrobenzenes, etc. can be used. can. Of these, iron ethylenediaminetetraacetate (
m) Aminopolycarboxylic acid iron (m) complex salts and persulfates, including complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention, and aminopolycarboxylic acid iron (m) complex salts are also effective in bleach-fixing in bleaching solutions. It is also particularly useful in liquids. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. .

A bleach accelerator may be used in the bleaching solution, B white fixing solution, and their pre-bath, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059.988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623, No. 53-28426, and Research Disclosure No. 17129 (July 1978), etc. Thiazolidine derivatives described in No. 50-140129; Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-2083
No. 2, No. 53-3741, U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61: West German Patent Nos. 1 and 12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966.410 and 2,748.4
Polyoxyethylene compounds described in No. 30: Polyamine compounds described in Japanese Patent Publication No. 45-8836: Other JP-A Nos. 49-42434, 49-59644, and 53
-94927, 54-35727, 55-26
Compounds described in No. 506 and No. 58-163940: bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat.
The compound described in No. 0 is preferred.

Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred, and these bleach accelerators may be added to the sensitive material. These bleach accelerators are particularly effective when bleaching and fixing color photographic materials.

Fixatives include thio, sulfate, and thiocyanate.

Examples include thioether compounds, thioureas, large amounts of iodide salts, etc., but thiosulfates are commonly used, and ammonium thiosulfate can be used most widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of washing tanks and the amount of water in multi-stage countercurrent method 3 is J
our own of the 5ociety of
MotionPicture and Te1evis
ion Engineers Volume 64, 9.248-2
53 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will grow and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems, the method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1980 is extremely effectively used. be able to. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use disinfectants described in ``Sterilization, sterilization, and anti-mold technology of microorganisms'', Hygiene Technology Extra Section, and ``Encyclopedia of Antibacterial and Antifungal Agents'', Japanese Antibacterial and Antibacterial Science Extra Section.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 25 to 45°C.
A temperature range of 30 seconds to 5 minutes at 40 DEG C. is selected.Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-148
All known methods described in No. 34 and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out. An example of this is a stabilization bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for image manipulation. can. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342
, No. 599, Research Disclosure 14850
Ship base-type compounds described in No. 1 and No. 15159, No. 1
Aldol compounds described in No. 3924, U.S. Patent No. 3.7
Metal salt complex described in No. 19,492, JP-A-53-135
Examples include urethane compounds described in No. 628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are JP-A-56-64339 and JP-A-57-144547 S.
and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, West German Patent No. 2.226,770 or U.S. Pat.
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

Furthermore, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention contains a novel yellow coupler that has a high dye formation rate and a high color density, and can achieve improved image sharpness and high sensitivity. .

Furthermore, the silver halide color photographic light-sensitive material of the present invention exhibits sufficient coupling activity and high color development even in a development processing system using a color developer to which benzyl alcohol is not added.

Furthermore, this silver halide color photographic light-sensitive material has excellent solubility of the yellow coupler in alkali or high-boiling organic solvents, dispersibility and stability in silver halide color photographic emulsions, and excellent storage stability.

Furthermore, in this silver halide color photographic light-sensitive material, even if the amount of the highly sensitive organic solvent used is reduced, there is little deterioration in color development, and therefore the thickness of the photosensitive layer can be reduced.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 A photographic element was prepared consisting of layers of the composition described below on a paper support laminated on both sides with polyethylene.

1-JW-...Mix yellow coupler and di-n-butyl phthalate so that the weight ratio is 2=1, add ethyl acetate and dissolve by heating, then add surfactant (sodium dodecylbenzenesulfonate). An emulsified dispersion of a yellow coupler was obtained by emulsifying and dispersing it in an aqueous gelatin solution containing a silver chlorobromide emulsion (silver bromide 80 mol%) with a molar ratio of silver to coupler of 3.5. : A mixed solution was prepared so that the ratio was 1.

Second layer: A gelatin aqueous solution mixed with a hardening agent (sodium 2-hydroxy-4,6-dichloro-5-)-lyazine) and a surfactant (Triton X-200) was prepared.

Coated samples 100 to 110 were prepared by changing the yellow coupler used in the first layer as shown in Table 1. The amount of coupler applied was adjusted to 1.30 mmol/m'.

Comparative coupler A using the following coupler as a comparative coupler Synthesized using the coupler described in US Pat. No. 3,841,880.

Comparative coupler B Coupler described in U.S. Patent No. 4,401,752 Comparative coupler C Coupler No. described in JP-A-56-151932
1 Table After exposing each sample to light at the mouth, development processing was performed using the following processing steps.

Processing process (33°C) Color development (A) or (B) Bleach fixing for 3 minutes and 30 seconds
Wash with water for 1 minute and 30 seconds
Dry for 3 minutes 1
0 minute The components of each treatment step are as follows.

Color developer (A) Benzyl alcohol 15ml Diethylene glycol 5ml Potassium carbonate
25g sodium chloride
0.1g sodium bromide
0.5g Anhydrous sodium sulfite 2g
Hydroxylamine sulfate 2gN-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4g Add water to 1
9. Then, add NaOH to make the pH 1O03.

Color developer (B) Same composition as color developer (A) except that benzyl alcohol was removed.

Bleach-fix solution Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g EDTA ferric ammonium salt
65 g of water was added to make IfL, and the developed sample was adjusted to pH 6 and 8. The color density of each sample was measured. Table 2 shows the fog, gamma, and Dmax of each sample.

From Table 2, samples 103 to 110 of the present invention are comparative sample 10.
It exhibits sufficient color development compared to 0 to 102, and has the characteristic that concentration and gamma hardly decrease when using a color developing agent (B) without benzyl alcohol.

Example 2 A photographic element was prepared consisting of layers of the composition described below on a cellulose acetate film support.

Layer - Yellow coupler and tricresyl phosphate are mixed at a weight ratio of 3:1, ethyl acetate is added and dissolved by heating, followed by an aqueous gelatin solution containing a surfactant (sodium dodecylbenzenesulfonate). An emulsified dispersion of a yellow coupler was obtained by emulsifying and dispersing a yellow coupler into a silver iodobromide emulsion (silver iodide 6 mol %) at a molar ratio of silver to coupler of 3.5:1. A liquid was prepared by mixing the following.

Second layer: gelatin aqueous solution with hardening agent (l,3-vinylsulfonyl-2-propanol) and surfactant (Tri
ton X-200) was prepared.

Coating samples 201 to 210 were produced by changing the yellow coupler used in the first layer as shown in Table 3. The amount of coupler applied was adjusted to 1.25 mmol/m'.

In addition, samples (211 to 220) were prepared in which the weight ratio of yellow coupler to tricresyl phosphate was 10=1. In addition, samples (211~
The emulsion of 220) was left at 5°C for 24 hours and observed.

This sample was subjected to wedge exposure with white light and developed at 38°C as follows.

1. Color development...3 minutes 15 seconds 2. Bleaching
...6 minutes 30 seconds 3, washing with water...3 minutes 15 seconds 4, fixing...6 minutes 30 seconds 5, washing with water...3 minutes 15 6 seconds, stable...3 minutes 15 seconds The composition of the processing solution used in each step is as follows.

Color developer Sodium nitrotriacetate i, 0g Sodium sulfite 4.0g Sodium carbonate
30.0g potassium bromide
1.4g hydroxylamine sulfate 2
．． 4g4-(N-ethyl-N-β hydroxyethylamino)-2-methyl-aniline sulfate Add 4.5g water
1! ;L bleaching solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0m Ethylenediamine
Sodium iron tetraacetate 130g Glacial acetic acid
Add 14ml water
11 Fixer Sodium tetrapolyphosphate 10g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0d Sodium bisulfite 4.6g Add water
1-exchange stabilizer formalin 8.011ii Add water 1 sentence Note that the coupler used in Example 1 was used as the comparative coupler.

As is clear from Table 3, by implementing the present invention, high gamma, high sensitivity, and high color development are exhibited without increasing fog. In addition, as seen from the comparison between samples 208 and 218, the comparative coupler (A) shows some color development when the tricresyl phosphate/coupler ratio is large, but when the amount of tricresyl phosphate used is reduced, the color develops significantly. In contrast, samples using the 2-equivalent coupler of the present invention show less dependence of color development on the amount of tricresyl phosphate, and this has the characteristic that the film thickness can be made thinner. It means that

In addition, as a result of conducting a 24-hour aging test at 5°C on the emulsions used to create samples (211-220), sample 218 (
Comparative coupler A) and sample 219 (comparative coupler B)
Coupler precipitation was observed in the sample of the present invention (211
-217), no coupler precipitation was observed, indicating that the emulsions had excellent storage stability.

Example 3 (Preparation of Sample 301) On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer having the following composition was prepared and designated as Sample 301.

1st layer: antihalation layer black colloidal silver 0.25g /rrr' ultraviolet absorber U -10,04g /d ultraviolet absorber U-2
0.1 g/rn' Ultraviolet absorber U-30.1 g/m'' Gelatin layer containing high boiling point organic solvent Qil-20.01 cc/m'' (dry film thickness 2 l) 2nd layer: Intermediate layer compound Cpd-C0 ,05g/rrr'Compound I-1
0.05g 1rrf Gelatin layer containing high boiling point organic solvent 0i1-1 0.05cc/m' (dry film thickness IIL) 3rd layer: 1st red-sensitive emulsion layer Spectral enhancement with sensitizing dyes S-1 and S-2 Sensitized silver bromide emulsion (average grain size 0.3 g AgI content 4 mol%) Silver amount...0.5 g/rn' Coupler F-10,2 g/rn' Coupler F-20,05 g/Go compound Gelatin layer containing I-22x 1G-3g/m' high-boiling organic solvent 0i1-1 0.12cc/m'' (dry film thickness 1u-) 4th layer: 2nd red-sensitive emulsion layer Sensitizing dye S-1 and Silver bromide emulsion spectrally sensitized with S-2 (average grain size 0.6 g).

AgI content 3 mol%) Silver amount...0.8 g/m' coupler F -10,55 g/rn' coupler F -
20.14g/Go compound I-21XI (1-3g/Go high boiling point organic solvent 0i1-1 0.33cc/Go dye D-10,02
gelatin layer (dry film thickness 2.5 g) containing g/m'' 5th layer: Intermediate layer compound Cpd-C0,1 g/rn' High boiling point organic solvent Oi11 0.1 cc/rn' Dye D -20,02 g/rn' gelatin layer containing rn' (dry film thickness 1 g) 6th layer: first green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (
Average particle size 0.3XIm.

AgI content: 4 mol%) Silver content: 0.7 g/Go coupler F -30,20 g/m' Coupler F -50,10 g/rn' Gelatin containing high boiling point organic solvent 0i1-1 0.26 cc/rn' Layer (dry film thickness: 1 l) 7th layer: 2nd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (
Average particle size 0.6XIm, AgI content 265 mol%) Silver amount...0.7 g 7m" Coupler F -40,10g /rn' Coupler F -
50,10g/rrf high boiling point organic solvent 0i1-2
0.05cc/m'' Dye D-30-05g/Gelatin layer containing Go (dry film thickness 2.5L) 8th layer: Intermediate layer compound Cpd-CO, 05g/Go High Fossa point organic solvent 0i1-2 0 Zeracene layer containing .1 cc/m" Dye D -40,01 g/rn" (dry film thickness 11 L) 9th layer: Yellow filter layer Yellow colloidal silver 0.1 g/rrf compound Cpd-CO, 02 g/m" Gelatin layer (dry film thickness IJL) containing 0.04 cc/m'' of Takasho point solvent 0i1-1 (dry film thickness IJL) 1st O layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dye S-5 (average Particle size 0.
3XIm, AgI content 2 mol%) Silver amount・
...0.6 g/rn' coupler F-6 (comparative coupler C) 0.4 g/m" gelatin layer containing high boiling point organic solvent 0i1-1 0.1 cc/rn' (dry film thickness 1-5= ) Eleventh layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion containing i-sensitive dye S-6 (average grain size 0.
6 gm, AgI content 2 mol%) Silver amount -1
, 1 g/rn' coupler F-6 (comparative coupler C) 0.8 g/m'' high boiling point organic solvent Oi1-1 0.23 cc/n'coupler D-50,
Gelatin layer containing 02g/m'' (dry film thickness 3JL) 12th layer: 1st protective layer UV absorber U -10,02g/rrfUV absorber U -20-32g/m'UV absorber U -30
-03g/m' High boiling point organic solvent 0i1-2 0.2
Gelatin M containing 8 cc/m'' (dry film thickness 2 IL) 13th layer: Fine grain silver iodobromide emulsion covered with the second protective layer Silver amount...0.1 g/g (Iodine content 1 mol%) , average particle size O, 0aIL) polymethyl methacrylate particles (average particle size i, sl) Gelatin layer (dry film thickness: z, sp) In addition to the above composition, each layer contains a gelatin hardening agent H-- 1 and a surfactant were added.

The compounds used to prepare the samples are shown below.

IN H F-6 (Comparative coupler C) Compound I-1 Compound 1-2 -C4H9 U-3 Cpd C H -L Oil -1 Tricresyl phosphate Oi+-2
Diptyl 7-talate (preparation of samples 302 to 308) Coupler F-6 in the 1st O layer and 11th layer of sample 301
Instead, replace the coupler shown in Table 4 so that the number of moles of the color forming unit is equal to that of coupler F-6, and change the amount of high boiling point organic solvent Oi1-1 to Oil-1 (g)/Coupler (g). Sample 30 except that it was added so that the ratio of
It was produced in the same manner as 1.

Samples 301 to 308 were cut into 351-inch pieces and each was subjected to a running test of 500 m using the processing method shown below, followed by wedge exposure with white light.

Development was performed using the method shown below, and color development was evaluated. The results are shown in Table 4.

First development 6 minutes 38℃ 12 sentences 2200mfl!
/ Washing with water 45 seconds 38℃ 21 2200d
/go reversal 45 seconds 38℃ 2 sentences 1
toon'g/ is color development 6 minutes 38℃ 12 minutes
2200711/Go bleach 2 minutes 38℃
4 1 860d/rn' bleach fixing 4 minutes 38
°C 8-way 1100d/rn' Second water wash (1) 1 minute
38℃ 29. □Second washing (2) 1 minute 386C21
110ro Tr1i! /rr1' stable 1 minute
25℃ 2 1 1100fi/m' drying
1 minute 65℃ □ □Here, the replenishment of the second water wash is a so-called countercurrent replenishment in which the replenisher is introduced into the second wash (2) and the overflow liquid from the second wash (2) is introduced into the second wash (1). The composition of each treatment solution was as follows.

1st development layer mother solution Replenisher Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 2.0g 2.0g
Sodium sulfite 30g 30g Hydroquinone/potassium monosulfonate 20g 20g Potassium carbonate 33g 33g1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0g 2.0g
Potassium bromide 2.5g 1.
4g potassium thiocyanate 1.2g 1
．． 2g potassium iodide 2.0g □
Add water 1000d 1000
Printing pH 9,609,60 PH was adjusted with hydrochloric acid or potassium hydroxide.

First washing liquid mother liquor Replenisher ethylenediaminetetra Add 2.0 g of methylene phosphonic acid and 5.0 g of the same disodium phosphate water to the mother liquor.
100071ip H7,00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Ward 5 Mother Liquor Replenisher Nitrilo-N, N, N- Trimethylenephosphonic Acid 5 Sodium Salt in Mother Liquor 3.0g Same Stannous Chloride Dihydrate 10 gp-Aminophenol
0.1g Sodium hydroxide 8g
Add 15ml of glacial acetic acid and 1 water
1000 pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developer mother solution Replenisher Nitrilo-N, N, N- Trimethylenephosphonic acid pentasodium salt 2.0g 2.0g
Sodium sulfite 7.0g 7.0
g Trisodium phosphate dodecahydrate 36 g 36 g Potassium bromide 1.0 g - Potassium iodide 90 mg □ Sodium hydroxide 3.0 g 3.0 g Citrazic acid 1-5 g 1.5 g N-ethyl-N-(β-methanesulfone Amidoethyl)-3-methyl-4-aminoaniline sulfate 11g 11g3.
6-cythiaoctane-1,8-diol 1.0g 1.0g
Add water 1000 d
P H11,8012,00 pH was adjusted with hydrochloric acid or potassium hydroxide.

) Wataru Kaoru mother liquor Replenisher ethylenediaminetetraacetic acid, mother liquor with disodium salt and dihydrate salt 10. Og Same ethylenediaminetetraacetic acid/Fe(III)/ammonium/dihydrate 120g ammonium bromide 100g ammonium nitrate
10g bleach accelerator o-oos
Add molar water to 1000dp H6
, 30 pH was adjusted with hydrochloric acid or aqueous ammonia.

Purulent fixer mother solution Replenisher ethylenediaminetetraacetic acid, iron (m), ammonium Dihydrate salt in mother solution
5. , Og Same ethylenediaminetetraacetic acid, disodium, dihydrate 5.0g Sodium thiosulfate 80g Sodium sulfite
Add 12.0g water and iooom
ap H6,60 pH was adjusted with hydrochloric acid or aqueous ammonia.

Second washing solution Both the mother solution and the replenisher were tap water filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through the mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg/fl or less, and then 20 mg/l of sodium isocyanurate dichloride and 5 g/liter of sodium sulfate were added. The pH of this solution is 6.5
~7.5.

Acquired axillary mother liquor Replenisher formalin (37%) 5.0% water Add the same polyoxyethylene p-monononylphenyl ether (average degree of polymerization 10) 0.5 ml water to the mother liquor 100071ipH without adjusting Table 4. It is evident that the sample using the coupler of the present invention has excellent color development.

Example 4 On a subbed cellulose triacetate film support,
Sample 401, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/m'' of silver for silver halide and colloidal silver, and the amount expressed in g/rn' for couplers, additives and gelatin. Sensitizing dyes are indicated by the number of moles per mole of silver halide in the same layer.The symbols indicating additives have the meanings shown below.However, if they have multiple effects, only one of them Posted on behalf of.

Uv; ultraviolet absorber, 5olvH high boiling point organic solvent, Ex
F: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Isanro coupler, Cpd: Additive 1st layer (antihalation layer) Black colloidal silver...0.15 gelatin ・-2,9UV-1-0
,03 UV-2-0,06 UV-3-0,07 Sol v-2---0,08 ExF-1...0.0I ExF-2---0,01 2nd layer (low Sensitive red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform equivalent sphere diameter 0.41L, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/thickness ratio 3.0
) Coated silver amount ・-0,4 Gelatin ・-0,8ExS-
1---2,3X 10-' ExS-2--1,4X 1O-4 ExS-5...2.3X10-4 ExS-7--8, Ox 10-6 ExC-1-- -0,17 ExC-2---0,03 ExC-3---0,13 Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 2:l) Internal height A
gI type, ball equivalent diameter 0.65 tiles, coefficient of variation of ball equivalent diameter 25
%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount - 0.65 Silver iodobromide emulsion (AgI 4 mol%, uniform - AgI type, equivalent sphere diameter 0.4
Coating silver amount -0.1 Gelatin...1.0ExS
-1...2xlO-'ExS-2...1.2X10-'ExS-5--2xlO' ExS-7--7x l 0-6 ExC-1--0,31 ExC-2 ---0,01 ExC-3---0,06 Fourth! j (High-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2:1 internal height A)
gT type, ball equivalent diameter 0. Full, coefficient of variation of equivalent ball diameter 25%
, plate-shaped particles, diameter/thickness ratio 2.5) Coated silver amount...0.9 gelatin ・
-0,8ExS-1---1,axio-4 ExS-2---1,5xio-4 ExS-5---1,sx 10-4 ExS-7---6xlO-4 ExC-1・-0,07 ExC-4---0,05 So 1v-1---0,07 Solv-2---0,20 Cpd-7・-4,6xlO-' 5th layer (middle layer) Gelatin ...0.6UV-
4-0,03 UV-5-0,04 cpct-t -0,1 polyethyl acrylate latex...0.08Sol
v-1---0.05 6th layer (low sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol% uniform type, equivalent sphere diameter 0.4 Hiro, coefficient of variation of equivalent sphere diameter 37%, Platy particles.

Diameter/thickness ratio 2.0) Coated silver amount...0.18 Gelatin -0.4ExS-
3---2x 10-' ExS-4---7x 10-'ExS-5-...lXl0-' ExM-5---0,11 ExM-7...0.03 ExY-8 ---0,01 Solv-1・-0,09 So 1 v-4 ---0,O1 7th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio l :L surface height A
gI type 1 ball equivalent diameter 0.5 way, coefficient of variation of ball equivalent diameter 20%
, plate-shaped particles, diameter/thickness ratio 4, o) Coated silver amount -0,27 gelatin -
0,6ExS-3...2xlO-' ExS-4...7xlO-4 ExS-5/-1xlO-4 ExM-5--0,17 ExM-7--0,04 ExY-8- --0,02 Solv-1---0,14 So 1v-4---0,02 8th F' (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 8.7 mol%, silver amount Multilayer structure particles with a ratio of 3:4:2, AgI content of 24 mol, 0 mol, 3 mol% from the inside, equivalent sphere diameter of 0.7 tiles, coefficient of variation of equivalent sphere diameter of 25%,
Plate-shaped particles, diameter/thickness ratio 1.6) Coated silver amount -0
,7 gelatin...0.8E
xS-4---5,2x 10-4 ExS-5---1xlO' ExS-8...0.3xlO-4 ExM-5---0,I ExM-6---0,03 ExY -8---0,02 ExC-1---0,02 ExC-4---0,Ol 5olv-1---0,25 So 1 v-2---0,06 Solv-4- --0,01 Cpd-7+++1xto-4 9th layer (middle layer) Gelatin...0.6Cpd
-1・-0,04 Polyethyl acrylate latex ・-0,12Solv
-1---0,02 1st O layer (toner layer with multilayer effect on red-sensitive layer) Silver iodobromide emulsion (Agl 6 mol%, core shell ratio 2:l internal height A)
gI type, equivalent ball diameter 0.7JL1 ball equivalent diameter coefficient of variation 25
%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount: 10.68 silver iodobromide emulsion (AgI 4 mol% uniform type, equivalent sphere diameter 0.4, coefficient of variation of one sphere equivalent diameter 37%) , plate-like particles, diameter/thickness ratio 3.0
) Coated silver amount -0,19 gelatin
-1,0ExS-3...6xlO-' ExM-10--0,19 Solv-1-0,20 11th layer (yellow filter layer) Yellow colloidal silver -0,06 gelatin...0 .8Cpd-2・
・・0.13 Solv-1-0,13 Cp d -1++・0.07 Cpd-6...0.002 H-1...0.13 12th layer (low sensitivity blue-sensitive emulsion layer) Iodine Silver bromide emulsion (AgI 4.5 mol%, uniform AgI type, equivalent sphere diameter 0
-7JL, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount -0.3 Silver iodobromide emulsion (AgI 3 mol%, equivalent to 1 sphere of uniform AgI type) Diameter 0, 3
1L, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter/thickness ratio 7.0) Coated silver amount -0.15 Gelatin °-1.8ExS-
6---9X10-4 ExC-1-0-06 ExC-4---0,03 ExY-9---0,14 ExY-11--・0.89 So l v -10,,0, 42 13th layer (middle layer) Gelatin...0.7ExY
-12--0,20 So l v -1--0,34 14th layer (highly sensitive blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type 5 sphere equivalent diameter 1
．． Coefficient of variation of 0μ1 ball equivalent diameter 25%.

Multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount -O
,S Gelatin...0.5ExS
-6---1xlO-' ExY-9--0,01 Coupler of the present invention (10)...0.2°Ex
C-1---0,02 Solv-1---0,10 15th layer (first protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.0
7. ) Coated silver amount - 0,12 gelatin
...0.9UV-4-0,11 UV-5-0,16 Solv-5...0.02 8-1 -0.13cpct
-s...-0-10 polyethyl acrylate latex,...◆0.09 16th layer (second protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, average -AgI type 5 sphere equivalent diameter 0.0
71L) Coated silver amount - 0.36 gelatin
... 0.55 volume ≠ methacrylate particle diameter 1. sIL...0.2H-1
-...0.17 In addition to the above components, each layer contains emulsion stabilizer Cpd-3 (
0,07 g/rn'), surfactant Cpd-4 (0,0
3 g/rn') was added as a coating aid.

V-1 V-2 V-3 V-4 N (x/y=7/3 (weight ratio)) V-5 Solv-1 tricresyl phosphate 5 olv-27 dibutyl talate olv-4 SOLv-5 trihexyl phosphate xF-1 xS -1 ExS-2 ExS-3 ExS-4 ExS-5 ExS-6 ExS-7 ExS-8 1) Sono 5 Mao X - Tashi ti3 Cpd-7 Cpd-1 8H17 Cpd -2 Cpd-6 Cpd-5 Cpd-3 Cpd-4 L, M2=L, ;M-:)LJ2-L, 12-L, (J
In Sample 461, the comparative coupler (A) was substituted for the inventive coupler (10) in the 14th layer.
.

Sample 4 except that (B) and coupler (10) were added in an equimolar amount
A sample prepared in the same manner as No. 01 was used as a comparative sample.

After the color photographic light-sensitive material was exposed to light as described above, it was processed by processing method A or B described below.

Processing method A Process Processing time Processing temperature Color development 3 minutes 15 seconds 38℃ bleaching
1 minute 00 seconds 38℃ bleach fixing 3 minutes 15
Seconds 38℃ water washing (1) 40 seconds 35
℃ water washing (2) 1 minute 00 seconds 35℃ stable
Dry for 40 seconds at 38°C. Dry for 1 minute and 15 seconds at 55°C. Next, the composition of the treated heel fluid will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.01-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate
30.0 Potassium Bromide
l·4 Potassium iodide 1.
5 g Hydroxylamine sulfate 2.44-
(N-Ethyl-N-β-hydroxyethylidene)-2-methylaniline sulfate 4.5 Add water
i, o or pH 10,05 (bleach solution) (unit g) ethylenediaminetetraacetic acid ferric ammonium dihydrate 120-0 ethylenediaminetetraacetic acid disodium salt 10.0 ammonium bromide Zoo, 0 ammonium nitrate
10.0 Ammonia water (27%)
Add 15.0mR water
1.0 exchange p) I 6
．． 3 (Bleach-fix solution) (Unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Thiosulfurized ammonium aqueous solution (70%) 240.07i Ammonium Sana water (27%) Add 6.0m2 water
1.0! ;Lp)i
7.2 (Washing liquid) A mixed bed type in which tap water was filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3 mg/n or less, and then 20 mg of sodium isocyanurate dichloride was added.
/l and 150 mg/4 sodium sulfate were added. The pH of this liquid is in the range of 6.5 to 7.5.

(Stabilizing liquid) (Unit: g) Formalin (37%) 2.0d Polyoxyethylene-p-monononylphenyl nityl (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1 .0 sentence pH 5.0 to 8.0 Processing method B Step Processing time Processing temperature Color development 2 minutes 30 seconds 40°C bleach-fixing 3
Minutes OO seconds 40℃ water washing (1) 20 seconds 35℃ water washing (2)
20 seconds Stable at 35℃ 20 seconds
Dry at 35℃ for 50 seconds 6
5°C Next, the composition of the treatment liquid will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 2.01-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate
30.0 Potassium Bromide
1.4 potassium iodide
1.5B hydroxylamine sulfate 2.44
-(N-ethyl-N-(β-hydroxyethyl)amino) -2-methylaniline sulfate 4.5 Add water
1.0 fL pH 10,05 (bleach-fix solution) (unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260. 0 diluted acetic acid (
98%>5.0d bleach accelerator
Add 0.01 mol water
1.09゜pH 6.0 (washing liquid) Fill tap water with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through the mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, followed by 20 mg of sodium isocyanurate dichloride.
/l and 1.5 g #L of sodium sulfate were added.

The pH of this liquid is in the range of 6.5 to 7.5.

(Stabilizing liquid) (Unit: g) Formalin (37%) 2.0d Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1. 0 pH 5, o to 8.0 Even in the above development process, the sample of the present invention showed excellent color development.

Claims (1)

[Scope of Claims] A silver halide color photographic material comprising a dye-forming coupler represented by the following general formula (I) in at least one layer on a support. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents the atomic group necessary to form a 5-membered nitrogen-containing unsaturated heterocycle with ▲There are mathematical formulas, chemical formulas, tables, etc.) , R_2 represents an aromatic group, B_1, B_
2 represents a ballast group;
Or represents 1. However, n+m=1. )