JPH06130597A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material high in sensitivity and superior in color image fastness and graininess by incorporating a specified coupler in a blue-sensitive silver halide emulsion layer. CONSTITUTION:The blue-sensitive silver halide emulsion layers comprise plural emulsion layers different in sensitivity among one another and one of them except the highest sensitive one is situated farthest from a support, and at least one of them contains the coupler represented by formula I or II, and they have an ISO sensitivity of >=160. In the formulae I and II, each of X1 and X2 is an alkyl, aryl, or heterocyclic group; X3 is an organic group necessary to form an N-containing heterocyclic group together with >N-; Y is an aryl or heterocyclic group; and Z is a group to be released by the reaction of this coupler with the oxidation product of a developing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a high-sensitivity silver halide color photographic light-sensitive material containing a novel yellow coupler having good color image fastness and having improved graininess.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, it is an important characteristic that an image obtained by using it is stable for a long period of time. The yellow coupler of the present invention is an excellent yellow coupler having high color forming property and good color image fastness. However, when a silver halide color photographic light-sensitive material is prepared using the yellow coupler, the following problems occur. Have been found by the inventor. That is, the graininess of the yellow image is deteriorated. Furthermore, when this problem was examined in detail, the following important findings were obtained. The deterioration of graininess due to the use of the yellow coupler of the present invention is remarkable as the grain size of the silver halide emulsion is larger.

Since silver halide color photographic light-sensitive materials are often used for photography, increasing the sensitivity thereof is an important issue in the sense of providing a user-friendly film. To achieve this task, increasing the grain size of the photosensitive silver halide emulsion is the most commonly used method. However, increasing the grain size has the consequence that the graininess of the image obtained at the same time is deteriorated. Therefore, improving the graininess is an important issue in the development of a high-sensitivity silver halide color photographic light-sensitive material.

The yellow coupler of the present invention is an excellent yellow coupler having high color developability and good color image fastness, but it has a characteristic that the graininess is greatly deteriorated particularly when the grain size of the silver halide emulsion is large. Makes the problem of achieving both high sensitivity and graininess more difficult, and solving this problem is a very important problem.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-sensitivity silver halide color photographic light-sensitive material excellent in color image fastness and graininess.

[0006]

It has been found that the above-mentioned object of the present invention can be achieved by the following constitution.

In a silver halide color photographic light-sensitive material having at least one of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, a blue-sensitive silver halide is used. The emulsion layer comprises a plurality of silver halide emulsion layers having different sensitivities, and blue-sensitive silver halide emulsion layers other than the blue-sensitive silver halide emulsion layer having the highest sensitivity among the blue-sensitive silver halide emulsion layers are blue-sensitive halogen. It is located farthest from the support in the silver halide emulsion layer, and at least one of the blue-sensitive silver halide emulsion layers contains a coupler represented by the following general formula (1) or general formula (2). A silver halide color photographic light-sensitive material having an ISO sensitivity of 160 or more.

General formula (1)

[0009]

[Chemical 3] General formula (2)

[0010]

[Chemical 4] (In the general formulas (1) and (2), X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, and X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-. In the formula, Y represents an aryl group or a heterocyclic group, and Z represents a group which is released when the coupler represented by the general formula (1) or (2) reacts with an oxidized product of a developing agent.) Of the general formula (1)
And the coupler represented by the general formula (2) shown in the above-mentioned "Chemical formula 2" will be described in detail.

When X ₁ and X ₂ represent an alkyl group,
Straight chain, branched chain, or branched chain having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms,
It is a cyclic, saturated, unsaturated, substituted or unsubstituted alkyl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, cyclopropyl, allyl, tert-octyl, iso-butyl, dodecyl, 2-hexyldecyl.

When X ₁ and X ₂ represent a heterocyclic group, the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
And 3 to 12 containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom.
Members, preferably 5- or 6-membered, saturated or unsaturated, substituted or unsubstituted, and monocyclic or condensed ring heterocyclic groups. Examples of the heterocyclic group include 3-pyrrolidinyl, 1,2,4-triazol-3-yl, 2-pyridyl, 4-pyrimidinyl, 3-pyrazolyl, 2-pyrrolyl, 2,4-dioxo-1,3- Imidazolidine-5-
Ill or pyranyl.

When X ₁ and X ₂ represent an aryl group,
It represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Typical examples of the aryl group are phenyl and naphthyl.

When X ₃ represents a nitrogen-containing heterocyclic group formed with> N-, this heterocyclic group has 1 to 20 carbon atoms,
It is preferably 1 to 15 and may contain, for example, an oxygen atom or a sulfur atom in addition to a nitrogen atom as a hetero atom, a 3 to 12 membered, preferably 5 or 6 membered, substituted or unsubstituted, saturated or unsaturated. , And monocyclic or condensed-ring heterocyclic groups. Examples of this heterocyclic group are pyrrolidino, piperidino, morpholino, 1-piperazinyl, 1-indolinyl, 1,2,3,4-tetrahydroquinolin-1-yl, 1-imidazolidinyl, 1-
Pyrazolyl, 1-pyrrolinyl, 1-pyrazolidinyl,
2,3-dihydro-1-indazoline, 2-isoindolinyl, 1-indolyl, 1-pyrrolyl, 4-thiazin-S, S-dioxo-4-yl or benzoxazin-4-yl are mentioned.

When X ₁ and X ₂ represent an alkyl, aryl or heterocyclic group having a substituent, and when the nitrogen-containing heterocyclic group formed with X ₃ together with> N- has a substituent, The following are mentioned as an example of those substituents. Halogen atom (for example, fluorine atom, chlorine atom), alkoxycarbonyl group (having 2 to 30 carbon atoms,
It is preferably 2 to 20, for example, methoxycarbonyl, hexadecyloxycarbonyl), an acylamino group (having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, for example, acetamide, tetradecane amide, 2- (2,
4-di-tert-amylphenoxy) butanamide, benzamide), sulfonamide group (having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, for example, methanesulfonamide, hexadecylsulfonamide, benzenesulfonamide), carbamoyl A group (having 1 to 30, preferably 1 to 20 carbon atoms, such as N-butylcarbamoyl,
N, N-diethylcarbamoyl), N-sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, for example, N-mesylcarbamoyl, N-dodecylsulfonylcarbamoyl), sulfamoyl group (having 0 carbon atoms). 30, preferably 1 to 20, for example N-
Butylsulfamoyl, N-hexadecylsulfamoyl, N-3- (2,4-di-t-amylphenoxy) butylsulfamoyl, N, N-diethylsulfamoyl), alkoxy group (having 1 carbon atom) -30, preferably 1-
Twenty, for example, methoxy, hexadecyloxy, isopropoxy), aryloxy group (having 6 to 6 carbon atoms)
20, preferably 6 to 10, such as phenoxy, 4-methoxyphenoxy, 3-tert-butyl-4-
Hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (having 7 to 21, preferably 7 to 11 carbon atoms, for example, phenoxycarbonyl), N-acylsulfamoyl group (having 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms) Two
0, for example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl), a sulfonyl group (having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms,
For example, methanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl), an alkoxycarbonylamino group (having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, for example, ethoxycarbonylamino), a cyano group, a nitro group, a carboxyl group. , A hydroxyl group, a sulfo group, an alkylthio group (having 1 to 30 carbon atoms, preferably 1
~ 20, such as methylthio, dodecylthio,
Dodecylcarbamoylmethylthio), ureido group (having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as N
-Phenylureido, N-hexadecylureido), an aryl group (having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, for example, phenyl, naphthyl, 4-methoxyphenyl), a heterocyclic group (having 1 to 20 carbon atoms). , Preferably 1-10
And a hetero atom, for example, at least one or more of nitrogen, oxygen or sulfur, which is a 3- to 12-membered, preferably 5- or 6-membered, monocyclic or condensed ring, for example, 2-pyridyl, 3-pyrazolyl , 1-pyrrolyl,
2,4-dioxo-1,3-imidazolidin-1-yl, 2-benzoxazolyl, morpholino, indolyl), alkyl group (having 1 to 30 carbon atoms, preferably 1 to 2 carbon atoms)
0, straight-chain, branched or cyclic, and saturated or unsaturated alkyl, such as methyl, isopropyl, cyclopropyl, tert-octyl, cyclopentyl, sec-butyl, 2-hexyldecyl), an acyl group (having 2 to 3 carbon atoms).
0, preferably 2 to 20, for example, acetyl, benzoyl), an acyloxy group (having 2 to 30 carbon atoms, preferably 2 to 20, for example, propanoyloxy, tetradecanoyloxy), an arylthio group (carbon Number 6 ~
20, preferably 6 to 10, for example, phenylthio, naphthylthio), sulfamoylamino group (having 0 to 30 carbon atoms, preferably 0 to 20 carbon atoms, for example, N
-Butylsulfamoylamino, N-dodecylsulfamoylamino, N-phenylsulfamoylamino) or N-sulfonylsulfamoyl group (having 1 to 3 carbon atoms)
0, preferably 1 to 20, for example, N-mesylsulfamoyl, N-ethanesulfonylsulfamoyl, N-dodecanesulfonylsulfamoyl, N-hexadecanesulfonylsulfamoyl). The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here.

Preferred substituents in the above are halogen atom, alkoxy group, alkoxycarbonyl group, acyloxy group, acylamino group, sulfonyl group, carbamoyl group, sulfamoyl group, sulfonamide group, nitro group, alkyl group or aryl group. Is mentioned.

When Y represents an aryl group in the general formulas (1) and (2), Y is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. For example, phenyl group and naphthyl group are typical examples.

When Y represents a heterocyclic group in the general formulas (1) and (2), Y has the same meaning as described above when X ₁ or X ₂ represents a heterocyclic group.

When Y represents a substituted aryl group or a substituted heterocyclic group, examples of the substituent include, for example, X ₁ mentioned above.
The examples of the substituents having a substituent include the substituents listed above. Preferred examples of the substituent of Y include:
One of the substituents is a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an N-sulfonylsulfamoyl group, an N-acylsulfamoyl group, an alkoxy group, an acylamino group, N-
This is when it is a sulfonylcarbamoyl group, a sulfonamide group or an alkyl group.

A particularly preferred example of Y is a phenyl group in which at least one substituent is in the ortho position.

The group represented by Z in the general formulas (1) and (2) may be any conventionally known coupling-off group. Preferred Z is a nitrogen-containing heterocyclic group that binds to the coupling position at a nitrogen atom, an aryloxy group, an arylthio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group or a halogen atom. Can be mentioned. These leaving groups are non-photographic useful groups or photographic useful groups or their precursors (for example, development inhibitors, development accelerators, desilvering accelerators, fogging agents, dyes, hardeners, couplers, developing agents). Oxidant scavenger, fluorescent dye, developing agent or electron transfer agent).

When Z is a photographically useful group, those conventionally known are useful. For example, U.S. Pat. No. 4,24
No. 8,962, No. 4,409,323, No. 4,4
No. 38,193, No. 4,421,845, No. 4,
No. 618,571, No. 4,652,516, No. 4,861,701, No. 4,782,012, No. 4,857,440, No. 4,847,185,
No. 4,477,563, No. 4,438,193
Issue No. 4,628,024, No. 4,618,57
No. 1, No. 4,741,994, European Published Patent Nos. 193,389A, No. 348,139A, or No. 272,573A, or a leaving group for releasing the photographically useful group. (Eg, timing group) is used.

When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, the nitrogen-containing heterocyclic group has a carbon number of 1 to 15, preferably 1 to 10, and has 5 or 6 members. , Substituted or unsubstituted, saturated or unsaturated,
And a monocyclic or condensed ring heterocyclic group is preferred. The hetero atom may contain an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group include 1-pyrazolyl, 1-imidazolyl, pyrrino, 1,2,4-triazol-2-yl, 1,
2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidin-2,4-dione-3-yl, oxazolidin-2,4-dione-3
-Yl, 1,2,4-triazolidine-3,5-dione-4-yl, imidazolidin-2,4,5-trione-
3-yl, 2-imidazolinon-1-yl, 3,5-dioxomorpholino or 1-yldazoline are mentioned. When these heterocyclic groups have a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. As a preferred substituent, a halogen atom, one alkyl group of the substituent, an alkoxy group, an alkoxycarbonyl group,
Aryloxycarbonyl group, alkylthio group, acylamino group, sulfonamide group, aryl group, nitro group,
This is when it is a carbamoyl group, a cyano group or a sulfonyl group.

When Z represents an aryloxy group, it is preferably a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms. A substituted or unsubstituted phenoxy group is particularly preferable. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, a preferable substituent is a case where at least one substituent is an electron-withdrawing group, and examples thereof include a halogen atom, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom and a carbamoyl group. , A nitro group, a cyano group or an acyl group.

When Z represents an arylthio group, it is preferably a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, preferable substituents are a halogen atom and at least one substituent which is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, or a nitro group.

When Z represents a heterocyclic oxy group, the heterocyclic group moiety has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. It is a 3- to 12-membered, preferably 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed-ring heterocyclic group containing 1 or more. Examples of the heterocyclic oxy group include a pyridyloxy group, a pyrazolyloxy group, or a furyloxy group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, a preferable substituent is a halogen atom, one alkyl group of the substituent, an aryl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Alkylthio group, acylamino group, sulfonamide group,
When it is a nitro group, a carbamoyl group, or a sulfonyl group.

When Z represents a heterocyclic thio group, the heterocyclic group portion has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. 3-12 members, including at least one or more,
Preferred are 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed-ring heterocyclic groups. Examples of the heterocyclic thio group include tetrazolylthio group, 1,3,4-thiadiazolylthio group, 1,3,4
Examples include an oxadiazolylthio group, a 1,3,4-triazolylthio group, a benzimidazolylthio group, a benzothiazolylthio group, and a 2-pyridylthio group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, preferable substituents are a halogen atom, at least one of which is an alkyl group, an aryl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, and a nitro group. When it is a group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

When Z represents an acyloxy group, the acyloxy group preferably has 6 to 10 carbon atoms and is a monocyclic ring or a condensed ring. It is a substituted or unsubstituted arylacyloxy group or a substituted or unsubstituted alkylacyloxy group having 2 to 30, preferably 2 to 20 carbon atoms. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

When Z represents a carbamoyloxy group, this carbamoyloxy group is an alkyl, aryl, heterocycle, substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example,
Mention may be made of N, N-diethylcarbamoyloxy, N-phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-pyrrolocarbonyloxy. When these have a substituent, examples of the substituent include the above-mentioned X.
Examples thereof include the substituents enumerated as the substituents which the group represented by ₁ may have.

When Z represents an alkylthio group, the alkylthio group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Which are linear, branched or cyclic, saturated or unsaturated, and substituted or unsubstituted alkylthio groups. When it has a substituent, examples of the substituent include the above-mentioned X.
Examples thereof include the substituents enumerated as the substituents which the group represented by ₁ may have.

Next, a particularly preferred range of the couplers represented by the general formulas (1) and (2) will be described below.

The group represented by X ₁ in the general formula (1) is preferably an alkyl group. Particularly preferably, it is an alkyl group having 1 to 10 carbon atoms.

The group represented by Y in the general formulas (1) and (2) is preferably an aryl group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. As the explanation of the substituent, those enumerated as the substituents which may be possessed when Y is an aryl group can be mentioned. The example of a preferable substituent is also the same.

The group represented by Z in the general formulas (1) and (2) is preferably a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, an aryloxy group, 5-6. And a 5- or 6-membered heterocyclic thio group.

Among the couplers represented by the general formula (1) or (2), preferred couplers are the couplers represented by the general formula (3), (4) or (5) shown in the following "Chemical formula 5" to "Chemical formula 7". is there. General formula (3)

[0036]

[Chemical 5] General formula (4)

[0037]

[Chemical 6] General formula (5)

[0038]

[Chemical 7] In formulas (3) to (5), Z represents the same meaning as described in formula (1), X ₄ represents an alkyl group,
X ₅ represents an alkyl group or an aryl group, Ar represents a phenyl group having at least one substituent at the ortho position, X ₆ represents —C (R ₁ R ₂ ) —N <in the formula, and a nitrogen-containing heterocycle. Represents an organic residue forming a group (monocyclic or condensed ring), and X ₇ is —C (R ₃ ) ═C (R ₄ ) —N <in the formula.
Represents an organic residue forming a nitrogen-containing heterocyclic group (monocyclic or condensed ring) together, and R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent.

In the general formulas (3) to (5), X _{4 to} X ₇
Regarding the detailed description and the preferable range of the group represented by Z and Z, they have the same meanings as the description of the corresponding group in the descriptions of the general formulas (1) and (2). R ₁ ~ R
_{When 4} represents a substituent, those enumerated as the substituent that X ₁ may have are mentioned as examples.

Particularly preferred couplers in the above general formula are the couplers represented by the general formula (4) or (5).

The couplers represented by the general formulas (1) to (5) are represented by X _{1 to} X ₇ , Y, Ar, R _{1 to} R ₄ and Z, and are bis or divalent or higher groups. Dimers or higher multimers (eg telomers or polymers) may be formed which are linked together via
In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

The couplers represented by the general formulas (1) to (5) are preferably non-diffusion type couplers. The diffusion-resistant coupler is a coupler having a group (diffusion-resistant group) in the molecule that increases the molecular weight sufficiently in order to immobilize the molecule in the added layer. As the diffusion resistant group, an alkyl group having a total carbon number of 8 to 30, preferably 10 to 20 or an aryl group having a substituent having a total carbon number of 4 to 20 is usually used. These diffusion resistant groups may be substituted in any of the molecules, or may have a hetero group.

The following general formulas (1) are represented in "Chemical formula 8" to "Chemical formula 25".
Specific examples of the yellow couplers represented by (5) to (5) are shown below, but the invention is not limited thereto.

[0044]

[Chemical 8]

[0045]

[Chemical 9]

[0046]

[Chemical 10]

[0047]

[Chemical 11]

[0048]

[Chemical 12]

[0049]

[Chemical 13]

[0050]

[Chemical 14]

[0051]

[Chemical 15]

[0052]

[Chemical 16]

[0053]

[Chemical 17]

[0054]

[Chemical 18]

[0055]

[Chemical 19]

[0056]

[Chemical 20]

[0057]

[Chemical 21]

[0058]

[Chemical formula 22]

[0059]

[Chemical formula 23]

[0060]

[Chemical formula 24]

[0061]

[Chemical 25] In addition, YB-24 in "Chemical formula 15", YB-25 in "Chemical formula 16", YB-29 and YB-30 in "Chemical formula 17", and YB-31, YB in "Chemical formula 18"
In -32 and YB-33, "}" indicates that the substituent is substituted at the 5- or 6-position of the benzotriazolyl group.

The yellow couplers represented by the general formulas (1) to (5) used in the present invention are represented by the following "formula 26".
~ Can be synthesized by the route shown in "Chemical Formula 29". Synthesis example-1

[0063]

[Chemical formula 26] Synthesis of Intermediate B Compound A357.5 g (3.0 mol), Compound B39
1.2 g of ethyl acetate was added to 6.3 g (3.0 mol),
It was dissolved in 0.6 liter of dimethylformamide. 631 g of dicyclohexylcarbodiimide while stirring
A solution of (3.06 mol) in acetonitrile (400 ml) was added dropwise at 15 to 35 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration.
500 ml of ethyl acetate and 1 liter of water were added to the filtrate, and the aqueous layer was removed. Next, the organic layer was washed twice with 1 liter of water. The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 692 g of Intermediate A as an oily substance.
(98.2%) was obtained.

692 g (2.97 mol) of intermediate A was dissolved in 3 liters of ethyl alcohol and stirred to give 75
430 g of 30% sodium hydroxide was added dropwise at -80 ° C. After dropping, the mixture was reacted at the same temperature for 30 minutes, and the precipitated crystals were collected by filtration. (Yield 658 g) This crystal was suspended in 5 liters of water and stirred at 40-
300 ml of concentrated hydrochloric acid was added dropwise at 50 ° C. After stirring at the same temperature for 1 hour, the crystals were collected by filtration to obtain 579 g of Intermediate B.
(95%) obtained. (Decomposition point 127 ° C.) Synthesis of intermediate D 45.1 g (0.22 mol) of intermediate B, compound C86.
6 g (0.2 mol) was dissolved in 400 ml of ethyl acetate and 200 ml of dimethylacetamide. While stirring, 66 g (0.32 mol) of dicyclohexylcarbodiimide
Acetonitrile solution (100 ml) was added dropwise at 15 to 30 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration.

The filtrate contains 400 ml of ethyl acetate and 600 m of water.
1 was added, the aqueous layer was removed, and the organic layer was washed twice with water.
The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 162 g of an oily substance.

This oily matter was mixed with 100 ml of ethyl acetate and n-
Crystallization from 300 ml of hexane gave 108 of Intermediate D.
g (87.1%) was obtained. (Melting point 132 to 134 ° C.) Elemental analysis values of Intermediate D are shown in Table 1 below.

[0067]

[Table 1] Synthesis of Exemplified Coupler YB-3 49.6 g (0.08 mol) of Intermediate D was dissolved in 300 ml of dichloromethane. Sulfuryl chloride 1 in this solution
1.4 g (0.084 mol) was added dropwise with stirring at 10 to 15 ° C.

After reacting for 30 minutes at the same temperature, 200 g of a 5% aqueous sodium bicarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 200 ml of water, and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 47 g of an oily substance.

47 g of this oily substance was added to 200 ml of acetonitrile.
It was dissolved in ml and 28.4 g (0.22 mol) of compound D and 22.2 g (0.22 mol) of triethylamine were added thereto with stirring. After reacting for 4 hours at 40 to 50 ° C., the mixture was poured into 300 ml of water, and the precipitated oily substance was extracted with 300 ml of ethyl acetate. The organic layer was washed with 200 g of a 5% aqueous sodium hydroxide solution, and then twice more with 300 ml of water.
Washed with water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and concentrated under reduced pressure to give a residue. (Yield 70 g) The obtained oily substance was crystallized with a mixed solvent of 50 ml of ethyl acetate and 100 ml of n-hexane to give an exemplary coupler YB.
-4 g (80%) was obtained. (Melting point 145-7
C) Elemental analysis values of the exemplified coupler YB-3 are shown in Table 2 below.

[0070]

[Table 2] Synthesis example-2

[0071]

[Chemical 27] Synthesis of Intermediate E 90.3 g of Intermediate B (0.44 mol), Compound E187
g (0.4 mol) was dissolved in 500 ml of ethyl acetate and 300 ml of dimethylformamide. While stirring, a solution of 131.9 g (0.64 mol) of dicyclohexylcarbodiimide in 15 to 30 of acetonitrile (200 ml) was added.
Dropwise at ° C.

After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration. After 500 ml of ethyl acetate and 600 ml of water were added to the filtrate to remove the aqueous layer, the organic layer was washed twice with water. The organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and an oily substance was added to the residue.
81 g was obtained.

This was dissolved by heating with 1.5 liter of n-hexane, and insoluble materials were removed by filtration. The n-hexane solution was cooled with water, and the precipitated intermediate E was collected by filtration. Yield 243.4
g (93%) melting point 103-5 ° C. Elemental analysis values of the intermediate E are shown in Table 3 below.

[0074]

[Table 3] Synthesis of Exemplified Coupler YB-7 39.3 g (0.06 mol) of Intermediate E was dissolved in 200 ml of dichloromethane. Sulfuryl chloride 8.
7 g (0.064 mol) was added dropwise with stirring at 10 to 15 ° C.

After reacting at the same temperature for 30 minutes, 200 g of a 4% aqueous sodium hydrogencarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 200 ml of water, and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 41.3 g of an oily substance.

41.3 g of this oily substance was added to acetonitrile 1
Dissolve in 00 ml, 200 ml of dimethylacetamide,
With stirring, 20.8 g (0.16 mol) of compound D and 16.2 g of triethylamine were added. 3 at 30-40 ° C
After reacting for time, it was poured into 400 ml of water, and the precipitated oily substance was extracted with 300 ml of ethyl acetate. 2% organic layer
After washing with 300 g of aqueous sodium hydroxide solution, 2 more
It was washed with water twice. The organic layer was acidified with diluted hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain 42 g of a residue.

This was crystallized with 200 ml of methanol to obtain 39.8 g (85%) of the exemplary coupler YB-7. (Melting point 110 to 112 ° C.) Elemental analysis values of the exemplified coupler YB-7 are shown in Table 4 below.

[0078]

[Table 4] Synthesis example-3

[0079]

[Chemical 28] Synthesis of intermediate F 104.7 g (0.51 mol) of intermediate B, compound F18
7.5 g (0.5 mol) was dissolved in 1 liter of ethyl acetate and 400 ml of dimethylformamide. While stirring, 107.3 g of dicyclohexylcarbodiimide
(0.525 mol) of dimethylformamide (100 m
l) The solution was added dropwise at 15-30 ° C. 1 at 20-30 ° C
After reacting for an hour, 500 ml of ethyl acetate was added,
It was heated to ~ 60 ° C and the dicyclohexylurea was filtered off.

After adding 500 ml to the filtrate and removing the aqueous layer, the mixture was washed twice with water. The organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and an oily substance was obtained at 290
g was obtained. This oily substance was heated with 1 liter of ethyl acetate and 2 liters of methanol, insoluble matter was removed by filtration, and the filtrate was water-cooled, and crystals of Intermediate F were precipitated, and were collected by filtration.
Yield 267 g (95%), melting point 163-4 [deg.] C. Elemental analysis values of Intermediate F are shown in Table 5 below.

[0081]

[Table 5] Synthesis of Intermediate G 114.0 g (0.2 mol) of Intermediate F was dissolved in 500 ml of dichloromethane. Sulfuryl chloride 2 in this solution
8.4 g (0.21 mol) was added dropwise with stirring at 10 to 15 ° C.

After reacting for 30 minutes at the same temperature, 500 g of a 6% aqueous sodium hydrogencarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 500 ml of water, and dried over anhydrous sodium sulfate. When dichloromethane was distilled off under reduced pressure, intermediate G was precipitated as crystals and was collected by filtration. Yield 108.6 g (91%) Synthesis of Exemplified Coupler YB-5 Intermediate G29.8 g (0.05 mol) was dissolved in dimethylformamide 80 ml to give compound D12.9 g (0.1
Mol) and then 10.1 g of triethylamine (0.
10 mol) was added dropwise with stirring at 20 to 30 ° C. Four
After reacting at 0-45 ° C for 1 hour, ethyl acetate 300m
1 and 200 ml of water were added. The organic layer was washed twice with 400 g of a 2% aqueous sodium hydroxide solution and then washed once with water. The organic layer was acidified with diluted hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain 34 g of a residue. This is ethyl acetate 50m
Crystallization with a mixed solvent of 1, n-hexane 150 ml,
19 g of the exemplified coupler YB-5 was obtained.

This crystal was mixed with ethyl acetate / n-hexane = 1
The mixed solvent having a volume ratio of / 3 was recrystallized from 120 ml to obtain 15 g (43.5%) of the exemplary coupler YB-5. (Melting point 1
35 to 6 ° C.) Elemental analysis values of the exemplified coupler YB-5 are shown in Table 6 below.

[0084]

[Table 6] Synthesis example-4

[0085]

[Chemical 29] Synthesis of Exemplified Coupler YB-22 Compound G 27.0 g (0.15 mol) and triethylamine 15.2 g (0.15 mol) were dissolved in dimethylformamide 50 ml. 29.8 g of intermediate G in this mixture
(0.05 mol) dimethylformamide (30 ml)
The solution was added dropwise with stirring.

After reacting at 30-40 ° C. for 4 hours, 400 ml of ethyl acetate was added to 300 ml of water. 2 organic layers
After washing with 400 g of an aqueous sodium hydroxide solution at 40%, it was washed twice with water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and dried over anhydrous sodium sulfate. The ethyl acetate was distilled off under reduced pressure to obtain 54 g of a residue.

This was crystallized with 300 ml of a mixed solvent of ethyl acetate / methanol (1/2 volume ratio), and the exemplified coupler YB-22 was collected by filtration. 200 ml of a mixed solvent of ethyl acetate / methanol (1/2 volume ratio) was recrystallized from the obtained crystals to give 28.8 g (77.8 g) of the exemplified coupler YB-22.
%)Obtained. Melting point 190-191 ° C. Elemental analysis values of the exemplified coupler YB-22 are shown in Table 7 below.

[0088]

[Table 7] In the present invention, the yellow couplers represented by the general formulas (1) to (5) are 1.0 parts per mol of silver halide.
It can be used in the range of up to 1.0 × 10 ⁻³ mol.
It is preferably 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻² mol, and more preferably 4.0 × 10 ^{−1 to} 5.0 × 10 ⁻² mol.

In the present invention, when the yellow couplers represented by the general formulas (1) to (5) are used as the main coupler, it is preferably added to the blue-sensitive silver halide emulsion layer or the adjacent non-photosensitive layer. When the coupler releases a photographically useful group, it is added to the silver halide photosensitive layer or the non-photosensitive layer according to the purpose.

In the present invention, the yellow couplers represented by the general formulas (1) to (5) may be used in combination of two or more kinds, or may be used in combination with other known couplers. In the present invention, the couplers represented by the general formulas (1) to (5) can be introduced into the color light-sensitive material by various known dispersion methods.

In the oil-in-water dispersion method, which is one of the known dispersion methods, an organic solvent having a low boiling point (eg, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol) is used to apply a fine dispersion and dry it. A method in which the low boiling point organic solvent does not substantially remain in the film can be used. When a high-boiling organic solvent is used, any of those having a boiling point of 175 ° C. or higher under normal pressure may be used, and one kind or two or more kinds may be arbitrarily mixed and used.
The ratio of the couplers represented by the general formulas (1) to (5) to these high-boiling organic solvents can be in a wide range, but the coupler 1
The weight ratio is in the range of 5.0 or more per gram. It is preferably 0 to 2.0, and more preferably 0.01 to 1.0.

The latex dispersion method described below can also be applied.

Further, various couplers and compounds described later can be mixed or used together.

The blue-sensitive silver halide emulsion layer of the present invention comprises a plurality of silver halide emulsion layers having different sensitivities. These blue-sensitive silver halide emulsion layers may be two layers or three layers,
It may be composed of more layers, and there may be a non-photosensitive layer or a layer having different spectral sensitivity between them. Among these blue-sensitive silver halide emulsion layers, the blue-sensitive silver halide emulsion layers other than the one having the highest sensitivity are located farthest from the support in the blue-sensitive silver halide emulsion layers.
As an example of the arrangement of the above blue-sensitive silver halide emulsion layers,
For example (but not limited to):

[0095] (IL: non-photosensitive layer, BH: high-sensitivity blue-sensitive silver halide emulsion layer, BM: medium-sensitivity blue-sensitive silver halide emulsion layer, B
L: Low-sensitivity blue-sensitive silver halide emulsion layer) With the layer arrangement as described above, the effect of improving the graininess of the present invention is realized.

The higher the ISO speed, the greater the grain improving effect by the arrangement of the blue-sensitive silver halide emulsion layers of the present invention.
When the ISO sensitivity is 160 or more, the grain improving effect of the present invention becomes clear, and more preferably when the ISO sensitivity is 320 or more, it becomes more remarkable. When the ISO sensitivity is less than 160, the granular effect of the present invention is small.

The color photographic light-sensitive material of the present invention is provided with at least one of a silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, a red-sensitive layer or an infrared-sensitive layer on a support. The number of silver halide emulsion layers and the non-photosensitive layer are not particularly limited and the order of layers is not particularly limited. A typical example is
A silver halide photographic light-sensitive material having at least one light-sensitive layer (unit light-sensitive layer) consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. is there. In that case, the photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that photosensitive layers having different color sensitivities are sandwiched between the same color sensitive layers.

A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, a coupler and a DIR compound as described in JP-A No. 61-20038 may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Furthermore,
For example, JP-A-57-112751, JP-A-62-200.
No. 350, No. 62-206541, No. 62-2065
As described in No. 43, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, the low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H or the like.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of red-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. A silver halide emulsion layer having a lower photosensitivity than that of the silver halide emulsion layer may be disposed, and the photosensitivity may be sequentially decreased toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / It may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer.

In addition, for example, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, BL, GL, RL
It is preferable to dispose a donor layer (CL) having a multi-layer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer, adjacent to or adjacent to the main photosensitive layer.

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

The silver halide grains in the photographic emulsion have a regular crystal form such as a cube, an octahedron and a tetradecahedron, and an irregular crystal form such as a sphere and a plate. It may have a crystal defect such as a twin plane or a composite form thereof.

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 18
716 (November 1979), p.648, ibid. Thirty
7105 (November 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemie et.
Phisique Photographique,
Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duf).
fin, Photographic Emulsion
Chemistry (Focal Press, 19
66), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
autographicEmulsion (Focal
It can be prepared using the method described in Press, 1964).

US Pat. Nos. 3,574,628, 3,655,364 and British Patent 1,413,7.
Monodisperse emulsions described in No. 48 and the like are also preferable.

Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described, for example, by Gatov, Photographic Science and Engineering (Gutoff, Photog.
radical Science and Engine
ering), Volume 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
No. 4,310, No. 4,433,048, No. 4,4
It can be easily adjusted by the method described in 39,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which has a latent image on both the surface and the inside. It must be a negative emulsion. In the case of an internal latent image type emulsion, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59 / 1985.
-133542. The thickness of the shell of this emulsion is 3 × 40 nm, although it varies depending on the development process.
Is preferable, and 5-20 nm is especially preferable.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used.
The additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

In the light-sensitive material of the present invention, the grain size of the light-sensitive silver halide emulsion, grain size distribution, halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
The thickness is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The particle shape is not particularly limited and may be regular particles. Although it may be a polydisperse emulsion, it is preferably a monodisperse emulsion (in which at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and is not fogged in advance. preferable.

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide, and preferably contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

Fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized and spectral sensitization is not required. However, prior to adding this to the coating liquid, for example, triazole-based,
It is preferable to add a known stabilizer such as an azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

The known photographic additives that can be used in the silver halide color photographic light-sensitive material of the present invention are described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Additive type RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, and stabilizer 6. Light absorber, page 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, ultraviolet absorber 7. Anti-staining agent, page 25, right column, page 650, left to right column, page 872 8. Dye image stabilizer, page 25, page 650, left column, page 872 9. Hardener, page 26, page 651, left column, pages 874-875 10. Binder page 26 page 651 left column page 873-874 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Antistatic agent Page 27 Page 650 Right column Page 876-877 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is fixed by reacting with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being converted into a light-sensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

In the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by development processing, JP-A-1-10605 is used.
It is preferable to contain a compound releasing a fog agent, a development accelerator, a silver halide solvent or a precursor thereof described in No. 2.

Various color couplers can be used in the silver halide color photographic light-sensitive material of the present invention. Specific examples thereof include Research Disclosure (R) mentioned above.
D) No. 17643, VII-C-G.

As other yellow couplers that can be used in combination with the yellow coupler of the present invention, benzoylacetanilide type and pivaloylacetanilide type are preferable, and, for example, US Pat. Nos. 3,933,501 and 4,02
No. 2,620, No. 4,326,024, No. 4,4
No. 01,752, No. 4,248,961, Japanese Patent Publication No. 5
8-10739, British Patent No. 1,425,020,
U.S. Pat. No. 1,476,760 and U.S. Pat. No. 3,973,9.
No. 68, No. 4,314, 023, No. 4,511,
Those described in EP No. 649 and EP 249,473A are preferable.

As the magenta coupler, 5-pyrazolone compounds and birazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,35.
No. 1,897, European Patent No. 73,636, US Patent Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (198
June, 4), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
Mon), JP-A-60-43659, JP-A 61-72238.
No. 60-35730, No. 55-118034,
No. 60-185951, U.S. Pat. No. 4,500,63.
No. 0, No. 4,540, 654, No. 4,556, 6
No. 30, those described in International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,223, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Furthermore, JP-A-64-553 and 64-55.
No. 4, 64-555, 64-556, and pyrazoloazole couplers described in US Pat. No. 4,818,
The imidazole coupler described in No. 672 can also be used.

Typical examples of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282 and 4,409. No. 320, No. 4,576,910,
British Patent 2,102,137, European Patent 341,1
88A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unnecessary absorption of color-forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 307105
VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,92.
No. 9, No. 4,138,258, and British Patent No. 1,14.
Those described in 6,368 are preferable. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,774,181 and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye.

Compounds which release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
D17643, VII-F section and No. 30710
5, the patents described in VII-F, JP-A-57-15
1944, 57-154234, 60-184.
No. 248, No. 63-37346, No. 63-37350.
U.S. Pat. Nos. 4,248,962 and 4,782.
The compounds described in No. 012 can be used in combination.

For example, R. D. No. 11449 and 2
The bleaching accelerator-releasing couplers described in JP-A No. 4241 and JP-A No. 61-201247 are effective for shortening the processing time having a bleaching ability, and particularly, the light-sensitive material using the tabular silver halide grains described above. The effect is great when added to. As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds which release, for example, a fogging agent, a development accelerator and a silver halide solvent by a redox reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include, for example, US Pat. No. 4,13.
Competitive couplers described in 0,427, for example, U.S. Pat. Nos. 4,283,472, 4,338,393,
Multiequivalent couplers described in JP-A No. 4,310,618; for example, JP-A-60-185950 and JP-A-64-2425.
No. 2, DIR redox compound releasing coupler, D
IR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound; European Patent Nos. 173,302A and 313,3
No. 08A, a coupler which releases a dye that recolors after release; for example, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477 and a leuco dye releasing coupler described in JP-A-63-75747. U.S. Pat. No. 4,7
The couplers which release the fluorescent dyes described in JP-A-74,181 can be exemplified.

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

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described, for example, in US Pat. No. 2,322,027. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , Bis (2,4-di-ter
t-amylphenyl) phthalate, bis (2,4-di-)
tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, Tri-2-ethylhexyl phosphate,
Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate); Benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate); Amides ( For example, N, N-diethyldodecaneamide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,
4-di-tert-amylphenol); aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl))
Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives (eg N, N-dibutyl-2-butoxy-5-tert-octylaniline); hydrocarbons (eg Paraffin, dodecylbenzene, diisopropylnaphthalene) can be exemplified. As the auxiliary solvent, for example, the boiling point is about 30 ° C.
Above, preferably an organic solvent of 50 ° C or higher and about 160 ° C or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide. To be

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541,
No. 274 and No. 2,541,230.

In the color photographic light-sensitive material of the present invention, phenethyl alcohol and JP-A-63-257747 and JP-A-6-257747 are used.
2-272248 and JP-A-1-80941, for example, 1,2-benzisothiazoline-3-
On, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2
It is preferable to add various preservatives or antifungal agents such as -phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Representative examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention can be particularly preferably used for a film for color duplication.

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid.
No. 18716, page 647, right column to page 648, left column, and ibid. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness here means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days). Further, the film swelling rate T _1/2 can be measured according to a method known in the art, for example, A. Green et al., Photography Science and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129. In addition, T _1/2 is a color developing solution of 30
The maximum swollen film thickness reached when treated at 3 ° C for 15 minutes
0% is defined as the saturated film thickness, which is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. .. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, page 651, left column to right column, and the same No. Thirty
The development can be carried out by a usual method described in 7105, pages 880 to 881.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, 4-amino-
3-Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-
N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy Propyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-
Methyl-N- (3-hydroxypropyl) aniline, 4
-Amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-
Ethyl-N- (4-hydroxybutyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-
Ethyl-N- (3-hydroxy-2-methylpropyl)
Aniline, 4-amino-3-methyl-N, N-bis (4
-Hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxy Butyl) aniline, 4
-Amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-
N, N-bis (5-hydroxypentyl) aniline, 4
-Amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p
-Toluene sulfonate and the like. Among these, especially 3-methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4
-Hydroxybutyl) aniline and their hydrochlorides,
P-toluenesulfonate or sulfate is preferred.
Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate,
It is common to include development inhibitors or antifoggants such as chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines; dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonos. Various chelating agents represented by carboxylic acids can be used. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitriletriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-.
Representative examples include diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. be able to.

When the reversal processing is carried out, black and white development is usually carried out before color development. This black-and-white developer contains, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-, for example.
Known black-and-white developing agents of aminophenols such as p-aminophenol can be used alone or in combination. P of these color developers and black and white developers
H is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the evaporation and air oxidation of the liquid by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷
[Volume of Treatment Liquid (cm ³ )] The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to a method of providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, the movable lid described in JP-A-1-82033 is used. And the slit development processing method described in JP-A-63-216050. Reducing the aperture ratio is preferably applied not only in both the color development and black and white development steps but also in the subsequent steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing,
Alternatively, the bleaching treatment after the bleach-fixing treatment can be arbitrarily carried out according to the purpose. As the bleaching agent, for example, polyvalent metal compounds such as iron (III), peracids (in particular, sodium persulfate is suitable for color negative films for motion pictures), quinones, and nitro compounds are used. As a typical bleaching agent, an organic complex salt of iron (III), for example, ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or, for example, citric acid, tartaric acid, malic acid Complex salts of can be used. Among these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts,
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
The aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
JP-A-53-32736 and JP-A-53-57831.
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53-95631, No. 53-.
No. 104232, No. 53-124424, No. 53-1
No. 41623, No. 53-18426, Research Disclosure No. No. 17129 (July 1978)
A compound having a mercapto group or a disulfide group described in JP-A No. 51-140129, a thiazolidine derivative described in JP-A No. 51-140129;
832, 53-32735, and U.S. Pat. No. 3,70.
Thiourea derivatives described in 6,561, West German Patent No. 1,
127,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,74.
No. 8,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40943, JP-A-49-59644,
53-94927, 54-35727, 55
Compounds described in -26506 and 58-163940; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and particularly, US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP-A-53
The compounds described in -95630 are preferred. Further, the compounds described in US Pat. No. 4,552,884 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specific examples thereof include acetic acid, propionic acid and hydroxyacetic acid.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Also, with thiosulfate, for example, thiocyanate,
A combined use of a thioether compound and thiourea is also preferable. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 2
The sulfinic acid compounds described in No. 94,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methyl. It is preferable to add 0.1 to 10 mol / liter of an imidazole such as imidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, or a stirring means using a rotating means in JP-A-62-183461 is used. There are ways to increase the effect. Furthermore, a method of further improving the stirring effect by moving the photosensitive material while making the emulsion surface contact with the wiper blade provided in the solution and making the emulsion surface turbulent, and increasing the circulation flow rate of the entire processing solution There is a method of making it. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the agitation improving means is more effective when a bleaching accelerator is used, and the accelerating effect can be remarkably increased, and the fixing inhibiting effect can be eliminated by the bleaching accelerator.

Automatic developing machines used for developing the light-sensitive material of the present invention are disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), application,
Furthermore, for example, the washing water temperature, the number of washing tanks (the number of stages),
It can be set in a wide range according to various conditions such as a replenishment method such as counterflow and forward flow. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows.
the Society of Motion Pi
movie and Television Engi
neers Vol. 64, p. 248-253 (1955
May issue). According to the multi-stage counter-current method described in the above document, the amount of washing water can be significantly reduced, but bacteria are propagated due to an increase in the residence time of water in the tank, and the produced suspended matter adheres to the photosensitive material. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Further, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorine-based germicides such as chlorinated sodium isocyanurate, and others, such as benzotriazole, by Horiguchi "The Chemistry of Antibacterial and Antifungal Agents" (1986
Sankyo Shuppan, Hygiene Society, edited by "Microbial sterilization, sterilization, and fungicide technology" (1982), Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) A bactericide can also be used.

P of washing water in the processing of the light-sensitive material of the present invention
H is 4-9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on, for example, the characteristics of the light-sensitive material and the use, but generally 15 to 45 ° C. and 20 seconds to 1
A range of 0 minutes, preferably 25 to 40 ° C. and 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used.

Further, after the water washing treatment, a stabilizing treatment may be performed in some cases. An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in another step such as a desilvering step.

For example, in processing using an automatic processor,
When each of the above treatment liquids is concentrated by evaporation, it is preferable to add water to correct the concentration.

A color developing agent may be incorporated in the silver halide color photographic light-sensitive material of the present invention for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, such as Research Disclosure No. 3,342,599. 14, 850 and the same No.
Schiff base type compounds described in Nos. 15 and 159, No. 1
Aldol compounds described in US Pat.
Metal salt complexes described in JP 719,492, JP-A-53-1.
The urethane compound described in No. 35628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described, for example, in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

Various processing solutions used in the present invention are 10 ° C. to 5 ° C.
Used at 0 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

Further, the silver halide color photographic light-sensitive material of the present invention is described in JP-B-2-32615 and JP-B-3-397.
When applied to the lens-equipped film unit described in No. 84 etc., it is more effective and more effective.

[0169]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 Preparation of Sample 101 On a 205 μm-thick cellulose triacetate film support having both surfaces of the film undercoated, a multilayer color light-sensitive material having the following composition was prepared to prepare Sample 101.
And

The coating amount of each composition is the value per 1 m ² of the sample. For silver halide and colloidal silver, the equivalent weight of silver is shown. First layer: antihalation layer Black colloidal silver 0.25 g of silver 1.9 g Gelatin 1.9 g UV absorber U-1 0.2 g UV absorber U-3 0.1 g UV absorber U-4 0.2 g High boiling organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g Second layer: intermediate layer Non-photosensitive fine grain silver iodobromide emulsion (average grain size 0.1 μm, AgI content) 1 mol%) Silver amount 0.15 g Surface and internal fogged fine grain silver iodobromide emulsion (average particle size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.05 g Compound Cpd-A 0.1 g Compound Cpd-M 0.05 g Gelatin 0.4 g Third layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 1 mg Compound Cpd-D 3 mg Dye D-4 0.4 mg High boiling point organic solvent Oil -3 40 mg Layer 4: Low Red-sensitive emulsion layer Emulsion A Silver amount 0.3 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.09 g Coupler C-2 0.03 g Coupler C-3 0.02 g Coupler C- 10 0.02 g Compound Cpd-D 1 mg Compound Cpd-K 0.05 g High boiling point organic solvent Oil-2 0.10 g Ethyl acrylate latex dispersion 0.5 g Fifth layer: middle-sensitive red-sensitive emulsion layer Emulsion B Silver Amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0. 1 g Ethyl acrylate latex dispersion 0.05 g Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Puller C-3 0.1 g Additive P-1 0.02 g Latex dispersion of ethyl acrylate 0.1 g Seventh layer: Intermediate layer Gelatin 1.0 g Compound Cpd-J 0.2 g Compound Cpd-L 0 0.05 g Compound Cpd-N 0.02 g Additive P-1 0.05 g Dye D-1 0.02 g Eighth layer: intermediate layer Silver iodobromide emulsion with a fogged surface and inside (average grain size 0.06 μm, Coefficient of variation 16%, AgI content 0.3 mol%) Silver amount 0.02 g Gelatin 0.4 g Compound Cpd-A 0.1 g Compound Cpd-D 1 mg Compound Cpd-M 0.05 g Layer 9: Low sensitivity Green-sensitive emulsion layer Silver iodobromide emulsion with fogged grains (average grain size 0.1 μm, AgI content 0.1 mol%) Silver amount 0.15 g Emulsion E Silver amount 0.3 g Emulsion F Silver amount 0. 1 g Emulsion G Silver amount 0.1 g Gelatin 2.0 g Coupler C-4 0.03 g Coupler C-7 0.05 g Coupler C-8 0.02 g Coupler C-9 0.05 g Coupler C-12 0.2 g Compound Cpd-B 0.03 g Compound Cpd- D 1 mg Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling point organic solvent Oil-2 0.2 g 10th layer: Medium sensitivity green sensitivity Emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.05 g Coupler C-8 0.05 g Coupler C-9 0 .02 g Coupler C-12 0.20 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g Compound Cp d-H 0.05 g Additive F-5 0.08 mg High-boiling-point organic solvent Oil-2 0.01 g 11th layer: high-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion with fog inside (average grain size 0 0.2 μm, AgI content 0.1 mol%) Silver amount 0.05 g Emulsion I Silver amount 0.5 g Gelatin 1.1 g Coupler C-4 0.1 g Coupler C-7 0.3 g Coupler C-80 0.07 g Coupler C-9 0.05 g Coupler C-12 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0 0.02 g High boiling point organic solvent Oil-2 0.04 g 12th layer: Intermediate layer Gelatin 0.4 g Ethyl acrylate latex dispersion 0.15 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D 3 0.07 g Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.08 g Gelatin 1.0 g Compound Cpd-A 0.04 g High boiling point organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 Material 0.05 g 14th layer: Intermediate layer Gelatin 0.6 g 15th layer: Low-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion with fog inside (average grain size 0.2 μm, AgI content 0.1 mol) %) Silver amount 0.1 g Emulsion J Silver amount 0.4 g Emulsion K Silver amount 0.1 g Emulsion L Silver amount 0.1 g Gelatin 1.0 g Coupler C-5 0.5 g Compound Cpd-K 0 .1 g 16th layer: Medium-sensitive blue-sensitive emulsion layer Emulsion L Silver amount 0.2 g Emulsion M Silver amount 0.3 g Gelatin 0.6 g Coupler C-5 0.4 g 17th layer: High-sensitivity blue-sensitive layer Emulsion layer Emulsion N Silver amount 0.6 g Gelatin 1.4 g Coupler C-5 0.9 g Eighteenth layer: First protective layer Gelatin 0.9 g UV absorber U-1 0.4 g UV absorber U-2 0.01 g UV absorber U-3 0.03 g UV absorber Agent U-4 0.03 g Ultraviolet absorber U-5 0.05 g Ultraviolet absorber U-6 0.05 g High boiling point organic solvent Oil-1 0.02 g Formalin scavenger Cpd-C 0.2 g Formalin scavenger Cpd-I 0 0.4 g Ethyl acrylate latex dispersion 0.05 g Dye D-3 0.05 g Compound Cpd-A 0.02 g Compound Cpd-J 0.02 g Compound Cpd-N 0.01 g 19th layer: 2nd protective layer Colloidal silver Silver amount 0.05 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.3 g 20th layer: Third protection Layer Colloidal silver Silver amount 0.05 mg Fine grain silver iodobromide emulsion (average particle size 0.07 μm, AgI content 1 mol%) Silver amount 0.05 g Gelatin 0.6 g Polymethylmethacrylate (average particle size 1.5 μm) 0 1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μm) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0. 03g Additives F-1 to F-1 to each silver halide emulsion layer and intermediate layer
F-9 was added.

In addition to the above composition, a gelatin hardening agent H-1 and coating surfactants W-3, W-4 and W-5, and an emulsifying surfactant W-6 were added to each layer.

Further, as an antiseptic / antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenyl isothiocyanate, and phenethyl alcohol were added.

[0173]

[Table 8]

[0174]

[Table 9]

[0175]

[Table 10]

[0176]

[Table 11]

[0177]

[Table 12]

[0178]

[Table 13]

[0179]

[Chemical 30]

[0180]

[Chemical 31]

[0181]

[Chemical 32]

[0182]

[Chemical 33]

[0183]

[Chemical 34]

[0184]

[Chemical 35]

[0185]

[Chemical 36]

[0186]

[Chemical 37]

[0187]

[Chemical 38]

[0188]

[Chemical Formula 39]

[0189]

[Chemical 40]

[0190]

[Chemical 41]

[0191]

[Chemical 42]

[0192]

[Chemical 43]

[0193]

[Chemical 44] A sample 102 was prepared in the same manner as the sample 101 except that the yellow coupler C-5 of the comparative example used in the fifteenth, 16th, and 17th layers of the sample 101 was replaced with an equal weight of the yellow coupler C-6 of the comparative example. did.

Instead of the yellow coupler C-5 of the comparative example used in the fifteenth, sixteenth and seventeenth layers of Sample 101, an equal weight of the yellow coupler C-11 (YB-5 of the present invention).
Sample 103 was prepared in the same manner as Sample 101 except that 5) was used.
It was created.

Emulsions A to N used for Samples 101 to 103
Samples 101 to 1 except that emulsions A'to N '(shown in Tables 10 and 11) were used instead of (shown in Tables 8 and 9).
Samples 201 to 203 were prepared in the same manner as 103.

Further, Samples 301 to 103 were prepared in the same manner as Samples 101 to 103, except that Emulsions A "to N" (shown in Tables 12 and 13) were used in place of the emulsions A to N used in Samples 101 to 103. Created 303.

Samples 102, 103, 202, 203, 3
The position where the 17th layer of each of 02 and 303 is installed is the first
Samples 102, 10 except that the change was made between layer 4 and layer 15
Samples 104, 105, 204, 205, 304 and 305 were prepared in the same manner as 3, 202, 203, 302 and 303.

Samples 101 to 105 obtained as described above
201 to 205 and 301 to 305 are developed by the following processing steps to obtain ISO sensitivity (daylight), maximum yellow density, and graininess of yellow image (RMS value of yellow image at yellow density of 1.0). It was

The developed sample was heated at a temperature of 80 ° C.
It was stored under a relative humidity of 70% (dark room) for 1 week, and the change in yellow density was examined to evaluate the storability of the color image (the change in density at the portion where the white density was 2.8 and the yellow density was 2.8 was read).

Table 14 shows the above results.

[0201]

[Table 14] The results of Table 14 show the following.

Samples 101, 201 and 301 using the yellow coupler C-5 of Comparative Example all had low maximum yellow densities and poor color image storability.

Samples 102, 202 and 30 in which the yellow coupler C-5 was replaced with the yellow coupler C-6 of the comparative example.
In Nos. 2 and 3, the maximum yellow density is high, but the graininess is poor and the color image storability is extremely poor.

Samples 103, 203 and 303 in which the yellow coupler C-5 of Samples 101, 201 and 301 were replaced by the yellow coupler C-11 of the present invention, the maximum yellow density,
Color image storability is good, but deterioration of graininess is a problem. The deterioration of the graininess is almost the same as that of the sample using the yellow coupler C-6 which shows a maximum yellow density which is almost the same as that of the sample 3
02 to 303 (ISO80), sample 202 to 203 (ISO160), sample 102 to 103
(ISO400), the degree is worse, but the degree is higher as the sensitivity is higher.

Although the graininess is improved by changing the arrangement of the blue-sensitive emulsion layer group, the degree of use of the yellow coupler C-11 of the present invention is higher than that of the case of using the comparative yellow coupler C-6. If it is, the degree is large. That is, the degree of improvement of the sample 105 with respect to the sample 103 is larger than the degree of improvement of the sample 104 with respect to the sample 102. Similarly, the degree of improvement of the sample 205 to the sample 203 is larger than that of the sample 204 to the sample 202, and the degree of improvement of the sample 305 to the sample 303 is larger than that of the sample 304 to the sample 302. The degree of improvement is larger.

The improvement of graininess by changing the arrangement of the blue-sensitive emulsion layer group is 205 (ISO16) for sample 203 compared to 305 (ISO80) for sample 303.
In 0), the degree is obviously large, which is 1 for sample 103.
In 05 (ISO400), it is extremely large. As a result, the granularity of sample 305 is inferior to that of sample 301 (comparison with ISO80), but the granularity of sample 205 is equivalent to that of sample 201 (comparison with ISO160), and the granularity of sample 105 is superior to that of sample 101. (Comparison with ISO400).

As described above, it was totally unexpected that the result of the comparison is greatly influenced by the sensitivity of the light-sensitive material.

As described above, Samples 105 and 205 having the constitution of the present invention showed good results in all of the maximum yellow density, graininess and color image fastness.

Further, instead of the yellow coupler C-11 (YB-55) of the present invention of Samples 203 and 205, other yellow couplers YB-1 and YB-9 of the present invention were used in the same weight. Table 15 shows the results of making 402, 403, and 404 and performing the same evaluation as in Table 14.

[0210]

[Table 15] From the results of Table 15, sample 402 having the constitution of the present invention,
As shown in 404, the yellow coupler YB- of the present invention.
It can be seen that 1, YB-9 also shows favorable results.

From the above, the usefulness of the present invention is clear.

The processing steps and processing liquid compositions are shown below. The composition of the treatment liquid is as follows. First developer water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid-5-sodium salt 2 g sodium sulfite 30 g sodium hydroquinone monosulfonate 20 g potassium carbonate 33 g 1-phenyl-4-methyl-4-hydroxymethyl- 3-Pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2 mg Water was added 1000 ml Inversion solution water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid-5-sodium salt 3 g Chloride chloride 1 Tin (dihydrate) 1 g P-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Water is added 1000 ml Color developer water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3 g Sulfite Sodium 7g Acid trisodium (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide 90 mg Sodium hydroxide 3 g Citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline. Sulfate 11 g 3,6-dithiaoctane-1,8-diol 1 g Water was added to 1000 ml Controlled water 700 ml Sodium sulfite 12 g Ethylenediamine-tetrasulfate sodium (dihydrate) 8 g Thioglycerin 0.4 ml Water was added to 1000 ml Bleach Water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2g Ethylenediaminetetraacetate Ammonium iron (III) (dihydrate) 120g Potassium bromide 100g Ammonium nitrate 10g Water is added 1000ml Fixer water 800ml Sodium thiosulfate Mu 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added 1000 ml Stabilizing water 800 ml Formalin (37% by weight) 5.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0 The same result was obtained by treating the washing with water with the following washing solution. Water washing solution Ethylenediamine tetraacetic acid disodium salt 0.4 g Water was added and 1000 ml sodium hydroxide was added to pH 7.0.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, wherein a blue-sensitive halogen is used. The silver halide emulsion layer comprises a plurality of silver halide emulsion layers having different sensitivities, and the blue-sensitive silver halide emulsion layers other than the blue-sensitive silver halide emulsion layer having the highest sensitivity among the blue-sensitive silver halide emulsion layers are blue. It is located farthest from the support in the light-sensitive silver halide emulsion layer and is represented by the following general formula (1) and / or general formula (2) in at least one layer of the blue-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material having an ISO speed of 160 or more, which contains a coupler. General formula (1) General formula (2) (In the general formulas (1) and (2), X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, and X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-. In the formula, Y represents an aryl group or a heterocyclic group, and Z represents a group which leaves when the coupler represented by the general formula (1) or (2) reacts with an oxidized product of a developing agent.)