JPH0934069A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material superior in storage stability of raw stock, little independence on humidity at the time of exposure, color development performance, and color reproduction performance, and stability to processing fluctuation. SOLUTION: The photographic constituent layers on the support of the photosensitive material comprise blue-, green-, and red-sensitive silver halide emulsion layers and the red-sensitive silver halide emulsion layer contains at least one kind of cyan coupler represented by formulae I and II, and the emulsion layer contains at least one kind of compound represented by formula III, and in the formulae I-III, each of R1 and R3 is a branched alkyl group or the like; each of R2 and R4 is a substituent; each of X1 and X2 is H atom or a group to be released by the reaction with the oxidation product of a color developing agent; each of R40 , R50 , and R60 is an aliphatic or aromatic group; and each of (l), (m), and (n) is 0 or 1 but they are not 0 at the same time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material. More specifically, it is excellent in raw storability of the light-sensitive material, humidity dependence upon exposure, color development, color reproducibility, and processing variability. And a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material for direct viewing, such as color photographic paper, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used as a color forming agent for forming a dye image. Used. These couplers are required to have basic properties such as color reproducibility, color developability and image storability in dye images to be obtained. In recent years, in particular, color reproduction is performed to faithfully reproduce the original color of the object. There is a growing demand from users to improve the quality.

To date, phenols or naphthols have been widely used as cyan image forming couplers.

However, the cyan image obtained from the conventionally used phenols and naphthols has a serious problem in color reproduction. That is, the sharpness of absorption on the short wave side is poor, and unnecessary absorption, that is, irregular absorption, is also present in the green region. As a result, it is unavoidable to correct irregular absorption due to masking or the like in the negative, and in the case of paper, there is no means for correction, and color reproducibility is considerably deteriorated at present.

For the purpose of improving color reproducibility, Japanese Patent Laid-Open No. Sho 64-64
-554, 63-250649, 63-250.
No. 650 and the like propose a pyrazoloazole type cyan coupler.

However, these couplers show good color reproducibility because electron-withdrawing groups and hydrogen-bonding groups are introduced in order to satisfy the absorption wavelength of the color-forming dye formed. However, the level of coupling activity was not sufficiently satisfactory, and color development and color reproducibility were not simultaneously satisfied.

Further, in recent years, the printing process and the developing process of the light-sensitive material for color photographing and printing have been shortened and accelerated, and the stability of the process is more and more required. .

In particular, the change in photographic performance associated with the change in the concentration of processing liquid components during continuous processing has become an increasingly serious problem in rapid processing.

However, the reality is that a silver halide photographic light-sensitive material satisfying this requirement has not yet been found.

[0010]

SUMMARY OF THE INVENTION The object of the present invention is to provide a silver halide color photograph which is excellent in raw storability of a light-sensitive material, humidity dependence upon exposure, color development, color reproducibility and processing variability. To provide a light-sensitive material.

[0011]

The above objects of the present invention have been attained by the following constitutions.

(1). The support has a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer having the following general formula ( 1) or at least one cyan coupler represented by the general formula (2), and at least one compound represented by the following general formula [SI] in the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material characterized in that

[0013]

[Chemical 6]

[Wherein R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, R ₂ and R ₄ each represent a substituent, and X ₁ and X ₂
Each represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

[0015]

[Chemical 7]

[Wherein R ₄₀ , R ₅₀ and R ₆₀ each represent an aliphatic group or an aromatic group, and l, m and n each represent 0 or 1]. However, l, m and n are not 1 at the same time. (2). On the support, there is provided a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer having the above general formula ( 1) or at least one cyan coupler represented by the general formula (2), and at least one compound represented by the following general formula [S-II] in the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material characterized in that

[0017] Formula [S-II], R _A -NHSO-R _B wherein, R _A and R _B are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,
Alkynyl group, aryl group, heterocyclic group, alkoxy group,
Aryloxy group, heterocyclic oxy group, or

[0018]

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## EQU1 ## Here, R _C and R _D each represent a hydrogen atom, an alkyl group or an aryl group. R _A and R _B may be different even in the same. ] (3). On the support, there is provided a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer having the above general formula ( 1) or at least one cyan coupler represented by the general formula (2), and at least one compound represented by the following general formula [S-III] in the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material characterized in that

[0020]

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[In the formula, J ′ represents a divalent organic group, and Y represents an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkenyl group, or a heterocyclic group. (4). On the support, there is provided a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer having the above general formula ( 1) or at least one cyan coupler represented by the general formula (2), and at least one compound represented by the following general formula [S-IV] in the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material characterized in that

[0022]

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[Wherein, R ₅₁ and R ₅₂ each represent an aliphatic group or —COR ₅₃ (R ₅₃ represents an aliphatic group), and J
₅ represents a divalent organic group or a simple bond, and l ₅ is 0 to
Represents an integer of 6. (5). On the support, there is provided a photographic constituent layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer having the above general formula ( 1) or at least one of the cyan couplers represented by the general formula (2), and at least one of a water-insoluble and organic solvent-soluble homopolymer or copolymer contained in the red-sensitive silver halide emulsion layer. A silver halide color photographic light-sensitive material characterized by containing.

The present invention will be described in detail below.

First, the cyan couplers represented by the general formulas (1) and (2) of the present invention will be described in detail.

In the general formulas (1) and (2), the branched alkyl group represented by R ₁ and R ₃ is i-
Examples thereof include a propyl group, a t-butyl group, a sec-butyl group, an i-butyl group and a t-octyl group.

As the alkyl component of the substituted alkyl group,
It may be linear, branched or cyclic alkyl group, such as methyl group, ethyl group, butyl group, i-propyl group, t-butyl group, sec-butyl group, i-butyl group, t-octyl group, cyclohexyl group and the like. Can be mentioned.

As the aryl component of the substituted aryl group,
A phenyl group etc. can be mentioned.

As the heterocyclic group, 2-furyl group, 2-thienyl group, 2-imidazolyl group, 2-thiazolyl group, 3
-Isoxazolyl group, 3-pyridyl group, 2-pyridyl group, 2-pyrimidyl group, 3-pyrazolyl group, 2-benzothiazolyl group and the like can be mentioned.

However, when R ₁ and R ₃ represent a substituted alkyl group or a substituted aryl group, these alkyl and aryl components always have a substituent.

When R ₁ and R _{3 each} represent a branched alkyl group or a heterocyclic group, these groups may have a substituent if necessary.

The substituents are not particularly limited, but typically include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl and cycloalkyl groups. A halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano,
Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, hetero Examples include groups such as ring thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues.

In the general formulas (1) and (2), R ₂
The substituent represented by and R ₄ is not particularly limited, but typical examples thereof include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups. A halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo and other groups, In addition, spiro compound residues, bridged hydrocarbon compound residues and the like are also included. These groups may be further substituted with the above substituents.

In the above-mentioned substituents for the branched alkyl group represented by R ₁ and R ₃ , the substituted alkyl group, the substituted aryl group or the heterocyclic group, and the substituents represented by R ₂ and R ₄ , The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the alkyl group and the aryl group in the substituent represented by R ₂ and R ₄ .

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7 are preferred.

Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc. A carbamoyloxy group as an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group as an alkylureido group, an arylureido group, etc .; sulfamoylamino As alkylsulfamoyl group, an aryl sulfamoylamino group such as, is preferably a 5- to 7-membered as heterocyclic group, specifically 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-
A benzothiazolyl group, a 1-pyrrolyl group, a 1-tetrazolyl group, etc .; a heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group , 1-phenyltetrazole-5-oxy group and the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy. -1,3,5-triazole-6-thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-heptadecylsuccinimide group , Phthalimide group, glutarimide group, etc .; spiro [3.3] heptan-1-yl, etc. as spiro compound residue; bridged hydrocarbon compound Examples of the group bicyclo [2.
2.1] heptan-1-yl, tricyclo [3.3.
1.1 ³⁷ ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

The substituent represented by R ₂ and R ₄ is preferably an alkyl group or an aryl group, and particularly preferably an aryl group.

The above groups may further have a substituent such as a long-chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

Examples of the group represented by X ₁ and X ₂ which can be removed by the reaction with the oxidation product of the color developing agent are, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy,
Aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, N Examples thereof include nitrogen-containing heterocycles bonded by atoms, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups. X ₁ and X ₂ are preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a nitrogen-containing heterocyclic group bonded by an N atom and the like.

Of the cyan couplers represented by the general formulas (1) and (2), those represented by the general formula (1) are preferable.

Specific examples of cyan coupler compounds represented by formulas (1) and (2) are shown below, but the invention is not limited thereto.

[0047]

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[0048]

[Chemical 12]

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

[Chemical 21]

[0058]

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[0059]

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The cyan coupler of the present invention is usually 1 × 10 ^-3 to 1 mol, preferably 1 ×, per mol of silver halide.
It can be used in the range of 10 ⁻² to 8 × 10 ⁻¹ mol.

First, the general formulas [SI] to [S-] of the present invention are described.
The compound represented by IV] will be described in detail.

Next, the compound represented by the general formula [SI] of the present invention will be described.

Examples of the aliphatic group represented by R ₄₀ , R ₅₀ and R ₆₀ include an alkyl group having 1 to 32 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group and a cycloalkenyl group. The alkyl group, alkenyl group and alkynyl group may be linear or branched. Further, these aliphatic groups include those having a substituent.

Examples of the aromatic group represented by R ₄₀ , R ₅₀ and R ₆₀ include an aryl group (eg phenyl group etc.), an aromatic heterocyclic group (eg pyridyl group, furyl group etc.) and the like. . These aromatic groups include those having a substituent.

[0065] R _40, R ₅₀ and R ₆₀ are each preferably an alkyl group or an aryl group, R _40, R ₅₀ and R
₆₀ may be the same or different, R ₄₀ , R ₅₀ and R
The total number of carbon atoms of ₆₀ is preferably 6 to 50.

The substituent of the aliphatic group or aromatic group represented by R ₄₀ , R ₅₀ and R ₆₀ is not particularly limited, but is preferably an alkoxy group, an aryloxy group, an acyl group, an acyloxy group, an alkoxycarbonyl. Group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, acylamino group, amino group and the like.

Each of l, m and n represents 0 or 1, but l, m and n cannot be 1 at the same time. That is, at least one of the aliphatic group or aromatic group represented by R ₄₀ , R ₅₀ and R ₆₀ is directly bonded to the phosphorus atom.
It is preferred that l, m and n are all 0.

The typical examples of the compounds represented by formula (SI) of the present invention are shown below, but the present invention is not limited thereto.

[0069]

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[0070]

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[0071]

[Chemical formula 26]

[0072]

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[0073]

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[0074]

[Chemical 29]

[0075]

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[0076]

[Chemical 31]

[0077]

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[0078]

[Chemical 33]

The compounds represented by the general formula [SI] of the present invention also include the compounds described on pages 4 to 5 of JP-A-56-19049.

Some compounds represented by the general formula [SI] of the present invention are commercially available, for example, JP-A-56-
19049; UK Patent 694,772; Journal of the American Chemical Society, 1957, Vol. 79, p. 6524 [J. Am. Chem. Soc. , 79 , 6524 (195
7)]; Journal of Organic Chemistry, 1960, Vol. 25, page 1000 [J. Org. C
hem. , 25 , 1000 (1960)]; Organic Synthesis, 1951, Vol. 31, p. 33 [Or
g. Synth. , 31 , 33 (1951)] and the like.

Next, the alkyl group represented by R _A and R _B for explaining the compound represented by the general formula [S-II] has a carbon number of 1 to 32, and the alkenyl group and the alkynyl group are carbon atoms. Examples of the number 2 to 32, cycloalkyl group and cycloalkenyl group include those having 3 to 12 carbon atoms. The alkyl group, alkenyl group and alkynyl group may be linear or branched. Further, these groups include those having a substituent.

The aryl group represented by R _A and R _B is preferably a phenyl group, and the group includes those having a substituent.

The heterocyclic group represented by R _A and R _B is 5
It is preferably a 7 to 7-membered one, which may be condensed, and these groups include those having a substituent.

The alkoxy group represented by R _A and R _B includes those having a substituent, and examples thereof include a 2-ethoxyethoxy group, a pentadecyloxy group, a 2-dodecyloxyethoxy group and a phenethyloxyethoxy group. To be

The aryloxy group is preferably a phenyloxy group, and the aryl nucleus may be substituted, and examples thereof include a phenoxy group, a pt-butylphenoxy group and an m-pentadecylphenoxy group.

Further, the heterocyclic oxy group is preferably one having a 5- to 7-membered heterocyclic ring, and the heterocyclic ring may further have a substituent, for example, 3,4,5,6-tetrahydro. Examples thereof include a pyranyl-2-oxy group and a 1-phenyltetrazole-5-oxy group.

Among the non-color forming compounds of the present invention, the compounds represented by the following general formula [S-II '] are particularly preferable.

[0088] In the formula [S-II '] R _E -NHSO ₂ -R _F type, R _E and R _F is are each an alkyl group or an aryl group, and these groups also include those substituted.
More preferably, at least one of R _E and R _F is an aryl group. Most preferably, R _E and R _F are both aryl groups, particularly preferably phenyl groups. here,
When R _E is a phenyl group, it is particularly preferable that the Hammett's σp value of the substituent at the para position of the sulfonamide group is −0.4 or more.

The alkyl group and aryl group represented by R _E or R _F have the same meaning as the alkyl group and aryl group represented by R _A or R _B in the above formula [S-II].

The non-color forming compound of the present invention may form a dimer or higher multimer in R _A or R _B ,
R _A and R _B may combine with each other to form a 5- or 6-membered ring.

The total number of carbon atoms of the non-color forming compound of the present invention is preferably 8 or more, particularly preferably 12 or more.

Typical specific examples of the non-color forming compound of the present invention are shown below.

[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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The non-color-forming compound represented by the general formula [S-II] of the present invention can be synthesized by a conventionally known method such as the method described in Japanese Patent Application No. 61-20589.

The amount of the non-color forming compound represented by the general formula [S-II] of the present invention to be used is preferably 5 to 500 mol%, more preferably 10 to 300 mol%, based on the coupler.

A part of the non-color forming compound represented by the general formula [S-II] of the present invention is described in JP-A-57-76543 and JP-A-57-543.
No. 7-179842, No. 58-1139, No. 62-1
No. 78258 and other publications.

Next, the general formula [S-II according to the present invention is used.
The compound represented by I] will be described.

Examples of the divalent organic group represented by J ′ include an alkylene group, an alkenylene group, a cycloalkylene group, an arylene group, a heterocyclic group and a —J ″ —NH— group (where J ″ is an arylene group. Which represents a group), and these groups may have a substituent. The alkyl group, cycloalkyl group, aryl group, alkenyl group, alkynyl group and cycloalkenyl group represented by Y are preferably those having 1 to 32 carbon atoms. These alkyl group, alkenyl group and alkynyl group may be linear or branched. These groups include those having a substituent.

The heterocyclic group represented by Y is preferably a nitrogen-containing heterocyclic group such as a pyrrolyl group, a pyrazolyl group, an imidazolyl group, a pyridyl group, a pyrrolinyl group, an imidazolidinyl group, an imidazolinyl group, a piperazinyl group,
And a piperidinyl group. These heterocyclic groups include those having a substituent.

The typical examples of the compounds represented by formula [S-III] are shown below.

[0115]

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[0116]

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[0117]

[Chemical 51]

Of the compounds represented by the general formula [S-IV], those particularly preferable in the present invention are those represented by the following general formula [IV-
I] to [IV-IV].

[0119]

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[0120] wherein R _'50 ~R' ₅₉ have the same meanings as R ₅₁ to R ₅₂ in the general formula respectively [S-IV]. m ₅ represents an integer of Less than six, n ₅ represents an integer of 1 to 10.

In the general formula [IV-III], R '
Any two selected from the ₅₄ to R _'57 may be bonded to each other to form a ring.

In the present invention, Japanese Patent Application No. 61-10167 is also used.
No. 5, No. 61-101676, No. 61-116342
The compounds described in the specification can also be preferably used.

Next, typical specific examples of the compound represented by the general formula [S-IV] are shown.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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Some of these compounds are commercially available, for example, Japanese Patent Publication No. 56-1616 and Japanese Patent Application No. 61-1.
No. 01675 and No. 61-116342.

Next, the water-insoluble and organic solvent-soluble homopolymer or copolymer of the present invention will be described in detail.

As the water-insoluble and organic solvent-soluble homopolymer or copolymer (hereinafter referred to as the copolymer of the present invention), various compounds can be used. For example, the compounds shown below can be preferably used. .

(1) Vinyl-based Polymer and Copolymer The monomers forming the vinyl-based polymer and copolymer of the present invention will be shown more specifically.

Acrylic acid ester: For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl. Acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-
Bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate,
Benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl Acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso
-Propoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (addition mole number n = 9), 1- Bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate; Methacrylic acid ester: For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, Isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Lolo benzyl methacrylate, octyl methacrylate,
Sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl. Methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate. , 2-ethoxyethyl methacrylate, 2-iso Propoxyethyl methacrylate,
2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy polyethylene glycol methacrylate (number of moles added n) =
6); Vinyl esters: for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate,
Vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate; acrylamide: for example, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl Acrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetoneacrylamide; methacrylamides: for example, methacrylamide, methylmethacrylamide, ethyl Methacryl Amide, propyl methacrylamide, butyl methacrylamide, ter
t-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide; olefins: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene; Styrenes: for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene,
Isopropylstyrene, chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzoic acid methyl ester; crotonic acid ester: for example, butyl crotonic acid, hexyl crotonic acid; itaconic acid diester: for example, dimethyl itaconic acid, Diethyl itaconic acid, dibutyl itaconic acid; maleic acid diesters: for example, diethyl maleate, dimethyl maleate, dibutyl maleate; difumarate: for example, diethyl fumarate, dimethyl fumarate, dibutyl fumarate; .

Examples of other monomers include the following.

Allyl compounds: for example, allyl acetate, allyl caproate, allyl laurate, allyl benzoate; vinyl ethers: for example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether; vinyl ketones: for example , Methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone; vinyl heterocyclic compounds: for example, vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N-vinyl pyrrolidone; glycidyl esters: for example , Glycidyl acrylate, glycidyl methacrylate; unsaturated nitriles: for example, acrylonitrile, methacrylonitrile; and the like.

The polymer used in the present invention may be a homopolymer of the above monomers, or may be a copolymer composed of two or more kinds of monomers, if necessary. Further, the polymer used in the present invention may contain a monomer having an acid group to such an extent that it does not become water-soluble (preferably 2).
0% or less. ), Those that do not contain at all.
Examples of the monomer having an acid group include acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconate (eg, monomethyl itaconate); monoalkyl maleate (eg, monomethyl maleate); citraconic acid; Acid; vinylbenzylsulfonic acid; acryloyloxyalkylsulfonic acid (eg, acryloyloxymethylsulfonic acid); methacryloyloxyalkylsulfonic acid (eg, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid); acrylamide Alkyl sulfonic acids (eg,
2-acrylamido-2-methylethanesulfonic acid, 2
-Acrylamido-2-methylpropanesulfonic acid, 2
-Acrylamido-2-methylbutanesulfonic acid); methacrylamidoalkylsulfonic acid (for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-) Acryloyloxyalkyl phosphate (e.g., acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate); methacryloyloxyalkyl phosphate (e.g., methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate) ).

The acid group-containing monomer may be a salt of an alkali metal (eg, Na, K, etc.) or ammonium ion.

As the monomer forming the polymer used in the present invention, acrylate type, methacrylate type, acrylamide type and methacrylamide type are preferable.

The polymer formed from the above monomers can be obtained by a solution polymerization method, a bulk polymerization method, a suspension polymerization method and a latex polymerization method. As the initiator used for these polymerizations, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used.

Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate, 4,4'-azobis-4-cyanovalerate sodium, 2,2'-azobis ( A water-soluble azo compound such as 2-amidinopropane) hydrochloride or hydrogen peroxide can be used.

Examples of the lipophilic polymerization initiator include azobisisobutyronitrile and 2,2'-azobis (2,4
-Dimethylvaleronitrile), 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 1,
1'-azobis (cyclohexanone-1-carbonitrile), dimethyl 2,2'-azobisisobutyrate, 2,2 '
-Lipophilic azo compounds such as diethyl azobisisobutyrate, benzoyl peroxide, lauryl peroxide, diisopropylperoxydicarbonate, and di-tert-butyl peroxide.

(2) Polyester Resin Obtained by Condensing Polyhydric Alcohol and Polybasic Acid As the polyhydric alcohol, HO—R ₁ —OH (R ₁ is a hydrocarbon having 2 to about 12 carbon atoms, particularly A glycol having a structure of (aliphatic hydrocarbons) or polyalkylene glycol is effective, and as the polybasic acid, HOOC-
Those having R ₂ —COOH (R ₂ represents a simple bond or a hydrocarbon having 1 to 12 carbon atoms) are effective.

Specific examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane and 1,4.
-Butane diol, isobutylene diol, 1,5-pentane diol, neopentyl glycol, 1,6-hexane diol, 1,7-heptane diol, 1,8-
Octanediol, 1,9-nonanediol, 1,10
-Decanediol, 1,11-undecanediol,
Examples thereof include 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol, and sorbit.

Specific examples of the polybasic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid,
Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid,
Examples thereof include citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohimeric acid, cyclopentadiene-maleic anhydride adduct, and rosin-maleic anhydride adduct.

(3) Polyester Obtained by Ring-Opening Polymerization Method These polyesters include β-propiolactone and ε-
It is obtained from caprolactone, dimethylpropiolactone and the like.

(4) Others Polycarbonate resin obtained by polycondensation of glycol or dihydric phenol with carbonic acid ester or phosgene, polyurethane resin obtained by polyaddition of polyhydric alcohol and polyvalent isocyanate or polyvalent amine. Examples thereof include polyamide resins obtained from polybasic acids.

The number average molecular weight of the polymer used in the present invention is not particularly limited, but it is preferably 200,000 or less, more preferably 5,000 or more and 100,000 or less.

Specific examples of the polymer used in the present invention are shown below, but the invention is not limited thereto. (The composition of the copolymer is shown by weight ratio.) P-1) Poly (N-sec-butylacrylamide) P-2) Poly (N-tert-butylacrylamide) P-3) Diacetone acrylamide-methyl methacrylate copolymer Polymer (25:75) P-4) Polycyclohexyl methacrylate P-5) N-tert-butylacrylamide-methyl methacrylate copolymer (60:40) P-6) Poly (N, N-dimethylacrylamide) P- 7) Poly (tert-butyl methacrylate) P-8) Polyvinyl acetate P-9) Polyvinyl propionate P-10) Polymethyl methacrylate P-11) Polyethyl methacrylate P-12) Polyethyl acrylate P-13) Vinyl acetate -Vinyl alcohol copolymer (90:10) P 14) Poly-n-butyl acrylate P-15) Poly-n-butyl methacrylate P-16) Polyisobutyl methacrylate P-17) Polyisopropyl methacrylate P-18) Polyoctyl acrylate P-19) n-butyl acrylate-acrylamide Polymer (95: 5) P-20) Stearyl methacrylate-acrylic acid copolymer (90:10) P-21) Methyl methacrylate-vinyl chloride copolymer (70:30) P-22) Methyl methacrylate-styrene copolymer Polymer (90:10) P-23) Methyl methacrylate-ethyl acrylate copolymer (50:50) P-24) n-butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:30) P-25 ) Vinyl acetate-acrylamide Copolymer (8
5:15) P-26) Vinyl chloride-vinyl acetate copolymer (65:
35) P-27) Methyl methacrylate-acrylonitrile copolymer (65:35) P-28) n-butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (3
8:38:24) P-29) Methyl methacrylate-n-butyl methacrylate-isobutyl-methacrylate-acrylic acid copolymer (37: 29: 25: 9) P-30) n-butyl methacrylate-acrylic acid (95: 5) P-31) Methyl methacrylate-acrylic acid copolymer (95: 5) P-32) Benzyl methacrylate-acrylic acid copolymer (93: 7) P-33) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate -Acrylic acid copolymer (35: 35: 25: 5) P-34) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (40: 3
0:30) P-35) Diacetone acrylamide-methyl methacrylate copolymer (50:50) P-36) Methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) P-37) Ethyl methacrylate-n-butyl Acrylate copolymer (70:30) P-38) Diacetone acrylamide-n-butyl acrylate copolymer (60:40) P-39) Methyl methacrylate-stearyl methacrylate-diacetone acrylamide copolymer (40:
40:20) P-40) n-butyl acrylate-stearyl methacrylate-diacetone acrylamide copolymer (7
0:20:10) P-41) Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) P-42) Methyl methacrylate-styrene-vinyl sulfonamide copolymer (70:20:10) P-43) Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) P-44) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35: 3)
5:30) P-45) n-butyl methacrylate-N-vinyl-
2-Pyrrolidone copolymer (90:10) P-46) Polypentyl acrylate P-47) Cyclohexyl methacrylate-methyl methacrylate-n-propyl methacrylate copolymer (37:29:34) P-48) Polypentyl methacrylate P -49) Methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-50) Vinyl acetate-vinyl propionate copolymer (75:25) P-51) n-butyl methacrylate-3-acryloxy Sodium butane-1-sulfonate copolymer (9
7: 3) P-52) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35: 35: 3)
0) P-53) n-butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) P-54) n-butyl methacrylate-styrene copolymer (82:18) P-55) tert- Butylmethacrylate-methylmethacrylate copolymer (70:30) P-56) Poly (N-tert-butylmethacrylamide) P-57) N-tert-butylacrylamide-methylphenylmethacrylate copolymer (60:40) P -58) Methyl methacrylate-acrylonitrile copolymer (70:30) P-59) Methyl methacrylate-methyl vinyl ketone copolymer (38:72) P-60) Methyl methacrylate-styrene copolymer (75:25) P-61) Methyl methacrylate-hexyl methacrylate (70:30) P-62) Butyl methacrylate-acrylic acid copolymer (85:15) P-63) Methyl methacrylate-acrylic acid copolymer (80:20) P-64) Methyl methacrylate Acrylic acid copolymer (98: 2) P-65) Methyl methacrylate-N-vinyl-2-
Pyrrolidone copolymer (90:10) P-66) n-butyl methacrylate-vinyl chloride copolymer (90:10) P-67) n-butyl methacrylate-styrene copolymer (70:30) P-68) 1,4-butanediol-adipate polyester P-69) Ethylene glycol-sebacate polyester P-70) polycaprolactam P-71) polypropiolactam P-72) polydimethylpropiolactone P-73) N-tert- Butylacrylamide-dimethylaminoethylalamide copolymer (85:15) P-74) N-tert-butylmethacrylamide-vinylpyridine copolymer (95: 5) P-75) Diethyl maleate-n-butyl acrylate Copolymer (65:35) P-76) N-tert-butyl Acrylamide-2
-Methoxyethyl acrylate copolymer (55:45) In the present invention, the copolymer of the present invention is in a state where it is present together with a coupler that forms a dye by coupling with an oxidized aromatic primary amine developing agent. And is preferably used as a dispersion existing in lipophilic fine particles. The dispersion is
It is obtained by dissolving the coupler and at least one of the copolymers of the present invention in a substantially water-insoluble high-boiling organic solvent and emulsifying and dispersing in a hydrophilic protective colloid.

Here, the substantially water-insoluble high-boiling point organic solvent is a compound immiscible with water having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, such as a phenol derivative, a phthalic acid ester or a phosphoric acid ester. And the like, organic acid amides, carbamates, kents and the like. These are disclosed in U.S. Pat. Nos. 2,322,027 and 2,35.
No. 3,262, No. 2,533,514, No. 2,8
No. 01,170, No. 2,801,171, No. 2,
No. 835,579, No. 2,852,383, No. 2,870,012, No. 2,991,171, No. 3,287,134, No. 3,554,755,
Nos. 3,676,137 and 3,676,142
No. 3,700,454, No. 3,748,14
No. 1, No. 3,779,765 and No. 3,83
No. 7,863.

Further, in order to assist the above-mentioned dissolution, a low boiling point organic solvent or an organic solvent miscible with water can be used.

As the low boiling point organic solvent, ethyl acetate, butyl acetate, cyclohexanone, isobutyl alcohol,
Examples include methyl ethyl ketone and methyl cellosolve. Examples of the water-miscible organic solvent include methyl alcohol, ethyl alcohol, acetone, phenoxyethanol, tetrahydrofuran, dimethylformamide and the like.

These low-boiling point organic solvents and water-miscible organic solvents can be removed by a method such as washing with water, or by coating and drying.

The above-mentioned organic solvents can be used in combination of two or more kinds.

In order to obtain lipophilic fine particles by emulsifying and dispersing in a hydrophilic protective colloid, a dispersing aid such as a surfactant is used by using a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device or the like. Spread. A step of removing the low-boiling organic solvent at the same time as the dispersion may be included.

An aqueous gelatin solution is preferably used as the hydrophilic protective colloid.

The average particle size of the lipophilic fine particles is 0.04
μm to 2 μm is preferred, but more preferably 0.06
μm to 0.4 μm. The particle diameter can be measured by Coulter Model N4 manufactured by Coulter, UK.

In the above, the mixing ratio of the coupler, the homo- or copolymer, the high-boiling solvent and the low-boiling solvent or the auxiliary solvent such as the organic solvent miscible with water is such that the coupler, the homo- or copolymer, or the high-boiling solvent is mixed. It may be selected so that the solution prepared by dissolving it in the auxiliary solvent has a viscosity suitable for being easily dispersed in the hydrophilic colloid. The value at this time depends on the solubility of the coupler used, the type and the degree of polymerization of the polymer, and cannot be determined uniformly. For example, the ratio (weight ratio) of the polymer to the coupler is 1:10 to 5: 1. , Preferably 1: 3 to 2: 1.

The ratio (weight ratio) of the high boiling point solvent to the coupler to be used is 1:20 to 5: 1, preferably 1: 1.
10 to 2: 1. The ratio (weight ratio) of the low boiling point solvent to the polymer is 1:10 to 10: 1, preferably 1: 4 to
5: 1.

The light-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material of the present invention contains a silver halide emulsion.

The silver halide emulsion of the present invention includes silver chloride, silver bromide, silver iodide or mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodide, and silver iodobromide. Can be applied. These silver halide emulsions are produced by a usual method, and an ammonia method, a neutral method, an acidic method, a halogen conversion method, a function addition method, a uniform precipitation method, and the like can be applied. The average diameter of the particles is not limited, but is preferably 0.01 μm to 5 μm. Two or more silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion used in the present invention is
Chemical sensitization can be performed using a usual method. Chemical sensitization includes a gold sensitization method using a gold complex salt, a reduction sensitization method using a reducing substance, a sulfur-containing compound capable of reacting with silver ions and a so-called sulfur sensitization method using active gelatin, A sensitization method using a salt of a noble metal belonging to Table VIII can be used.

The silver halide emulsion used in the present invention is
Spectral sensitization can be performed. The method can be carried out by using cyanine dyes such as monomethine cyanine, pentamethine cyanine, merocyanine and carbocyanine alone or in combination, or by combining them with a styryl dye or an aminostilbene compound.

The silver halide emulsion used in the present invention includes stabilizers, antifoggants, surfactants, defoamers, antistatic agents, hardeners, film physical property improvers, brighteners and stain inhibitors. ,
Additives such as ultraviolet absorbers and irradiation inhibitors can be included. For these various additives, see Research Disclosure 176
Vol. All those described in 17643 (1978) can be used.

The support of the color photographic light-sensitive material of the present invention comprises
It can be appropriately selected according to the purpose. For example, a cellulose acetate film, a polyethylene terephthalate film, a polystyrene film, a polycarbonate film, or a laminate thereof, paper, baryta paper, α-
Paper, synthetic paper, glass, coated with olefin polymer,
There are metals, etc.

In the above color photographic light-sensitive material, it is advantageous to use gelatin as the binder or protective colloid, but other hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, and hydroxy. Cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, etc. It is possible to mix and use various types of synthetic hydrophilic polymer substances.

[0169]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 On a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, a polyethylene layer containing titanium oxide was added to each layer having the following constitution. Samples 1 to 20 of multilayer silver halide color photographic light-sensitive material were prepared by coating on the side of. The coating liquid was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST
-2) 6.67 g, additive (HQ-1) 0.67 g, anti-irradiation dye (AI-3) 0.33 g, high boiling organic solvent (DNP) 6.67 g, and ethyl acetate 60 ml.
To dissolve the solution, and add 20% surfactant (SU-
1) 220 ml of 10% gelatin aqueous solution containing 7 ml
The mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardener, the second and fourth layers (H
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. The amount added in the silver halide photographic light-sensitive material indicates the number of grams per 1 m ² unless otherwise specified.

[0174]

[Table 1]

[0175]

[Table 2]

[0176]

[Chemical formula 61]

[0177]

Embedded image

[0178]

Embedded image

[0179]

Embedded image

[0180]

Embedded image

[0181]

Embedded image

[0182]

Embedded image

(Method for preparing blue-sensitive silver halide emulsion) 4
The following (solution A) and (solution B) were pAg = 6.5 and pH = 3 in 1000 ml of a 2% aqueous gelatin solution kept at 0 ° C.
The solution was added simultaneously over 30 minutes while controlling to 0, and the following (Solution C) and (Solution D) were further pAg = 7.3 and pH = 5.
5 and simultaneously added over 180 minutes. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. For control of pAg, a control solution having the following composition was used. The composition of the control liquid is a mixed halide salt aqueous solution consisting of sodium chloride and potassium sulfide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentrations of the control liquid are A liquid and B liquid. The amount was 0.1 mol / liter when the liquids were mixed, and 1 mol / liter when the liquids C and D were mixed.

(Liquid A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to make up to 200 ml.

(Solution B) Silver nitrate 10 g Water was added to make up to 200 ml.

(Liquid C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to make a final volume of 600 ml.

(Solution D) Silver nitrate 300 g Water was added to make 600 ml.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
a Desalting was performed using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle size of 0.85 μm, a coefficient of variation (σ / F) = 0.07, and containing silver chloride. Cubic Emulsion EMP with 99.5 mol%
-1 was obtained.

The above emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodispersed cubic emulsion EMP-2 having a thickness of 3 μm, a coefficient of variation (σ / F) = 0.08 and a silver chloride content of 99.5 mol% was obtained.
For EMP-2, 120 at 55 ° C. using the following compounds
Chemical ripening is carried out to obtain a green-sensitive silver halide emulsion (Em-
G) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation method of red-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (liquid C) and (liquid D) were changed in the same manner as in EMP-1 except that the average particle diameter was 0.5.
A monodisperse cubic emulsion EMP-3 having a thickness of 0 μm, a coefficient of variation (σ / F) = 0.08 and a silver chloride content of 99.5 mol% was obtained.
EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compound to give a red-sensitive silver halide emulsion (Em-
R) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0193]

[Equation 1]

[0194]

Embedded image

The samples thus obtained were evaluated by the following methods.

<< Evaluation of Relative Sensitivity >> Each sample was subjected to gradation exposure for sensitometry for 0.5 seconds through a red filter, and then subjected to the following development processing. The concentration of the obtained sample was measured using an optical densitometer (PDA-65 type manufactured by Konica Corp.) to determine the sensitivity and the maximum concentration (Dmax).

<< Evaluation of storability >> One day after application of each sample, after aging storage for 3 months in an environment of 25 ° C. and 60% (relative humidity), exposure and treatment were performed in the same manner as described above, and sensitivity of both samples was evaluated. Were compared.

For sensitivity comparison, the sensitivity of the sample one day after application was set to 10
It was set to 0 and the sensitivity of the sample after storage for 3 months was represented by relative sensitivity.

<< Evaluation of Sensitivity Fluctuation due to Humidity Change during Exposure >> The ambient temperature during exposure was kept constant at 25 ° C., the ambient humidity was changed to 15% and 18%, and the sensitivities were compared. The change in sensitivity due to the change of was tested. For comparison of sensitivities, the sensitivity when the humidity was 15% was 100, and the sensitivity when the humidity was 18% was represented by the relative sensitivity.

The obtained sample was exposed to light in the same manner as above, except that the amount of CD-3 as a color developing agent in the color developing solution in the processing step was 3.5 g / l. Processing was performed by the same process, and the maximum density (Dmax ') of the red-sensitive photosensitive layer was measured.

The color reproducibility of each of Samples 1 to 20 was evaluated by the following method.

First, a color negative film (Konica Color LV-400: manufactured by Konica Corporation) and a camera (Konica F)
T-1 MOTOR: manufactured by Konica Corporation) was used to photograph a Macbeth color checker. Subsequently, color negative development processing (CNK-4: manufactured by Konica Corporation) was performed, and the obtained negative image was converted to a Konica Color Printer CL-P.
Sample No. 2000 (manufactured by Konica Corporation).
Prints were made on each of Nos. 1 to 20 to a size of 82 mm × 117 mm, and practical prints were obtained in the same manner as described above. Printer conditions at the time of printing were set for each sample so that the gray on the color checker became gray on the print.

The color reproducibility of the obtained practical prints was visually evaluated.

The results are summarized in Table 3.

The processing conditions are as follows.

Treatment process Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleach fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Dry 60-80 ° C. 60 seconds Color development Developer solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1. 0 g catechol-3,5-disulfonic acid disodium salt 1.0 g diethylene glycol 10 g N-ethyl-N-β-methanesulfonamide ethyl-3-methyl-4-aminoaniline sulfate (CD-3) 4.5 g fluorescence enhancement Whitening agent (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter and carbonic acid. Adjust to pH = 5.7 with potassium or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 2.0 g o-phenylphenol sodium 1.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

[0209]

[Table 3]

[0210]

Embedded image

As can be seen from Table 3, Sample No. 1 using the cyan coupler outside the present invention and HBS outside the present invention. 1
And No. No. 2 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and HBS of the present invention
Sample No. 3 and No. 3 In No. 4, although the maximum density and the color reproducibility are slightly improved, it cannot be said that the raw storability and the humidity dependency during exposure are sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. In No. 5, although a slight effect is recognized in terms of color developability and raw storability, it cannot be said that processing variability and color reproducibility are sufficient.

On the other hand, the sample No. 6 to sample N
o. No. 20 has a high sensitivity, a high maximum density, a good raw storability, and a very good humidity dependency at the time of exposure, processing variability, and color reproducibility.

Example 2 A sample was prepared in the same manner as in Example 1 except that the HBS of the fifth layer was changed as shown in Table 4, and the same evaluation as in Example 1 was performed. went. The results are also shown in Table 4.

[0215]

[Table 4]

As is clear from Table 4, Sample No. 1 using the cyan coupler outside the present invention and HBS outside the present invention. Two
1 and No. 1 No. 22 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and H of the present invention
Sample No. using BS. 23 and No. 23. In No. 24, although the maximum density and color reproducibility are slightly improved, it cannot be said that the raw storability and the humidity dependency during exposure are sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. Sample No. 25 has some effects in color development and raw storability, but it cannot be said that the processing variability and color reproducibility are sufficient.

On the other hand, the sample No. 26-Sample No. No. 40 has a high sensitivity, a high maximum density, a good raw storability, and a very good humidity dependency at the time of exposure, processing variability, and color reproducibility.

Example 3 A sample was prepared in the same manner as in Example 1 except that the HBS of the fifth layer was changed as shown in Table 5, and the same evaluation as in Example 1 was performed. went. The results are shown in Table 5.

[0220]

[Table 5]

As is clear from Table 5, Sample No. 1 using the cyan coupler outside the present invention and HBS outside the present invention. Four
1 and No. 1 No. 42 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, processing variability, and color reproducibility. Further, cyan couplers other than the present invention and H of the present invention
Sample No. using BS. 43 and No. 43. Sample No. 44 shows some improvement in maximum density and color reproducibility, but it cannot be said that raw storage stability and humidity dependency during exposure are sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. Sample No. 45 has some effects in color development and raw storage stability, but it is difficult to say that processing variability and color reproducibility are sufficient.

On the other hand, the sample No. 1 of the present invention. 46-Sample No. No. 60 has high sensitivity, high maximum density, good raw storability, and very good humidity dependency at the time of exposure, process variability, and color reproducibility.

Example 4 A sample was prepared in the same manner as in Example 1 except that the HBS of the fifth layer was changed as shown in Table 6, and the same evaluation as in Example 1 was performed. went. Table 6 also shows the results.

[0225]

[Table 6]

As is clear from Table 6, Sample No. 1 using the cyan coupler outside the present invention and HBS outside the present invention. 6
1 and No. 1 62 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and H of the present invention
Sample No. using BS. 63 and No. No. 64 shows some improvement in maximum density and color reproducibility, but it cannot be said that raw storage stability and humidity dependency during exposure are sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. Sample No. 65 has some effects on color development and raw storability, but it cannot be said that processing variability and color reproducibility are sufficient.

On the other hand, Sample No. 66-Sample No. No. 80 has high sensitivity, high maximum density, good raw storability, and very good humidity dependency during exposure, process variability, and color reproducibility.

Example 5 A sample was prepared in the same manner as in Example 1 except that the HBS of the fifth layer was changed as shown in Table 7, and the same evaluation as in Example 1 was performed. went. The results are also shown in Table 7.

[0230]

[Table 7]

As is clear from Table 7, Sample No. 1 using the cyan coupler outside the present invention and HBS outside the present invention. 8
1 and No. 1 No. 82 is not sufficient in terms of sensitivity, maximum density, raw storability, humidity dependency during exposure, process variability, and color reproducibility. Further, cyan couplers other than the present invention and H of the present invention
Sample No. using BS. 83 and No. Sample No. 84 has some improvement in the maximum density and color reproducibility, but it is hard to say that the raw storability and the humidity dependency during exposure are sufficient.

On the other hand, Sample No. 1 using the cyan coupler of the present invention and HBS other than the present invention. No. 85 has a slight effect on color development and raw storability, but it cannot be said that processing variability and color reproducibility are sufficient.

On the other hand, the sample No. 1 of the present invention. 86-Sample No. No. 100 has high sensitivity, high maximum density, good raw storability, and very good humidity dependency during exposure, process variability, and color reproducibility.

[0234]

According to the present invention, there is provided a silver halide color photographic light-sensitive material which is excellent in raw storability of the light-sensitive material, humidity dependency upon exposure, color development, color reproducibility and processing variability. I was able to.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03C 7/396 G03C 7/396

Claims (5)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the following general formula (1) or general formula (2). A silver halide color photographic light-sensitive material containing at least one cyan coupler, and at least one compound represented by the following general formula [SI] in the red-sensitive silver halide emulsion layer. . Embedded image [In the formula, R ₁ and R ₃ each represent a branched alkyl group, a substituted alkyl group, a substituted aryl group or a heterocyclic group, R ₂ and R ₄ each represent a substituent, and X ₁ and X ₂ each represent a hydrogen atom. Alternatively, it represents a group capable of splitting off upon reaction with an oxidized product of a color developing agent. [Chemical formula 2] [In the formula, R ₄₀ , R _50, and R ₆₀ each represent an aliphatic group or an aromatic group, and l, m, and n each represent 0 or 1. However, l, m and n are not 1 at the same time. ] 2. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the above general formula (1) or general formula (2). A silver halide color photographic light-sensitive material containing at least one cyan coupler and at least one compound represented by the following general formula [S-II] in the red-sensitive silver halide emulsion layer. . In the formula [S-II], R _A -NHSO-R _B [wherein, R _A and R _B are each a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group,
Alkynyl group, aryl group, heterocyclic group, alkoxy group,
An aryloxy group, a heterocyclic oxy group, or Represents Here, R _C and R _D each represent a hydrogen atom, an alkyl group or an aryl group. R _A and R _B may be different even in the same. ] 3. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the above general formula (1) or general formula (2). A silver halide color photographic light-sensitive material comprising at least one cyan coupler and at least one compound represented by the following general formula [S-III] in the red-sensitive silver halide emulsion layer. . Embedded image [In the formula, J ′ represents a divalent organic group, Y is an alkyl group,
Represents a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, a cycloalkenyl group, or a heterocyclic group. ] 4. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the above general formula (1) or general formula (2). A silver halide color photographic light-sensitive material comprising at least one cyan coupler and at least one compound represented by the following general formula [S-IV] in the red-sensitive silver halide emulsion layer. . Embedded image [Wherein R ₅₁ and R ₅₂ are each an aliphatic group or —COR
₅₃ (R ₅₃ represents an aliphatic group), J ₅ represents a divalent organic group or a simple bond, and l ₅ represents an integer of 0 to 6. ] 5. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is represented by the above general formula (1) or general formula (2). A silver halide color photograph containing at least one kind of cyan coupler and containing at least one kind of a water-insoluble organic solvent-soluble homopolymer or copolymer in the red-sensitive silver halide emulsion layer. Photosensitive material.