JP2002062624A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material excellent in preservability in the product shape. SOLUTION: In the silver halide color photographic sensitive material with at least one blue-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one red-sensitive emulsion layer on a transparent base, the transparent base is a plastics base with both faces undercoated with an undercoating liquid containing at least one compound selected from water- miscible organic solvents other than alcohols, substituted phenols each having a molecular weight of <=200 and acetic acid having a halogen atom substituted for at least one hydrogen atom on the methyl group and at least one of the sensitive emulsion layers contains a specified coupler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color reversal photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is usually coated on a support made of cellulose triacetate, and then processed into a product form. Sealed in the case. In the case of a sheet film, usually, several films are stacked (in most cases, 10 sheets), and after placing thick paper on both sides, the film is sealed in a light-shielding paper bag laminated with plastic. In the case of a so-called brownie-sized film, the film is usually wound together with light-shielding paper and filled in a plastic-laminated bag.

[0003] The film is stored in such a sealed state from the time it is manufactured until it is loaded into a camera by a user, and therefore, storage stability as a product form is an important quality. In many cases, storage stability is different between a sealed state and storage in an open system. For example, the volatile organic solvent used in the process of manufacturing the support and the volatile organic solvent used in emulsifying and dispersing the organic compound contained in the hydrophilic colloid layer such as the photosensitive emulsion layer remain in the photosensitive material. However, the solvent gas generated from these may affect the film in the sealed container.

[0004] The plastic support used for the photosensitive material is
Before coating the photosensitive emulsion layer, it is usually undercoated with gelatin for the purpose of improving the adhesion between the plastic support and the hydrophilic colloid layer constituting the photosensitive material. The liquid often contains gelatin, water, and a water-miscible organic solvent in addition to water, and a ketone such as acetone may be used as the water-miscible organic solvent. However, conventional silver halide color photographic light-sensitive materials, particularly films using 4-equivalent pyrazolone magenta couplers, are susceptible to these residual solvents, and have the problem that photographic properties fluctuate during storage of product forms.

[0005] As a result of studies by the present inventors, it has been found that a product form in which both sides of a plastic support need to be primed, such as a sheet film or a brownie film, usually has a thickness of about 2 mm.
In the case of a sheet film using a plastic support having a thickness of 00 μm, the effect of the residual solvent was found to be much greater than the problem with the 135 size. Since sheet films and brownie films are often used by professional photographers, high storage stability quality has been strongly desired in this regard. It is theoretically possible to reduce the influence of the solvent remaining on the base by enhancing the drying in the step of manufacturing the base.
However, when the drying is strengthened, the brittleness of the base is deteriorated, so that in reality, the remaining of the solvent is an unavoidable problem.

On the other hand, in order to improve the color reproducibility of a color film, studies have been made on a coloring material (specifically, a photographic coupler) which gives a preferable hue. As a magenta coupler with little side absorption, a pyrazolotriazole magenta coupler is widely known. Regarding the base type and undercoat of a silver halide photosensitive material containing a 2-equivalent pyrazolotriazole coupler, see, for example, JP-A-7-64257.
No. However, as a result of investigations by the present inventors, when a pyrazolotriazole coupler is used, unevenness that occurs when a photosensitive emulsion layer is coated tends to be more noticeable after processing than when a conventionally used pyrazolone magenta coupler is used. In a film having a relatively large screen such as a sheet film, such unevenness is more conspicuous, and improvement has been desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent storage stability in a product form.

[0008]

Means for Solving the Problems The present inventors have studied to solve the above-mentioned problems, and as a result, have found that a photosensitive material having the following constitution is excellent in storage stability in a product form, thereby completing the present invention. Reached.

(1) A silver halide color photographic material having at least one blue-sensitive emulsion layer, one green-sensitive emulsion layer and one red-sensitive emulsion layer on a transparent support,
The transparent support comprises a water-miscible organic solvent other than alcohol on both sides, a substituted phenol having a molecular weight of 200 or less, and at least one compound selected from acetic acid in which at least one hydrogen atom on a methyl group is substituted with a halogen atom. A silver halide color photograph, characterized in that it is a plastic support undercoated with an undercoating solution containing at least one of the following, and wherein at least one photosensitive emulsion layer contains a coupler represented by the following formula (MC-I): Photosensitive material.

[0010]

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In the formula, R ₁ represents a hydrogen atom or a substituent, _one of G ₁ and G ₂ represents a carbon atom and the other represents a nitrogen atom, and R ₂ represents a carbon atom of G ₁ and G _2. Wherein R ₁ and R ₂ may further have a substituent, and a plurality of couplers represented by the general formula (MC-I) are bonded via R ₁ or R ₂ To form a multimer, or may be bonded to the polymer chain via R ₁ or R ₂ .

(2) In a silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer on a transparent support, at least one of the transparent supports is provided. Liquid containing a water-miscible organic solvent other than alcohol, a substituted phenol having a molecular weight of 200 or less, and at least one compound selected from acetic acid in which at least one hydrogen atom on a methyl group is substituted with a halogen atom. Wherein the silver halide color is a plastic support having a thickness of 150 μm or more and 2000 μm or less, wherein at least one photosensitive emulsion layer contains a coupler represented by the following formula (MC-I): Photosensitive material.

[0013]

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In the formula, R ₁ represents a hydrogen atom or a substituent, _one of G ₁ and G ₂ represents a carbon atom and the other represents a nitrogen atom, and R ₂ represents a carbon atom of G ₁ and G ₂ Wherein R ₁ and R ₂ may further have a substituent, and a plurality of couplers represented by the general formula (MC-I) are bonded via R ₁ or R ₂ To form a multimer, or may be bonded to the polymer chain via R ₁ or R ₂ .

(3) A silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer on a transparent support, including the support, Has a mass ratio of 0.05% or more and 3.0% or less, and at least one photosensitive emulsion layer contains a coupler represented by the following general formula (MC-I). Silver halide color photographic light-sensitive material.

[0016]

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In the formula, R ₁ represents a hydrogen atom or a substituent, _one of G ₁ and G ₂ represents a carbon atom and the other represents a nitrogen atom, and R ₂ represents a carbon atom of G ₁ and G _2. Wherein R ₁ and R ₂ may further have a substituent, and a plurality of couplers represented by the general formula (MC-I) are bonded via R ₁ or R ₂ To form a multimer, or may be bonded to the polymer chain via R ₁ or R ₂ .

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The light-sensitive material provided by the present invention is a silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer on a transparent support. One of the features is that at least one of the layers contains a coupler represented by the following general formula (MC-I).

[0019]

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In the formula, R ₁ represents a hydrogen atom or a substituent;
₂ represents a substituent, _one of G ₁ and G ₂ is a carbon atom,
The other represents a nitrogen atom, and R ₂ represents a substituent that substitutes the carbon atom of G ₁ and G ₂ . Examples of the substituent represented by R ₁ and R ₂ include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, and an aryl group. Group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group , Amino group (including anilino group), acylamino group, aminocarbonylamino group,
An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl and arylsulfinyl group, Alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups,
Examples include carbamoyl, aryl and heterocyclic azo, imide, phosphino, phosphinyl, phosphinyloxy, phosphinylamino, and silyl groups.

Hereinafter, examples of the substituents represented by R ₁ and R ₂ will be described in more detail. A halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom) and an alkyl group [representing a linear, branched, or cyclic substituted or unsubstituted alkyl group; An alkyl group (preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2- Ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms,
For example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a hydrogen atom is converted from a bicycloalkane having 5 to 30 carbon atoms) This is a monovalent group that has been removed.
For example, bicyclo [1,2,2] heptan-2-yl,
Bicyclo [2,2,2] octan-3-yl)].

Alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group; An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms); An alkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms, for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group ( It is a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. , Bicyclo [2, 2,
1] Hept-2-en-1-yl, bicyclo [2,2,
2] Oct-2-en-4-yl)].

Alkynyl group (preferably having 2 to 3 carbon atoms)
0 substituted or unsubstituted alkynyl group, for example, ethynyl, propargyl, trimethylsilylethynyl group, aryl group (preferably substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m- Chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound) And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, Isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy).

Aryloxy group (preferably substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoyl Aminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted heterocyclic oxy group, for example, 1-
Phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted having 6 to 30 carbon atoms) Arylcarbonyloxy groups such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy).

A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy,
N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
An alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group ( Preferably, a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy).

An amino group (including an anilino group) (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, Methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substitution having 6 to 30 carbon atoms) Or an unsubstituted arylcarbonylamino group such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably carbon Number 1 to 30
Substituted or unsubstituted aminocarbonylamino, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino).

An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino,
N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms)
A substituted or unsubstituted aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably having 0 to 30 carbon atoms) A substituted or unsubstituted sulfamoylamino group, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn
-Octylaminosulfonylamino)).

Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methylsulfonylamino, butylsulfonyl Amino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, Ethylthio, n-hexadecylthio), arylthio group (preferably having 6 to 30 carbon atoms)
A substituted or unsubstituted arylthio group, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 3 to 30 carbon atoms, for example,
2-benzothiazolylthio, 1-phenyl-tetrazol-5-ylthio).

Sulfamoyl group (preferably substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl , N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkyl having 1 to 30 carbon atoms) Sulfinyl group, 6 to 30
A substituted or unsubstituted arylsulfinyl group, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl).

Alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, phenyl Sulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, for example, acetyl , Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably having 7 to 3 carbon atoms)
0 substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p
-T-butylphenoxycarbonyl) and an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl).

Carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (Methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, 3 to 3 carbon atoms)
0 substituted or unsubstituted heterocyclic azo group, for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimido) ), A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably substituted or unsubstituted having 2 to 30 carbon atoms or An unsubstituted phosphinyl group, for example,
Phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl).

Phosphinyloxy group (preferably substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group (Preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted or unsubstituted having 3 to 30 carbon atoms). Substituted silyl groups such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

Among the above substituents, those having a hydrogen atom may be removed and further substituted with the above group. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

R ₁ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an arylthio group, an alkylthio group, an aminocarbonylamino group, an alkoxycarbonylamino group, a carbamoyloxy group. And a heterocyclic thio group, which may have a substituent.

R ₁ is more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group (including an anilino group), and further preferably a secondary or tertiary group having 3 to 15 carbon atoms in total. It is an alkyl group, and a tertiary alkyl group having 4 to 10 carbon atoms in total is most preferable.

_One of G ₁ and G ₂ is a nitrogen atom,
The other is a carbon atom, and the one having a carbon atom has the general formula (M
_{R 2} is substituted indicated by C-I).

[0037] Preferably the R _2, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an aminocarbonylamino group, an alkoxycarbonylamino group include acylamino group, further R ₂ having a carbon number of 6 It is a group having a total carbon number of 6 or more and 70 or less containing an alkyl group or an aryl group of 30 or less as a partial structure, and preferably imparts immobility to the coupler of the general formula (MC-I).

Preferred among the couplers represented by the general formula (MC-I) are those in which R ₁ is a secondary or tertiary alkyl group or aryl group, and R ₂ is a substituted alkyl group or a substituted alkyl group. An aryl group, wherein R ₂ is substituted with an alkoxy group, an aryloxy group, an acylamino group, an aminocarbonylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkyl and an arylsulfonylamino group; A carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an acyloxy group,
Those having a group selected from a carbamoyloxy group, a sulfinyl group, a phosphonyl group, an acyl group and a halogen atom are preferred.

More preferable examples of the general formula (MC-I) include compounds in which R ₂ is a substituent represented by the following general formula (BL-1) or (BL-2).

[0040]

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[0041]

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In the general formula (BL-1), R ₃ , R ₄ ,
R ₅ , R ₆ , and R ₇ represent a hydrogen atom or a substituent, and at least one of them represents a group having 4 to 70 carbon atoms in total;
A substituent containing a substituted or unsubstituted alkyl group as a partial structure, or a substituent containing a substituted or unsubstituted aryl group having 6 to 70 carbon atoms in total as a partial structure.

The group represented by formula (BL-1) will be described below. In the formula, R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ each independently represent a hydrogen atom or a substituent, and when it is a substituent, examples of the substituent include those described in the section of R _2. No. At least one of R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ has a total number of carbon atoms of 4 to 70, a substituent containing a substituted or unsubstituted alkyl group as a partial structure, or a total number of carbon atoms of 6 or more. It is a substituent containing a substituted or unsubstituted aryl group as a partial structure of 70 or less, preferably a substituted or unsubstituted alkyl group having a total carbon number of 4 or more (6 or more when an aryl group is contained) or 70 or less. Alkoxy group containing an aryl group as a partial structure, aryloxy group, acylamino group, aminocarbonylamino group, carbamoyl group, alkoxycarbonylamino group, sulfonyl group, alkyl and arylsulfonylamino group, sulfamoyl group, sulfamoylamino group, alkoxy A carbonyl group, an alkyl group, and an aryl group. Above all, the total number of carbon atoms is 4 or more (6 or more when containing an aryl group)
Alkoxy groups, acylamino groups, alkyl and arylsulfonylamino groups each having a partial structure of 70 or less alkyl groups or aryl groups are preferred.

Next, the group represented by formula (BL-2)
Will be described. Where G₃Is substituted or unsubstituted methyl
A represents an integer of 1 to 3;₈Is hydrogen
Represents an atom, an alkyl group, or an aryl group;₄Is -C
O- or -SO₂-Represents R₉Is 6 to 7 carbon atoms in total
0 or less, substituted or unsubstituted alkyl group or ant
A substituent containing a thiol group as a partial structure. R₉Is replaced
When having a group, R₂The items listed in the section
Is mentioned. When a is 2 or more, a plurality of G ₃Is all
They may be the same or different. Preferably
(G₃The group represented by a) is -CH₂-, -C (CH₃)
H-, -C (CH₃)₂-, -C₂H₄-, -C (CH
₃) H-CH₂-, -C (CH₃)₂-CH₂-, -C
(CH₃)₂-C (CH₃) H-, -C (CH₃) H-
C (CH₃) H-, -C (CH₃)₂-C (CH₃)₂
-, -C (i-C₃H₇) H-, -C (i-C₃H₇)
H-CH ₂-And R₈Is a hydrogen atom, G₄Is -CO
-, -SO₂-And R₉Is 10 to 70 carbon atoms in total
Substituted or unsubstituted alkyl or aryl below
Group.

In the compound represented by the general formula (MC-I), when G ₁ is a nitrogen atom and G ₂ is a carbon atom,
R ₁ is a tertiary alkyl group, and R ₂ is a group represented by the general formula (BL-1)
And a group represented by general formula (BL)
-1) wherein, R ₄ and R ₆ are substituted or unsubstituted alkyl groups having 4 or more carbon atoms or substituted or unsubstituted aryl groups having 6 or more carbon atoms, acylamino group, sulfonamide group, ureido It is preferably a group selected from a group, an alkoxycarbonylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfamoylamino group, and an alkoxycarbonyl group.

The compound represented by the general formula (MC-I)
Chi, G₁Is a carbon atom and G₂Is a nitrogen atom, R
₁Is a tertiary alkyl group, and R₂Is the general formula (BL-1)
Or a group represented by general formula (BL-2).
New Especially R₂Is a base field represented by the general formula (BL-1)
In the formula, R₃And R₇Has 1 to 6 carbon atoms
A kill group,₄, R₅, R₆At least one of
Is a substituted or unsubstituted a having 6 to 70 carbon atoms in total.
A group containing a alkyl group or an aryl group as a partial structure.
Are preferred. Also R₂Is represented by the general formula (BL-2)
In the case of a group represented by the formula:₉Has 6 or more carbon atoms 5
At least a group containing an alkyl group of 0 or less as a substituent
A phenyl group having one, wherein a is 1 or 2 is preferable.
Best of all, further R₉Is -OH, -SO₂NH₂,
-SO₂NHR₁₀, -NHSO ₂R₁₀, -SO₂N
HCOR₁₀, -COOH, -CONH₂Chosen from
Particularly preferred are groups having a group as a partial structure.
No.

R ₁₀ represents a substituted or unsubstituted alkyl group or aryl group. When R ₁₀ is an aryl group, it is preferably a phenyl group, and the phenyl group is substituted by at least one electron-withdrawing group. Is preferred. Preferred electron withdrawing groups include a halogen atom, a cyano group, an alkyl group substituted with at least one halogen atom, an aryl group, an acyl group, a carbamoyl group, an alkyl or aryloxycarbonyl group substituted with at least one halogen atom. , A sulfonyl group, an alkyl or arylaminosulfonyl group.

When R ₁₀ is an alkyl group, it preferably has 1 to 50 carbon atoms, more preferably 1 to 3 carbon atoms.
It is a substituted or unsubstituted linear or branched alkyl group having 0 or less.

Specific examples of the compound represented by formula (MC-I) (couplers (1) to (40)) are shown below, but the present invention is not limited to these specific examples.

[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]

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The coupler of the general formula (MC-I) of the present invention can be synthesized by a known method. For example, U.S. Pat. Nos. 4,540,654, 4,705,863, 5,451,501, JP-A-61-65245, JP-A-62-209457, JP-A-62-249155, and 6
3-41851, Tokuhei 7-122744, 5-
No. 105682, No. 7-13309, No. 7-8225
No. 2 or U.S. Pat. Nos. 3,725,067 and 4,7
77, 121, JP-A-2-201442, 2-1.
No. 01077, No. 3-125143, No. 4-2422
No. 49.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling solvent in combination), and emulsified and dispersed in an aqueous gelatin solution to form a silver halide. An oil-in-water dispersion method to be added to the emulsion is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Also, the steps of the latex dispersion method as one of the polymer dispersion methods, the effects, and specific examples of the latex for impregnation,
U.S. Pat. No. 4,199,363, West German Patent Application No. (O
LS) 2,541,274, 2,541,230
No. JP-B-53-41091 and European Patent Publication No. 02
No. 9104, etc., and the dispersion with an organic solvent-soluble polymer is described in PCT International Publication No. WO8.
No. 08/00723.

Examples of the high-boiling solvents that can be used in the above-mentioned oil-in-water dispersion method include phthalic acid esters (eg, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, bis (2-ethylhexyl))
Phthalate, decyl phthalate, bis (2,4-di-te
rt-amylphenyl) isophthalate, bis (1,1-
Diethyl propyl) phthalate), esters of phosphoric or phosphonic acids (eg, diphenyl phosphate,
Triphenyl phosphate, tricresyl phosphate (synonymous with tricresyl phosphate), 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Bis (2-ethylhexyl) phenyl phosphate),
Benzoic acid esters (for example, 2-ethylhexyl benzoate, 2,4-dichlorobenzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecaneamide, N, N-diethyl) Laurylamide, N,
N, N, N-tetrakis (2-ethylhexyl) isophthalic acid amide), alcohols or phenols (for example, isostearyl alcohol, 2,4-di-ter
t-amylphenol), aliphatic esters (for example,
Dibutoxyethyl succinate, bis (2-ethylhexyl) succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl tosylate), aniline derivatives (for example, N, N-dibutyl) -2-butoxy-5-te
rt-octylaniline), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic esters (eg, tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4 -Di-tert-amylphenol, 4-
Dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2-
(2,4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkyl phosphoric acids (for example,
Bis (2-ethylhexyl) phosphoric acid, diphenylphosphoric acid) and the like. It is also preferable to use, for example, the compounds described in JP-A-6-258803 as a high-boiling solvent in addition to the above-mentioned high-boiling solvents.

Of these, phosphates, amides and aliphatic esters of aliphatic alcohols are preferred.
It is also preferable to use alcohols or phenols in combination therewith. The amount ratio of the high boiling organic solvent used for the coupler of the present invention is from 0 to 2.0 by mass.
Is preferred, more preferably 0 to 1.0, and particularly preferably 0 to 0.4. If tricresyl phosphate is used in a large amount as a high boiling point organic solvent, the effect of improving the storage stability of the present invention is reduced.When tricresyl phosphate is used, the amount thereof is preferably 0.4% by mass relative to the coupler of the present invention. Or less, more preferably 0.2 or less. As an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or more and about 160 ° C. or less (for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone,
2-ethoxyethyl acetate, dimethylformamide) may be used in combination. The content of the coupler of the present invention in the light-sensitive material is preferably 0.01 g to 10 g per m ² .
g, more preferably 0.1 g to ² g per m ² , and more preferably 1 g per mol of silver halide in the same photosensitive emulsion layer.
X 10 ^-3 mol to 1 mol is appropriate, preferably 2 x
It is 10 ⁻³ mol to 3 × 10 ⁻¹ mol.

When the photosensitive layer is a unit photosensitive layer (unit composition) composed of two or more photosensitive emulsion layers having different sensitivities, the content of the coupler of the present invention per mol of silver halide is low. 2 × 10 ⁻³ mol to 2 × 10 ^{3 in the} layer
^-1 mol is preferable, and 3 × 10 ⁻² mol to
3 × 10 ⁻¹ mol is preferred. When the unit photosensitive layer comprises three photosensitive emulsion layers having different sensitivities, the silver halide
The content of the coupler of the present invention per mol is preferably 2 × 10 ⁻³ mol to 1 × 10 ⁻¹ mol (more preferably 1 × 10 ⁻² mol to 1 × 10 ⁻¹ mol) in the low-sensitivity layer. 1 × ^{10 -2} mol to 2 × ^{10 -1} mole sensitivity layer (more preferably 3 × ^{10 -2} mol to 2 × 10 ^{- 1} mol) is preferably, 3 × ^{10 -2} mol to 3 × the sensitive layer 10 ^-1
Mol (more preferably 5 × 10 ⁻² mol to 2 × 10 ⁻¹⁾
Mol) is preferred.

The present invention contains a coupler represented by formula (MC-I), but may be used in combination with other couplers.
However, the higher the contribution of the coloring dye of the coupler of the present invention to the total concentration of the coloring matter which forms substantially the same color, the more preferable results are obtained. Specifically, at least the contribution to the color density is preferably 30% or more, more preferably 50% or more.
It is more preferable to use an amount occupying 70% or more.

In the light-sensitive material of the present invention, a competing compound (a compound which competes with an image forming coupler and reacts with an oxidized color developing agent and does not form a dye image) may be used in combination. Competing compounds include hydroquinones, catechols,
Reducing compounds such as hydrazines and sulfonamidophenols, or compounds that couple with oxidized color developing agents but do not substantially form a color image (eg, German Patent 1,155,675, British Patent 861,13)
No. 8, U.S. Pat. Nos. 3,876,428 and 3,912,
No. 513, or an outflow coupler as disclosed in JP-A-6-83002).

The competitor compound is preferably added to the light-sensitive emulsion layer containing the magenta coupler of the present invention or the non-light-sensitive layer, particularly preferably to the same light-sensitive emulsion layer as the coupler of the present invention. The amount of the competing compound to be added is preferably 0.01 g to 10 g, more preferably 0.10 g to 5.0 g, per 1 m ² of the light-sensitive material, and preferably 1 to 1000 mol% based on the coupler of the present invention. More preferably, it is used at 20 to 500 mol%. The light-sensitive material of the present invention may have a non-color-forming intermediate layer in a unit light-sensitive layer composed of a plurality of the same color-sensitive layers having different sensitivities. It is preferable to include a compound that can be used. The light-sensitive material of the present invention is disclosed in U.S. Pat. No. 4,411,987 to prevent deterioration of photographic performance due to formaldehyde gas.
And a compound which can be fixed by reacting with formaldehyde gas described in JP-A No. 4,435,503.

The light-sensitive material of the present invention may have at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. It is preferable to coat the support in this order from the far side, but the order may be different from this. Each color-sensitive layer is a unit photosensitive layer including two or more photosensitive emulsion layers having different sensitivities (unit composition).
In particular, it is preferable to form a three-layer unit comprising three light-sensitive emulsion layers, that is, a low-sensitivity layer, a medium-degree layer, and a high-sensitivity layer from the side close to the support.

One of the preferred embodiments of the present invention is as follows: an undercoat layer / antihalation layer / first intermediate layer / unit red-sensitive emulsion layer (low-sensitive red-sensitive layer / Middle-level red-sensitive layer / High-sensitivity red-sensitive layer) / Second intermediate layer / Unit green-sensitive emulsion layer (Low-sensitivity green-sensitive layer / Medium-level green-sensitive layer / High sensitivity from the side close to the support) 3 layers of green-sensitive layer) / third intermediate layer / yellow filter layer / unit blue-sensitive emulsion layer (from the side close to the support, low-sensitive blue-sensitive layer / intermediate blue-sensitive layer / high-sensitive blue-sensitive layer 3) Layers) / first protective layer / second protective layer.

The first, second, and third intermediate layers may each be a single layer, or may have a configuration of two or more layers. It is preferable that the first intermediate layer is further divided into two or more layers, and the layer directly adjacent to the red-sensitive layer contains yellow colloidal silver. Similarly, the second intermediate layer also has two or more layers, and it is preferable that the layer immediately adjacent to the green sensitive layer contains yellow colloidal silver. It is also preferable that a fourth intermediate layer is further provided between the yellow filter layer and the unitary blue-sensitive emulsion layer. It is also preferable that the protective layer has a three-layer structure of a first protective layer to a third protective layer. When the protective layer is composed of two or three layers, the second protective layer preferably contains fine grain silver halide having an average equivalent spherical diameter of 0.10 μm or less. The silver halide is preferably silver bromide or silver iodobromide.

Next, the support used in the present invention will be described. The thickness of the support used in the present invention is 60 μm or more and 20 μm or more.
It is preferably not more than 00 μm, more preferably not less than 80 μm and not more than 1000 μm. When the light-sensitive material of the present invention is used for a so-called roll film (browney film form or 135 size), the thickness is particularly preferably 80 μm or more and 150 μm or less, and when it is used for a sheet film (for example, 4 × 5 size or 8 × 10 size). Is particularly preferably 150 μm or more and 300 μm or less. When the undercoat is only on one side, the thickness of the transparent support is 150 μm to 2000 μm.
μm is preferable, and 150 μm to 300 μm is more preferable. When the undercoat is on both sides, the thickness is preferably from 60 μm to 2000 μm, more preferably from 80 μm to 500 μm,
μm to 150 μm are particularly preferred. The support used in the present invention is a transparent plastic support, and preferable materials include cellulose acetate, polyester (polyethylene terephthalate, polyethylene naphthalate, etc.).

First, cellulose acetate will be described. The cellulose acetate that can be used for the support of the present invention has an average degree of acetylation (acetylation degree) of 58.0 to 62.
A so-called triacetyl cellulose (sometimes described as cellulose triacetate) of 5% is preferable. The acetylation degree means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like). As described above, the range of the degree of acetylation of cellulose acetate is a value required to satisfy the quality required as a photographic support or an optical film.

In order to produce a cellulose acetate film used as a support, a solution is used as a dope in a solvent casting method. The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%. It is preferable that the surface of the drum or the band is finished in a mirror state. The casting and drying methods in the solvent casting method are described in US Pat.
No. 603, No. 2492078, No. 2492977,
No. 2492978, No. 2607704, No. 2739
Nos. 069 and 2739070, British Patent 640731
Nos. 736892 and JP-B-45-455.
No. 4, No. 49-5614, JP-A-60-176834.
And JP-A-60-203430 and JP-A-62-115035.

A plasticizer can be added to the cellulose acetate support in order to improve the mechanical properties or to increase the drying speed. As a plasticizer,
Phosphate or carboxylate esters are used. Examples of phosphate esters include triphenyl phosphate (TPP) and tricresyl phosphate (TCC).
P) is included. Representative carboxylic esters include phthalic esters and citric esters. Examples of phthalate esters include dimethyl phthalate (DM
P), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate, (DOP) and diethylhexyl phthalate (DEHP). Examples of citrate esters include acetyltriethyl citrate (OACTE) and acetyltributyl citrate (OACTB). Examples of other carboxylic esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic esters. Among them, TPP and TCP are preferable.

The amount of the plasticizer to be added is preferably 0.1 to 25% by mass of the amount of the cellulose acetate.
And more preferably 3 to 1% by mass.
Most preferably, it is 5% by mass. Further, a deterioration inhibitor (for example, a peroxide decomposer, a radical inhibitor, a metal deactivator, an acid scavenger) or an ultraviolet inhibitor may be added to the cellulose acetate support. The deterioration inhibitor is described in JP-A-5-1907073. The UV inhibitors are described in JP-A-7-11056. Other preferable properties of cellulose acetate as a photographic support are described in JP-A-10-4877.
No. 9 describes this.

Next, the polyester support will be described. Among polyesters composed of diols and dicarboxylic acids, preferred are homopolymers such as poly (ethylene terephthalate), poly (ethylene naphthalate), poly (cyclohexane dimethanol terephthalate) (PCT), and particularly preferred aromatic dicarboxylic acids. 2,6-naphthalenedicarboxylic acid (NDCA) as an acid,
Terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), biphenyl-4,4'-dicarboxylic acid (PPDC), ethylene glycol (EG) as a diol, cyclohexane dimethanol (CHD)
M), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), parahydroxybenzoic acid (PHBA) as a copolymerizable hydroxycarboxylic acid, 6-hydroxy-2-naphthalenecarboxylic acid (HNCA) Are copolymerized.

Of these, more preferred are:
Terephthalic acid, copolymer of naphthalenedicarboxylic acid and ethylene glycol (mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is 0.9: 0.1 to 0.1: 0.9
Is preferable, and 0.8: 0.2 to 0.2: 0.8 is more preferable. ), Terephthalic acid and ethylene glycol,
Copolymer of bisphenol A (mixing molar ratio of ethylene glycol to bissuenol A is 0.6: 0.4 to 0:
It is preferably between 1.0 and 0.5: 0.5 to 0.1.
~ 0.9 is preferred. ), Isophthalic acid, biphenyl-4,4'-dicarboxylic acid, copolymer of terephthalic acid and ethylene glycol (isophthalic acid; biphenyl-
The molar ratio of 4,4'-dicarboxylic acid is 0.1 to 0.5 and 0.1 to 0.5, respectively, assuming that terephthalic acid is 1, more preferably 0.2 to 0.3 and 0.1 to 0.5, respectively. 2-0.3
Is preferred. ), Terephthalic acid, a copolymer of neopentyl glycol and ethylene glycol (neopentyl glycol and ethylene glycol have a molar ratio of 1: 0 to 0.
7: 0.3 is preferred, and 0.9: 0.1 is more preferred.
０．６0.6: 0.4) Terephthalic acid, copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol to biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1 : 0.9-0.7:
0.3. ), Parahydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of parahydroxybenzoic acid and ethylene glycol is from 1: 0
0.1: 0.9 is preferred, and more preferably 0.9: 0.9.
0.1-0.2: 0.8).

These homopolymers and copolymers can be synthesized according to a conventionally known polyester production method. For example, when an acid component is directly esterified with a glycol component, or when a dialkyl ester is used as an acid component, first, a transesterification reaction is performed with the glycol component, and this is heated under reduced pressure to remove excess glycol components. By doing so, it can be synthesized. Alternatively, an acid component may be used as an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction, a catalyst or a polymerization reaction catalyst may be used, or a heat resistance stabilizer may be added. These polyester synthesis methods are described, for example, in Polymer Experiments, Vol. 5, “Polycondensation and Polyaddition” (Kyoritsu Shuppan, 1980), pp. 103-136, “Synthetic Polymer V” (Asakura Shoten, 1971). Years) 187-286
It can be performed with reference to the description on the page. The preferred average molecular weight (weight) range for these polyesters is about 10.0
00 to 500,000.

Further, these polyesters may be partially blended with another polyester, copolymerized with a monomer constituting another polyester, or In these polyesters, a monomer having an unsaturated bond can be copolymerized to form a radical crosslink. Polymer blends obtained by mixing two or more kinds of the obtained polymers are described in JP-A-49-5482, JP-A-64-4325, JP-A-3-192718, Research Disclosure,
83, 739-41, 284, 779-82, 29
According to the method described in US Pat. No. 4,807-14, molding can be easily performed.

In order to further enhance the function of the polyester of the present invention as a photographic support, it is preferable to coexist various additives. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability over time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the amount of the ultraviolet absorber is usually 0.01% by mass to 20% by mass, preferably 0.05% by mass, based on the mass of the polyester film.
It is about 10% by mass to 10% by mass. If it is less than 0.01% by mass, the effect of suppressing the deterioration of ultraviolet rays cannot be expected.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, and 2,2 '. Benzophenones such as 2,4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;
(2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-t
-Butylphenyl) benzotriazole, 2- (2'-
Benzotriazoles such as (hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole;
Salicylic acid 2,4,6-tris [2'-hydroxy-4'- such as phenyl salicylate and methyl salicylate
(2 "-ethylhexyloxy) phenyl] triazine, 2-phenyl-4,6-di [2'-hydroxy-
And triazine-based ultraviolet absorbers such as 4 '-(2 "-ethylhexyloxy) phenyltriazine.

Further, a method of incorporating inert inorganic particles and the like into a polyester film and a method of adding a dye are known. In the present invention, a method by adding a dye which does not significantly increase the film haze is preferable. The dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general properties of the photosensitive material, and the dye has excellent heat resistance in the film forming temperature range of the polyester film, and polyester. Those having excellent compatibility with are preferred. From the above viewpoints, it is possible to achieve the object by mixing dyes commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, it is necessary that the color density in the visible light range is measured with a color densitometer manufactured by Macbeth Co., and that it is at least 0.01. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be provided with lubricity according to the application, and the means for imparting lubricity is not particularly limited.
The kneading of an inert inorganic compound or the application of a surfactant is used as a general method. Examples of such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. In addition to the lubricity imparted by the external particle system in which inert particles are added to the polyester synthesis reaction system described above, a lubricity imparting method using an internal particle system in which a catalyst or the like to be added during the polymerization reaction of the polyester is precipitated can also be adopted. It is. Although there is no particular limitation on these means for imparting lubricity, transparency is an important requirement for the support for a photographic light-sensitive material. It is desirable to select SiO ₂ having a refractive index relatively close to the above or an internal particle system capable of relatively reducing the particle diameter of precipitation.

The plastic support of the present invention is subjected to a surface treatment or an undercoat to improve the adhesion between the support and the hydrocolloid layer constituting the photosensitive element. This includes (1) surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc. After that, a method of directly applying a photographic emulsion to obtain an adhesive force, and (2) providing an undercoat layer after these surface treatments once or without surface treatment, and coating a photographic emulsion layer thereon There are two methods (for example, U.S. Pat. Nos. 2,698,241 and 2,764,520).
2,864,755, 3,462,335, 3,475,193, 3,143,421, 3,501,301, 3,460,944, and 3 No. 6,674,531, British Patent No. 788,365,
No. 804,005, No. 891,469, Tokubo 48
-43122, 51-446, etc.).

All of these surface treatments are thought to be due to the formation of polar groups to some extent on the originally hydrophobic support surface and to increase the crosslink density of the surface. It is considered that the affinity of the components contained in the undercoat liquid with the polar group increases, or the fastness of the adhesive surface increases. Various modifications have been made to the structure of the undercoat layer, and a layer (hereinafter, abbreviated as the first undercoat layer) that adheres well to the support is provided as the first layer, and a second layer is formed thereon as a second layer. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter abbreviated as a second undercoat layer) in good contact with the layer, and a single layer of applying only one resin layer containing both a hydrophobic group and a hydrophilic group. There is a law.

Among the surface treatments (1), the corona discharge treatment can be performed by any of the conventionally known methods, for example, Japanese Patent Publication No. 48-50 / 1972.
No. 43, No. 47-51905, JP-A-47-2086
No. 7, No. 49-83767, No. 51-41770,
It can be achieved by the method disclosed in JP-A-51-131576 and the like.

The glow discharge treatment can be performed by any of the conventionally known methods, for example, Japanese Patent Publication Nos.
No.-10336, No.45-22004, No.45-22
No. 005, No. 45-24040, No. 46-43480
No. 3,057,792, U.S. Pat.
No. 95, No. 3,179,482, No. 3,288,63
8, 3,309,299, 3,424,735
Nos. 3,462,335 and 3,475,307
No. 3,761,299, British Patent 997,093
And JP-A-53-129262 can be used.

Next, the undercoating method of the present invention will be described. In the present invention, at least one surface of the plastic support is undercoated with an undercoat solution. The undercoat liquid of the present invention is
A water-miscible organic solvent other than alcohol, a substituted phenol having a molecular weight of 200 or less, and at least one compound selected from acetic acid in which at least one hydrogen atom on a methyl group is substituted with a halogen atom. Comprises a hydrophilic undercoat polymer which simultaneously functions as an undercoat layer after drying. Examples of the hydrophilic undercoat polymer used in the present invention include a water-soluble polymer, a cellulose ester, a latex polymer, and a water-soluble polyester. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, and maleic anhydride copolymer.Examples of cellulose esters include carboxymethyl cellulose and hydroxyethyl cellulose. And so on. Latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylate-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Most preferred in the present invention is gelatin.

The compound selected from the group consisting of a water-miscible organic solvent other than alcohol, a substituted phenol having a molecular weight of 200 or less, and acetic acid in which at least one hydrogen atom on a methyl group is substituted with a halogen atom is used. It is a compound that can penetrate into the plastic constituting the support as a property. As these compounds, water-miscible organic solvents other than alcohols are preferably water-miscible ketones or aldehydes, and specific examples thereof include acetone, formaldehyde, and chloral. Of these, acetone is the most preferred. preferable. In the present invention, the term “water-miscible” refers to an organic solvent that can be mixed uniformly when pure water and the organic solvent are mixed at a temperature of 25 ° C. at a volume ratio of 50:50.

Examples of the substituted phenol having a molecular weight of 200 or less include resorcinol, chlorresorcinol, methylresorcinol, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol and trichlorophenol. Phenol and the like are preferable, and resorcin is preferable. Preferred examples of acetic acid in which at least one of the hydrogen atoms on the methyl group is substituted with a halogen atom include monochloroacetic acid, dichloroacetic acid, and trifluoroacetic acid.

The undercoat liquid of the present invention preferably contains at least acetone, more preferably contains acetone, and further has a substituted phenol having a molecular weight of 200 or less, and at least one hydrogen atom on the methyl group is a halogen atom. At least one selected from acetic acid substituted with
Contains two compounds.

For the undercoat layer of the present invention, known gelatin hardeners can be used. Examples of gelatin hardeners include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, epichlorohydrin resins, cyanuric chloride compounds (for example, JP-B-47-6151 and 47-333).
Nos. 80 and 54-25411, JP-A-56-1307
No. 40), vinyl sulfone or sulfonyl compounds (for example, JP-B-47-24259,
Compounds described in JP-A-50-35807, JP-A-49-24435, JP-A-53-41221 and JP-A-59-18944), carbamoyl ammonium salt-based compounds (for example, JP-B-56-12853, JP-B-58-32699)
And JP-A-49-51945 and 51-59625.
Nos. 61-9641), amidinium salt compounds (for example, compounds described in JP-A-60-225148), and carbodiimide-based compounds (for example, JP-A-51-126125, 52-104). No. 48311), pyridinium salt compounds (for example, compounds described in JP-B-58-50699, JP-A-52-54427, JP-A-57-44140 and JP-A-57-46538), and others Belgian Patent No. 825,726,
U.S. Pat. No. 3,321,313, JP-A-50-385
No. 40, No. 52-93470, No. 56-43353
And the compounds described in JP-A-58-113929.

The undercoat layer of the present invention may contain inorganic or organic fine particles as a matting agent to such an extent that the transparency and the granularity of the image are not substantially impaired. Silica (SiO ₂ ), titanium dioxide as matting agent for inorganic fine particles
(TiO ₂ ), calcium carbonate, magnesium carbonate and the like can be used. As organic fine particle matting agents,
Polymethyl methacrylate, cellulose acetate propionate, polystyrene, US Pat. No. 4,142,
No. 894 can be used, and the polymer described in U.S. Pat. No. 4,396,706 can be used. The average particle diameter of these fine particle matting agents is preferably 1 to 10 μm. In addition, the undercoat layer may contain various additives as necessary. Examples include surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like.

The undercoating liquid according to the present invention can be prepared by a well-known coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or US Pat. It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 2,681,294. Optionally, U.S. Pat. No. 2,761,791
Nos. 3,508,947 and 2,941,898
No. 3,526,528, Yuji Harasaki,
Two or more layers can be simultaneously coated by a method described in “Coating Engineering”, page 253 (1973, published by Asakura Shoten).

In the production of the photosensitive material according to the present invention,
After coating the silver halide photographic element, it is dried,
At this time, the content of acetone in the light-sensitive material including the support after coating and drying the silver halide photographic light-sensitive element is preferably 0.05% or more and 3.0% or more with respect to the light-sensitive material.
%, More preferably 0.1% or more and 2.0% or less. If the drying is further strengthened, the brittleness of the support becomes worse, and if the acetone remains more than 3.0%, the influence on the photosensitive emulsion layer becomes too large. In the present invention, triacetyl cellulose is used as a main component, and at least one phosphate ester as a plasticizer is used in a mass ratio of 3% to 1% based on triacetyl cellulose.
A support obtained by subbing a plastic support containing 5% of the support with an undercoat solution containing acetone, formalin and gelatin is preferred. Further, a silver halide photographic light-sensitive element is coated on the support, and the content of acetone in the light-sensitive material including the support is 0.1% by mass relative to the light-sensitive material.
A silver halide color photographic light-sensitive material produced by drying to the extent that it remains in the range of from 0.05% to 3.0% is preferred.

Regarding various techniques and inorganic and organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same, generally, Research Disclosure No. 308119 (19)
1989), 37038 (1995), 40145
(1997) can be used. In addition to this, more specifically, for example, the technology and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in European Patent No. 436,938A2. It is described below and in the patents cited below.

Item The present section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Can be used in combination Page 147, line 26 to page 148, line 12 Silver halide emulsion 3) Page 137, line 35 to page 146, line 33; 149 yellow coupler, page 21 to line 23 4) Can be used in combination, page 149, lines 24 to 28; European Patent 42 Magenta Coupler 1,453A1, page 3, line 5 to page 25, line 5 5) Can be used together, page 149, lines 29 to 33; EP 432, page 3 of cyan coupler 804A2 Line 28 to page 40, line 6) Polymer coupler, page 149, lines 34 to 38; EP 435, 334A2, page 113, line 39 to page 123, line 7 7) Colored Coupler page 53, line 42 to 13 Page 34, line 149, page 39, line 45 to line 8 8) Can be used together Page 7, line 1 to page 53, line 41, page 149, 46 Functional coupler line to page 150, line 3 From EP 435,334A2, page 3, line 1 to page 29, line 50 9) Antiseptic and antifungal agents, page 150, lines 25 to 28 10) Formalin, page 149, line 15 to Line 17 Scavenger 11) P.153, Lines 38 to 47, which can be used in combination; EP 421, Other additives 453A1, page 75, line 21 to page 84, line 56, page 27, 40 Lines to page 37, line 40 12) Dispersion method Page 150, lines 4 to 24 13) Support: page 150, lines 32 to 34 14) Film thickness / film properties Page 150, line 35 To 49th line 15) Color development step, page 150, line 50 to page 151, line 47 16) Desilvering step, 15th Page 48 line, second 152 page 53 line 17) automatic developing machine # 152, page 54 line-page 153, line 2 18) washing and stabilizing steps page 153, line 3 to 37 rows.

[0096]

EXAMPLES (Example 1) Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Preparation of Sample 101 (i) Preparation of Triacetyl Cellulose Film Triacetyl cellulose was dissolved in dichloromethane / methanol = 92/8 (mass ratio) by ordinary solvent casting method (mass ratio: 13/13).
%), Plasticizers triphenyl phosphate and biphenyl diphenyl phosphate at a mass ratio of 2: 1 and a total of 14% with respect to triacetyl cellulose were prepared by a band method. A film having a thickness as shown in Table 1 below was prepared by the same production method.

(Ii) Contents of Undercoat Layer An undercoat was applied to the triacetyl cellulose film using an undercoat liquid having the following composition. The number represents the mass contained per 1.0 liter of the undercoat liquid (hereinafter, referred to as L). (Before undercoat A.) Before applying undercoat, both surfaces were subjected to corona discharge treatment.

Gelatin 10.0 g Salicylic acid 0.5 g Glycerin 4.0 g Acetone 700 mL (hereinafter referred to as mL) Methanol 200 mL Dichloromethane 80 mL Formaldehyde 0.1 mg Add water 1.0 L.

The undercoat solution described above was applied to a triacetylcellulose support as shown in Table 1 to prepare bases A to H. 50 ml of the above-mentioned undercoating liquid is applied per 1 m ² of the support, and then heated at 35 ° C. and 50% humidity for 2 hours.
Dried for minutes. Further, after blowing dry air at 100 ° C. for 20 seconds, the temperature was adjusted to 25 ° C. and the film was wound up, and then a photosensitive emulsion layer was applied and used. Further, as (undercoat B), an undercoat in which the acetone and formaldehyde of undercoat A were removed and methanol was replaced by an equivalent mass was used for comparative experiments. Further, resorcinol was added in an amount of 5.0 g per 1.0 L to (Undercoat A) to give (Undercoat C).

[0101]

[Table 1]

The bases A to H prepared as described above were coated with a photosensitive emulsion layer and, if necessary, a back layer. On the side indicated as a photosensitive emulsion coated surface in Table 1, a multilayer color photosensitive material comprising the following layers was prepared. The sample using the base A was designated as a sample 101, and the sample 1 in the following order
02 to 108. Number indicates the addition amount per m ^2. The effect of the added compound is not limited to the use described. On the back surface of the base D, a back layer shown below was applied on the undercoat layer.

First layer Binder: acid-treated gelatin (isoelectric point 9.0) 1.00 g Polymer latex: B-1 (average particle size 0.1 μm) 0.13 g Polymer latex: B-2 (average particle size 0.2 μm) 0.23 g UV absorber U-1 0.030 g UV absorber U-3 0.010 g UV absorber U-4 0.020 g High boiling organic solvent Oil-2 0.030 g Surfactant W-3 0.010 g Surfactant W-6 3.0 mg Second layer Binder: acid-treated gelatin (isoelectric point 9.0) 3.10 g Polymer latex: B-2 (average particle size 0.2 μm) 0.11 g UV absorber U-1 0.030 g UV absorber U-3 0.010 g UV Absorbent U-4 0.020 g High boiling organic solvent Oil-2 0.030 g Surfactant W-3 0.010 g Surfactant W-6 3.0 mg Dye D-2 0.10 g Dye D-10 0.12 g Potassium sulfate 0.25 g Hydroxide 0.03 g of sodium.

Third layer Binder: acid-treated gelatin (isoelectric point 9.0) 3.30 g Surfactant W-3 0.020 g potassium sulfate 0.30 g sodium hydroxide 0.03 g Fourth layer binder: lime-treated gelatin (isoelectric point 5.4) 1.15 g 1: 9 copolymer of methacrylic acid and methyl methacrylate (average particle size 2.0 μm) 0.040 g 6: 4 copolymer of methacrylic acid and methyl methacrylate (average particle size 2.0 μm) 0.030 g Surfactant W-3 0.060 g Surfactant W-2 7.0 mg Curing agent H-1 0.23 g.

On the bases E, F, G and H, the following back layers were applied.

First layer Binder: acid-treated gelatin (isoelectric point 9.0) 0.70 g Polymer latex: B-1 (average particle size 0.1 μm) 0.080 g Polymer latex: B-2 (average particle size 0.2 μm) 0.15 g UV absorber U-1 0.020 g UV absorber U-3 0.010 g UV absorber U-4 0.010 g High boiling organic solvent Oil-2 0.020 g Surfactant W-3 0.010 g Surfactant W-6 3.0 mg Second layer Binder: acid-treated gelatin (isoelectric point 9.0) 5.50 g Polymer latex: B-2 (average particle size 0.2 μm) 0.20 g UV absorber U-1 0.050 g UV absorber U-3 0.010 g UV Absorbent U-4 0.030 g High boiling organic solvent Oil-2 0.050 g Surfactant W-3 0.030 g Surfactant W-6 5.0 mg Potassium sulfate 0.50 g Sodium hydroxide 0.070 g.

Third Layer Binder: Acid-treated gelatin (isoelectric point 9.0) 5.00 g Surfactant W-3 0.020 g Potassium sulfate 0.40 g Sodium hydroxide 0.07 g Fourth layer Binder: lime-treated gelatin (isoelectric point 5.4) 0.80 g 1: 9 copolymer of methacrylic acid and methyl methacrylate (average particle size 2.0 μm) 0.020 g copolymer of methacrylic acid and methyl methacrylate 6: 4 (average particle size 2.0 μm) 0.020 g Surfactant W-3 0.030 g Surfactant W-2 4.0 mg Hardener H-1 0.35 g On the photosensitive emulsion surfaces of bases A to H, the following layers were applied.

First layer: Antihalation layer Black colloidal silver 0.20 g Gelatin 2.00 g UV absorber U-1 0.10 g UV absorber U-3 0.10 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.050 g High-boiling organic solvent Oil-2 0.050 g Dye D-4 1.0 mg Dye D-8 2.5 mg 0.05 g of a microcrystalline solid dispersion of Dye E-1.

Second layer: Intermediate layer Gelatin 0.50 g Compound Cpd-A 0.2 mg Compound Cpd-K 3.0 mg Compound Cpd-M 0.030 g Ultraviolet absorber U-6 6.0 mg High boiling organic solvent Oil-3 0.010 g High boiling organic Solvent Oil-4 0.010 g High boiling organic solvent Oil-7 2.0 mg High boiling organic solvent Oil-8 5.0 mg Dye D-7 4.0 mg Third layer: middle layer Yellow colloidal silver 0.020 g Gelatin 0.60 g Compound Cpd-M 0.010 g Compound Cpd-D 0.020 g High boiling organic solvent Oil-3 0.010 g.

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.10 g Emulsion B silver amount 0.20 g Emulsion C silver amount 0.20 g gelatin 0.70 g Coupler C-1 0.030 g Coupler C-2 0.070 g Coupler C-6 6.0mg Coupler C-9 5.0mg Coupler C-11 0.020g UV absorber U-3 0.010g Compound Cpd-A 1.0mg Compound Cpd-I 0.020g Compound Cpd-J 2.0mg High boiling organic solvent Oil-2 0.050g added Thing P-1 0.020g.

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion C silver amount 0.20 g Emulsion D silver amount 0.25 g gelatin 0.70 g coupler C-1 0.10 g coupler C-2 0.040 g coupler C-3 0.010 g coupler C-6 7.0 mg Coupler C-11 0.030 g Ultraviolet absorber U-3 0.010 g High boiling organic solvent Oil-2 0.070 g Additive P-1 0.020 g.

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion E silver amount 0.20 g Emulsion F silver amount 0.20 g gelatin 1.70 g Coupler C-1 0.020 g Coupler C-2 0.010 g Coupler C-3 0.60 g Coupler C-6 0.010 g Coupler C-11 0.20 g UV absorber U-1 0.010 g UV absorber U-2 0.010 g High boiling organic solvent Oil-2 0.030 g High boiling organic solvent Oil-9 0.010 g Compound Cpd-D 5.0 mg Compound Cpd -K 1.0 mg Compound Cpd-L 1.0 mg Compound Cpd-F 0.030 g Additive P-1 0.10 g.

Seventh layer: Intermediate layer Gelatin 1.00 g Additive P-2 0.10 g Compound Cpd-I 0.010 g Dye D-5 0.020 g Dye D-9 6.0 mg Compound Cpd-M 0.040 g Compound Cpd-O 3.0 mg Compound Cpd-P 5.0mg High boiling organic solvent Oil-6 0.050g Eighth layer: Intermediate layer Yellow colloidal silver Silver amount 0.020g Gelatin 1.20g Additive P-2 0.05g UV absorber U-1 0.010g UV absorber U- 3 0.010 g Compound Cpd-A 0.050 g Compound Cpd-D 0.030 g Compound Cpd-M 0.050 g High boiling organic solvent Oil-3 0.010 g High boiling organic solvent Oil-6 0.050 g.

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion G Silver amount 0.20 g Emulsion H Silver amount 0.35 g Emulsion I Silver amount 0.30 g Gelatin 1.50 g Coupler C-7 0.13 g Coupler C-8 0.070 g Coupler C-12 0.010 g Compound Cpd-B 0.030 g Compound Cpd-D 5.0 mg Compound Cpd-E 5.0 mg Compound Cpd-G 2.5 mg Compound Cpd-F 0.010 g Compound Cpd-K 2.0 mg Ultraviolet absorber U-6 5.0 mg High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-6 0.030 g High boiling organic solvent Oil-4 8.0 mg Additive P-1 5.0 mg.

Tenth Layer: Medium-Sensitive Green-Sensitive Emulsion Layer Emulsion I Silver content 0.20 g Emulsion J Silver content 0.30 g Internally covered silver bromide emulsion (cubic, sphere-equivalent mean particle size 0.11 μm) Silver content 5.0 mg Gelatin 0.70 g Coupler C-4 0.40 g Coupler C-8 0.020 g Coupler C-12 0.010 g Compound Cpd-B 0.030 g Compound Cpd-F 0.010 g Compound Cpd-G 2.0 mg High boiling organic solvent Oil-2 0.050 g High Boiling point organic solvent Oil-5 6.0 mg.

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion K Silver amount 0.65 g Gelatin 0.70 g Coupler C-3 5.0 mg Coupler C-4 0.50 g Coupler C-8 0.010 g Compound Cpd-B 0.050 g Compound Cpd-F 0.010 g Compound Cpd-K 2.0 mg High boiling organic solvent Oil-2 0.050 g 12th layer: Intermediate layer Gelatin 0.50 g Compound Cpd-M 0.05 g High boiling organic solvent Oil-3 0.025 g High boiling organic solvent Oil-6 0.025 g Dye D-6 5.0 mg.

13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.030 g Gelatin 1.00 g Compound Cpd-C 0.010 g Compound Cpd-M 0.030 g High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-6 0.030 g Microcrystalline solid dispersion of dye E-2 0.030 g 14th layer: intermediate layer gelatin 0.40 g compound Cpd-Q 0.20 g 15th layer: low-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.30 g Emulsion M silver amount 0.20 g gelatin 0.80 g Coupler C-5 0.020 g Coupler C-6 5.0 mg Coupler C-10 0.30 g Compound Cpd-B 0.10 g Compound Cpd-I 8.0 mg Compound Cpd-K 1.0 mg Compound Cpd-M 0.010 g Ultraviolet absorber U-6 0.010 g High boiling organic solvent Oil-2 0.010 g.

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.20 g Emulsion O Silver amount 0.20 g Silver bromide emulsion with a cover (cube, sphere equivalent average particle diameter 0.11 μm) Silver amount 3.0 mg Gelatin 0.90 g Coupler C-5 0.020 g Coupler C-6 0.010 g Coupler C-10 0.25 g Compound Cpd-B 0.10 g Compound Cpd-N 2.0 mg High boiling organic solvent Oil-2 0.010 g 17th layer: High sensitivity blue Sensitive emulsion layer Emulsion O Silver content 0.20 g Emulsion P silver content 0.25 g Gelatin 2.00 g Coupler C-3 5.0 mg Coupler C-5 0.10 g Coupler C-6 0.020 g Coupler C-10 1.00 g High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-6 0.020 g Ultraviolet absorber U-6 0.10 g Compound Cpd-B 0.20 g Compound Cpd-N 5.0 mg.

Eighteenth layer: First protective layer Gelatin 0.80 g UV absorber U-1 0.15 g UV absorber U-2 0.050 g UV absorber U-5 0.20 g Compound Cpd-O 5.0 mg Compound Cpd-A 0.030 g Compound Cpd-H 0.20 g Dye D-1 8.0 mg Dye D-2 0.010 g Dye D-3 0.010 g High boiling organic solvent Oil-3 0.10 g 19th layer: 2nd protective layer Colloidal silver Silver amount 3.0 mg Fine particle odor Silver halide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.10 g Gelatin 0.80 g Ultraviolet absorber U-1 0.010 g Ultraviolet absorber U-6 0.010 g High boiling organic solvent Oil-3 0.010 g.

20th layer: 3rd protective layer Gelatin 1.20 g Polymethyl methacrylate (average particle size 1.5 μm) 0.10 g Copolymer of methyl methacrylate and methacrylic acid 6: 4 (average particle size 1.5 μm) 0.15 g Silicone oil SO-1 0.20 g Surfactant W-1 3.0 mg Surfactant W-2 8.0 mg Surfactant W-3 0.040 g Surfactant W-7 0.015 g In addition, the above composition was added to all emulsion layers. Additive F-
1-F-8 were added. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer.

Further, phenol, 1,1 as antiseptic and antifungal agent
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added.

[0122]

[Table 2]

[0123]

[Table 3]

[0124]

[Table 4]

[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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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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Preparation of Dispersion of Organic Solid Disperse Dye (Preparation of Dispersion of Dye E-1) A wet cake of dye E-1 (270 g as a net amount of E-1) was prepared using BASF P.
100 g of luronic F88 (an ethylene oxide-propylene oxide block copolymer) and water were added thereto, followed by stirring to obtain 4000 g. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the slurry was passed through the slurry at a peripheral speed of about 10 m / sec and a discharge rate of 0.51 / min for 2 hours. Crushed. The beads were removed by filtration, and water was added to the dye to give a dye concentration of 3.
After dilution to 10%, the mixture was heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained fine dye particles is 0.30 μm.
And the breadth of the particle size distribution (particle size standard deviation × 100 / average particle size) was 20%.

(Preparation of Solid Dispersion of Dye E-2)
270 g of water and W-4 were added to 1400 g of a wet cake of E-2 containing 0% by mass and stirred to obtain a slurry having an E-2 concentration of 40% by mass. Next, a crusher, IMEX Co., Ltd.
Ultra Viscomil (UVM-2) with an average particle size of 0.5
mm of zirconia beads, the peripheral speed is about 10 m / sec through the slurry, and the discharge rate is 0.5 L / m.
The mixture was ground for 8 hours to obtain a solid fine particle dispersion of E-2. This was diluted to 20% by mass with ion-exchanged water to obtain a solid fine particle dispersion. Average particle size is 0.15 μm
Met.

Next, the couplers C-4, 7, 8, 12 and the high-boiling organic solvents in the ninth, tenth, and eleventh layers of the sample 101 were replaced as shown in Table 5 to obtain samples 201 to 208,
01 to 308, 401 to 408, and 501 to 508 were created. For replacement, the coupler, the high-boiling organic solvent and the oil-soluble component contained in the same layer are dissolved in ethyl acetate four times the total weight of these components, and the surfactant W is added thereto.
-3, W-5 and an aqueous gelatin solution were added, and emulsified and dispersed.

[0146]

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[0147]

[Table 5]

(Supplement) In Samples 201 to 208, tricresyl phosphate was added in an amount of 0.5 times by mass relative to Comparative Coupler A. In Samples 301 to 308, tricresyl phosphate was added in a 0.5-fold amount by mass relative to coupler (7).
In Samples 401 to 408, tricresyl phosphate was added in an amount of 0.1 times the mass of coupler (7). Sample 501
-508, a high boiling organic solvent O for coupler (14)
il-6 was added in a 0.2-fold amount by mass ratio. In this embodiment, the following developing process (developing process A) was performed.

Processing Step Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 L 2200 mL / m ² First water wash 2 minutes 38 ° C. 4 L 7500 mL / m ² Reversal 2 minutes 38 ° C. 4 L 1100 mL / m m ² color development 6 minutes 38 ° C. 12 L 2200 mL / m ² pre-bleaching 2 minutes 38 ° C. 4 L 1100 mL / m ² bleaching 6 minutes 38 ° C. 12 L 220 mL / m ² fixed 4 minutes 38 ° C. 8 L 1100 mL / m ² Second water washing 4 minutes 38 ° C. 8 L 7500 mL / m ² Final rinse 1 minute 25 ° C. 2 L 1100 mL / m ² The composition of each treatment liquid was as follows.

[First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid · pentasodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Potassium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 mL 1000 mL pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversal solution] [Tank solution] [Replenishment solution] Nitrilo-N, N, N-trimethylenephosphonic acid tank solution • Same as 3.0 g of pentasodium salt 1.0 g of stannous chloride / dihydrate p-amino acid Phenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 mL Water was added to 1000 mL pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 dehydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazinic acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Add water 1000 mL 1000 mL pH 11.80 12.00 Adjust pH with sulfuric acid or potassium hydroxide did.

[Pre-bleaching] [Tank liquid] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g Sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g sodium formaldehyde sodium bisulfite adduct 30 g 35 g Water was added and 1000 mL 1000 mL pH 6.30 6.10 pH was adjusted with acetic acid or sodium hydroxide. [Bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 mL 1000 mL pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate 80 g Same as the tank solution Sodium sulfite 5.0 g The same as the tank solution Sodium bisulfite 5.0 g The same water was added to the tank solution and the same as the 1000 mL tank solution pH 6.60 pH was adjusted with acetic acid or aqueous ammonia. [Stabilizing solution] [Tank solution] [Replenisher] 1,2-benzisothiazolin-3-one 0.02 g 0.03 g polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g 0.3 g polymaleic acid (weight) (Average molecular weight 2,000) 0.1 g 0.15 g Water is added to 1000 mL 1000 mL pH 7.0 7.0 In the above development processing step, each bath is continuously circulated and stirred, and the bottom surface of each tank has a diameter of 0.1 mL. A foaming tube having 3 mm small holes spaced at 1 cm intervals was arranged, and nitrogen gas was continuously bubbled and stirred.

(Evaluation of Sample) (Evaluation of Storage) Samples 101 to 508 were 10.5 cm wide.
Cut into 12.5 cm long rectangles, stack 10 sheets in the same direction in a room conditioned at 25 ° C and 55%, put in a light-shielding paper bag laminated with polyethylene on both sides of the paper, and remove the inside. After having noticed, the opening was heat-sealed and sealed. Two sets of the samples processed as described above are prepared, and one set includes four sets.
Store for 3 months in an atmosphere of 0 ° C and 55%, and keep another set in a freezer at -20 ° C for the same period. After a lapse of time, remove the fifth film from the top of the stacked samples, and continuously Exposure with white light having a color temperature of 4800 degrees through a wedge whose density is changing (exposure time 1/100
Sec), the above development was performed, and the density was measured. (Maximum magenta concentration when frozen and stored) − (Maximum magenta concentration when stored at 40 ° C. and 55%) is calculated by ΔDG
(A).

[0156] Samples 101 to 508 were processed into strips, and stored for 3 months in an atmosphere of 40 ° C and 55% without sealing as described above, and compared with the case of being stored frozen for the same period. Take the maximum magenta density as the characteristic value,
The difference between the sample stored frozen and the sample stored at high temperature was calculated in the same manner and defined as ΔDG (B).

Further, the value of ΔDG (B) was subtracted from the value of ΔDG (A), and the degree of deterioration of storage stability due to sealing was calculated. For example, when ΔDG (A) −ΔDG (B) is −0.15, it indicates that the reduction range of the maximum magenta density is deteriorated by the density of 0.15 by sealing. (Evaluation of unevenness) Samples 101 to 508 were cut into a rectangle having a width of 10.5 cm and a length of 12.5 cm, and a neutral gray density of 0.
Exposure was performed uniformly under exposure conditions giving 6 to 0.7, followed by development processing A. After processing, the entire surface of the sample is 1 cm
The density was measured at intervals, and the difference in the magenta density between the low magenta density area and the high magenta density area was measured (5 points were selected from the lower and higher areas, respectively, and the average of the 5 points was taken). The results are shown in Table 6.

[0158]

[Table 6]

In the comparison of Samples 101 to 108 in Table 6, when the substrate has an undercoat layer containing acetone, when the undercoat is applied to both sides of the cellulose triacetate support, or when the thickness of the support is thick, the sealed form is used. This indicates that there was a problem that storage stability deteriorated.
On the other hand, when the coupler of the present invention is replaced with the comparative coupler A and the coupler of the present invention, deterioration of storage stability due to this sealed form is almost not observed. However, in the case of the comparative coupler A, the magenta color unevenness was worse than that of the samples 101 to 108. In contrast, the sample of the present invention in which the coupler of the present invention is used in combination with an undercoat using acetone is preferable because the degree of unevenness is remarkably improved.

That is, by using the combination of the present invention, the problem (unevenness) when using a pyrazolotriazole coupler and the problem of deterioration in storage stability due to undercoating were simultaneously solved.

In the present invention, samples 301 to 308
Sample 4 in which the amount of tricresyl phosphate added was reduced
It can be seen that 01 to 408 gives more preferable results.

(Example-2) The base D was exposed to dry air at 100 ° C after the undercoating for a longer time to obtain a base I. The base I was coated with a light-sensitive emulsion layer in the same manner as in Example 1, and samples 109, 209, 309, 409, and 5 were coated.
09 was created. In the sample using Base D, the residual amount of acetone was 0.30% by mass percent, and in the sample using Base I, the residual amount of acetone was 0.03%. When the same shelf life was evaluated as in Example-1,
Also in sample 109, the difference between when stored in a sealed form and when stored in an open system was reduced.

Next, samples 104, 204, 304 and 40
4,504 and samples 109,209,309,40
9,509 is cut into a width of 8 cm and a length of 1.5 m.
5 cm was bent and fixed, and a 100 g weight was attached to the other end, lifted to an appropriate height, and dropped to evaluate the ease of film breakage.

In the sample using the result base I, the base D
The film was broken from a place where the height for lifting the weight was lower than that of the sample using the film.

As described above, due to the requirement for the brittleness of the base, there is a limit in enhancing the drying after the undercoating, and it can be said that the improvement of the storage stability by the coupler of the present invention is significant.

(Embodiment 3) First of Samples 101 to 508
Samples 2101 to 2508 were made in the same manner except that the two layers and the fourteenth layer were removed. When the same evaluation as in Example 1 was performed on the samples 2101 to 2508, the present invention gave preferable results.

(Example-4) Fourth sample Nos. 101-508
Samples 3101 to 3508 were made in the same manner except that the configurations of the layers, the fifth layer, and the sixth layer were changed as follows.

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.10 g Emulsion B silver amount 0.15 g Emulsion C silver amount 0.15 g gelatin 0.70 g Coupler CC-1 0.10 g Coupler C-6 6.0 mg Coupler C-9 5.0 mg UV absorber U-3 0.010 g Compound Cpd-I 0.020 g Compound Cpd-D 3.0 mg Compound Cpd-J 2.0 mg High boiling organic solvent Oil-A 0.025 g Additive P-1 0.020 g Fifth layer: Medium sensitivity Red-sensitive emulsion layer Emulsion C Silver content 0.15 g Emulsion D silver content 0.15 g Gelatin 0.70 g Coupler CC-1 0.15 g Coupler C-6 7.0 mg Compound Cpd-D 4.0 mg Ultraviolet absorber U-3 0.010 g High boiling organic solvent Oil -A 0.035 g Additive P-1 0.020 g Sixth layer: high-sensitivity red-sensitive emulsion layer Emulsion E silver amount 0.15 g emulsion F silver amount 0.15 g gelatin 1.50 g Coupler CC-1 0.60 g Coupler C-6 0.010 g Ultraviolet absorption Agent U-1 0.010g Ultraviolet absorber U-2 0.010 g High boiling organic solvent Oil-6 0.050 g High boiling organic solvent Oil-A 0.050 g Compound Cpd-D 5.0 mg Compound Cpd-K 1.0 mg Compound Cpd-L 1.0 mg Compound Cpd-F 0.030 g Additive P-1 0.10g

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When the samples 3101 to 3508 were evaluated in the same manner as in Example 1, the sample of the present invention gave a preferable result.

(Example-5) Sample 1 using base D
04, 204, 304, 404, 504 and 310
4, 3204, 3304, 3404, 3504 to width 6
Example 1-Cut into 1 mm and 830 mm in length, wound in a brownie film form together with light-shielding paper, sealed in a bag of a material laminated with aluminum foil and polyethylene,
The same evaluation as in Example 1 was performed. As a result, the combination with the coupler of the present invention gave excellent results with excellent storage stability.

(Example-6) Samples 3504, 3506,
Three types of photosensitive materials having different supports were prepared in the same manner except that the coupler (14) of 3508 and the high boiling point organic solvent were changed as shown in Table 7.

When each sample was evaluated in the same manner as in Example 1, the present invention gave preferable results.

[0173]

[Table 7]

(Example-7) Samples 3504, 3506,
Three kinds of photosensitive materials having different supports were prepared in the same manner except that the coupler (14) of 3508 and the high boiling point organic solvent were changed as shown in Table 8.

When each sample was evaluated in the same manner as in Example 1, the present invention gave a preferable result.

[0176]

[Table 8]

[0177]

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Claims (3)

[Claims] 1. A silver halide color photographic material having at least one blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer on a transparent support, wherein the transparent support has a structure other than alcohol on both sides. Of a water-miscible organic solvent,
A plastic support subbed with an undercoating liquid containing a substituted phenol having a molecular weight of 200 or less and at least one compound selected from acetic acid in which at least one hydrogen atom on a methyl group is substituted with a halogen atom, and One photosensitive emulsion layer has the following general formula (MC-
A silver halide color photographic light-sensitive material containing a coupler represented by I). Embedded image In the formula, R ₁ represents a hydrogen atom or a substituent, _one of G ₁ and G ₂ represents a carbon atom, and the other represents a nitrogen atom, and R ₂ substitutes a carbon atom of G ₁ and G ₂ represents a substituent, _{R 1} and _{R 2} further may have a substituent group, also via the _{R 1} or _{R 2} more formula (MC-
The coupler represented by I) may form a multimer by bonding, or may bond to the polymer chain via R ₁ or R ₂ . Further, a plurality of couplers represented by the general formula (MC-I) may be bonded via R ₁ or R ₂ to form a multimer. 2. A silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, one green-sensitive emulsion layer and one red-sensitive emulsion layer on a transparent support, wherein the transparent support has at least one side. Is an undercoating solution containing a water-miscible organic solvent other than alcohol, a substituted phenol having a molecular weight of 200 or less, and at least one compound selected from acetic acid in which at least one hydrogen atom on a methyl group is substituted with a halogen atom. Thickness 150μm
A plastic support having a thickness of at least 2000 μm and at least one photosensitive emulsion layer having the following general formula (MC-
A silver halide color photographic light-sensitive material containing a coupler represented by I). Embedded image In the formula, R ₁ represents a hydrogen atom or a substituent, _one of G ₁ and G ₂ represents a carbon atom, and the other represents a nitrogen atom, and R ₂ substitutes a carbon atom of G ₁ and G ₂ represents a substituent, _{R 1} and _{R 2} further may have a substituent group, also via the _{R 1} or _{R 2} more formula (MC-
The coupler represented by I) may form a multimer by bonding, or may bond to the polymer chain via R ₁ or R ₂ . 3. A silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer on a transparent support, wherein the acetone is used for the light-sensitive material including the support. The content is 0.0
A silver halide color photographic light-sensitive material comprising 5% or more and 3.0% or less, and wherein at least one photosensitive emulsion layer contains a coupler represented by the following formula (MC-I). Embedded image In the formula, R ₁ represents a hydrogen atom or a substituent, _one of G ₁ and G ₂ represents a carbon atom, and the other represents a nitrogen atom, and R ₂ substitutes a carbon atom of G ₁ and G ₂ represents a substituent, _{R 1} and _{R 2} further may have a substituent group, also via the _{R 1} or _{R 2} more formula (MC-
The coupler represented by I) may form a multimer by bonding, or may bond to the polymer chain via R ₁ or R ₂ .