JPH09197636A - Photographic material for halogenated silver color photograph - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photographic material, which can maintain the low fog and while of which sensitivity can be improved and which has the excellent color reproducibility and the excellent grain condition and of which the shelf life with aging for a long time is improved, by including two kinds of specified compound in a photographic emulsion layer. SOLUTION: A support has at least one layer of photosensitive emulsion layer and one layer of non-photosensitive colloid layer. One layer of the photosensitive emulsion layer includes one kind of the compound expressed with a formula I and one kind of the compound expressed with a formula II. In the formula I, Z means -COOR<11> , -CONR<11> R<11> or the like, and R<11> , R<12> respectively means hydrogen atom and alkyl group or the like. In the formula II, L1 , L2 respectively means methylene chain, and A1 , A2 respectively means -CO2 -, -SO2 - or the like. R<21> , R<22> respectively means hydrogen atom, alkyl group or the like, and R<23> means a substituent group, x1 , x2 , y1 , y2 , respectively means a numeric among 0-20. With this structure, sensitivity can be improved, maintaining the low fog.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material), and more specifically, it achieves high sensitivity with low fog and is excellent in color reproducibility and graininess. , A silver halide color photographic light-sensitive material having improved storability.

[0002]

2. Description of the Related Art Conventionally, conventional silver halide color photographic light-sensitive materials are exposed to light and then subjected to color development processing to react with an oxidation product of a para-phenylenediamine color developing agent and a coupler to form a dye, thereby forming a color image. Is formed.

Generally, in this photographic method, color reproduction by a subtractive color method is used to form yellow, magenta and cyan color images.

For example, as a magenta dye forming coupler (magenta coupler), pyrazolone type, pyrazolinobenzimidazole type, indanone type and the like are known, and various 5-pyrazolone derivatives have been widely used. .

Examples of the substituent at the 3-position of the 5-pyrazolone ring of the 5-pyrazolone derivative include an alkyl group, an aryl group, an alkoxyl group described in US Pat. No. 2,439,098, and 2,369,489. Same as 2,600,78
No. 8, etc., acylamino groups, 3,558,319
The ureido group described in No. is used. However, the above-mentioned couplers have low coupling activity with the oxidized product of the developing agent and it is difficult to obtain a high density magenta color image, and the secondary absorption in the blue light region of the magenta color image obtained by color development is large. There were drawbacks such as poor cutting on the long wave side of absorption.

In addition, 3-described in US Pat. Nos. 2,311,081, 3,677,764, 3,684,514, British Patents 956,261, 1,173,513, etc. The anilino-5-pyrazolone type coupler has advantages such as high coupling activity, high color development, and small unnecessary absorption in the red light region. However, these conventionally known 3-anilino-5-pyrazolone type couplers have a main absorption in a relatively short wave, and therefore when used in a color negative silver halide photographic light sensitive material, the print color reproducibility is deteriorated.

Various investigations have been made for the purpose of improving the above-mentioned drawbacks. For example, JP-A-52-8002.
No. 7 has 1-pentahalogenophenyl-3-anilino-
5-Pyrazolone couplers have been proposed. The coupler has high coupling activity, high color development, and good spectral characteristics, but it has a drawback that the color development is deteriorated by storage in the presence of formalin gas. Further, it cannot be said that the demand for high sensitivity of the light-sensitive material is increasing year by year.

On the other hand, as a result of efforts to improve the sensitivity of couplers and silver halide emulsions in response to the demand for higher sensitivity over the years, it is also true that the increase in fog cannot be ignored at the same time as the higher sensitivity. Is.

As a technique for reducing fog, a technique of adding an antifoggant typified by mercaptoazoles is well known, but if a large amount of these antifoggants are added, the fog is reduced, but the sensitivity is low. The decrease is large and the amount used is limited.

Other than the above, a fog is reduced by adding a small amount of a developing agent oxidant represented by polyhydroxybenzenes (eg, hydroquinone derivative, pyrogallol derivative, etc.) and a compound for cross-oxidizing to the photosensitive layer. The technology to do is done.

[0011] The hydroquinone derivative has a high cross-oxidation rate, but its storage potential is low because of its low oxidation potential.
Although it is used in the non-photosensitive layer for the purpose of preventing color turbidity, it is rarely contained in the photosensitive layer.

Pyrogallol derivatives (eg, gallic acid ester) have been used for the photosensitive layer because they have a high oxidation potential but a high cross-oxidation rate and are stable. However, with the increase in the speed of couplers and silver halide emulsions, the effect of reducing fog has not always been sufficient.

Further, when the speed of couplers and silver halide emulsions is increased, the color-sensitive layer containing them is less affected by the interlayer effect from other photosensitive layers, and the color reproducibility is deteriorated, or There was a problem such as deterioration of graininess.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material capable of achieving high sensitivity while maintaining low fog, and further, color reproducibility and graininess. It is an object of the present invention to provide a silver halide color photographic light-sensitive material which is excellent in storage stability and excellent in long-term storage stability of the light-sensitive material.

[0015]

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

(1). A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer and at least one non-light-sensitive colloid layer on a support, wherein at least one of the light-sensitive emulsion layers is represented by the following general formula [I]. Silver halide color photographic light-sensitive material containing at least one compound represented by the following general formula [II].

[0017]

Embedded image

[In the formula, Z is -COOR ¹¹ or -CONR ^{11
_{R 12, -SO 2 NR 11 R}} 12, -SO 2 R 11 or -COR
Represents ^11, R ^11, R ¹² are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. ]

[0019]

Embedded image

[In the formula, L ₁ and L ₂ each represent a methylene chain, and A ₁ and A ₂ represent —CO ₂ —, —SO ₂ —, and —C, respectively.
ONR ^24- , -NR ²⁴ CO-, -SO ₂ NR ^24- , -N
_{^{R 24 SO 2 -, - O}} -, - NR 24 CO 2 - or -NR ²⁴
Represents CONR ²⁵ −. R ²¹ , R ²² , R ²⁴ and R ²⁵ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ²³ represents a substituent. x ₁ , x ₂ , y ₁ , and y ₂ each represent an integer of 0 to 20. (2). The halogenation according to (1), wherein the photosensitive emulsion layer containing the compound represented by the general formula [I] and the compound represented by the general formula [II] is a green photosensitive emulsion layer. Silver color photographic light-sensitive material.

(3). The silver halide color photographic light-sensitive material according to (2), wherein the green light-sensitive emulsion layer contains at least one compound represented by the following general formula [III].

[0022]

[Chemical 6]

[Wherein R ³¹ is a hydrogen atom or aromatic 1
Represents a group capable of splitting off upon reaction with an oxidation product of a primary amine color developing agent. R ³² represents an aryl group. R ³³ represents a substituent, and n ₃ represents an integer of 1 to 5. R when n ₃ is 2 or more
³³ may be the same or different. Hereinafter, the present invention will be described in detail.

First, the general formula [I] will be described.

In the above general formula [I], Z is --COO.
R ¹¹ , —CONR ¹¹ R ¹² , —SO ₂ NR ¹¹ R ¹² , —SO ₂
R ¹¹ or —COR ¹¹ is represented, and R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Z is preferably -C
OOR ¹¹ —CONR ¹¹ R ¹² or —SO ₂ NR ¹¹ R ¹² is preferred, but —COOR ¹¹ or —CONR ¹¹ R is more preferred.
It is ¹² .

In the general formula [I], examples of the alkyl group represented by R ¹¹ and R ¹² include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl,
Each group such as cyclopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl and the like can be mentioned. These alkyl groups further include halogen atoms (eg chlorine, bromine, fluorine etc.), alkoxy groups (eg methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy etc.), aryloxy groups (eg phenoxy). , Naphthyloxy etc.), aryl groups (eg phenyl, naphthyl etc.), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl etc.), aryloxycarbonyl groups (eg phenoxycarbonyl, naphthyloxycarbonyl etc.) ), Alkenyl groups (eg vinyl, allyl etc.), heterocyclic groups (eg 2
-Pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, pyrimidyl, pyrazolyl, furyl etc.), alkynyl group (eg propargyl), amino group (eg amino, N, N-dimethylamino, anilino etc.), hydroxyl It may be substituted with a group, a cyano group, a sulfo group, a carboxyl group, a sulfonamide group (for example, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.).

Examples of the alkenyl group represented by R ¹¹ and R ¹² include vinyl and allyl.

Examples of the alkynyl group represented by R ¹¹ and R ¹² include a propargyl group.

Examples of the aryl group represented by R ¹¹ and R ¹² include phenyl and naphthyl.

The heterocyclic group represented by R ¹¹ and R ¹² is
For example, pyridyl group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, etc.), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, cenyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group,
Examples thereof include a selenazolyl group, a sulforanyl group, a piperidinyl group, a pyrazolyl group, and a tetrazolyl group.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group may be substituted with the same groups as the alkyl group represented by R ¹¹ and R ¹² and the groups shown as the substituents of the alkyl group. it can.

Specific examples of the compound represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0033]

Embedded image

[0034]

Embedded image

Next, the general formula [II] will be described.

In the above general formula [II], R ²¹ , R ²² ,
Examples of the alkyl group represented by R ²⁴ and R ²⁵ include groups such as methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc. Is mentioned. These alkyl groups further include halogen atoms (eg chlorine, bromine, fluorine etc.), alkoxy groups (eg methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy etc.), aryloxy groups (eg phenoxy). , Naphthyloxy, etc.),
Aryl group (eg phenyl, naphthyl etc.), alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl etc.) aryloxycarbonyl group (eg phenoxycarbonyl, naphthyloxycarbonyl etc.),
Alkenyl groups (eg vinyl, allyl etc.), heterocyclic groups (eg 2-pyridyl, 3-pyridyl, 4-pyridyl,
Morpholyl, piperidyl, piperazyl, pyrimidyl, pyrazolyl, furyl etc.), alkynyl group (eg propargyl), amino group (eg amino, N, N-dimethylamino, anilino etc.), hydroxyl group, cyano group, sulfo group, carboxyl group, It may be substituted with a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) and the like.

Examples of the alkenyl group represented by R ²¹ , R ²² , R ²⁴ and R ²⁵ include vinyl and allyl.

Examples of the alkynyl group represented by R ²¹ , R ²² , R ²⁴ and R ²⁵ include a propargyl group.

Examples of the aryl group represented by R ²¹ , R ²² , R ²⁴ and R ²⁵ include phenyl and naphthyl.

The heterocyclic group represented by R ²¹ , R ²² , R ²⁴ and R ²⁵ is, for example, a pyridyl group (eg 2-pyridyl,
3-pyridyl, 4-pyridyl, etc.), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, thienyl group,
Examples thereof include a pyrrolyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulforanyl group, a piperidinyl group, a pyrazolyl group and a tetrazolyl group.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group are all the same as the alkyl group represented by R ²¹ , R ²² , R ²⁴ and R ²⁵ and the groups shown as the substituents of the alkyl group. It can be replaced by a group.

The substituent represented by R ²³ may be any group capable of substituting on the benzene ring. For example, an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, Pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg propargyl group etc.), aryl group (eg phenyl group) , Naphthyl group, etc.), heterocyclic group (eg, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group , Tetrazolyl group, etc.), halogen atom (eg chlorine atom, bromine) Child, iodine atom, fluorine atom, etc.), alkoxyl group (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group, etc.) , Aryloxy groups (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl groups (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryl Oxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group, butylsulfonylamino group, hexyls) Honiruamino group, cyclohexyl sulfonylamino group, octyl sulfonylamino group, dodecyl sulfonylamino group,
Phenylsulfonylamino group etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group,
Dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group) Group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc., acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl) Group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (for example, aminocarbonyl group,
Methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group Group, 2-pyridylaminocarbonyl group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group,
Methylcarbonyl-N-methylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group,
Naphthylcarbonylamino group, 4-pyridylcarbonylamino group, etc.), sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group,
Naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group,
Dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group Etc. may be substituted. These groups may be further substituted by the above substituents.

Specific examples of the compound represented by the general formula [II] are shown below, but the invention is not limited thereto.

[0044]

Embedded image

[0045]

Embedded image

The polyhydroxybenzene compounds represented by the general formulas [I] and [II] according to the present invention are silver halide 1
1 × 10 ^{−5 to} 0.1 mol per mol, preferably 1 × 1
It is desirable to add 0 ^-4 to 1 × 10 ^-2 mol. These polyhydroxybenzene compounds must be added to the photosensitive layer in order to achieve the object of the present invention, but may be added to the non-photosensitive layer. In order to introduce the polyhydroxybenzene compound according to the present invention into a light-sensitive material, it may be added by dispersing it by various known dispersion methods described later. For example, known high boiling points such as dibutyl phthalate and tricresyl phosphate can be used. A mixture of a solvent and a low boiling point solvent such as butyl acetate or ethyl acetate, or a solvent containing only a low boiling point solvent, alone or in combination with the compound represented by the general formula [I] or [II], or with a coupler. After melting together,
It is possible to employ a method in which it is mixed with an aqueous gelatin solution containing a surfactant, then emulsified and dispersed using a high speed rotary mixer, a colloid mill or an ultrasonic disperser, and directly added to the silver halide emulsion. Alternatively, the above emulsion dispersion may be set, shredded, washed with water and then added to the silver halide emulsion.

When the polyhydroxybenzene compounds represented by the general formulas [I] and [II] according to the present invention are used in the same color-sensitive layer, the color-sensitive layers are two or more photosensitive layers having different sensitivities. And a compound containing the compound represented by the general formula [II] in the highest sensitivity layer and the compound represented by the general formula [I] in the same color-sensitive layer other than the highest sensitivity layer, It is preferable for achieving the object of the invention more effectively.

Next, the general formula [III] will be described. In the general formula [III], R ³¹ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. R ³¹ is preferably a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent, and more preferably an arylthio group, from the viewpoints of saving silver and improving resistance to harmful gases.

R ³² represents an aryl group, for example, phenyl group, pentachlorophenyl group, 2,4,6-trichlorophenyl group, 2,5-dichlorophenyl group, 2,4-
Dichlorophenyl group, 2,6-dichloro-4-methylphenyl group, 2,6-dichloro-4-methanesulfonylphenyl group, 2,6-dichloro-4-cyanophenyl group,
2,6-dichloro-4-morpholinosulfonylphenyl group, 2,4-dichloro-6-methoxyphenyl group, 2,
4-dichloro-6-methylphenyl group and the like can be mentioned.

When the compound of the present invention is used in a color negative film, R ³² is a pentachlorophenyl group and 2,6-in terms of the spectral absorption wavelength of a color forming dye obtained by reacting with an oxidized product of a color developing agent. It is preferably a dichloro-4-methanesulfonylphenyl group, a 2,6-dichloro-4-cyanophenyl group or a 2,6-dichloro-4-morpholinosulfonylphenyl group.

R ³³ represents a substituent, for example, chlorine, bromine,
Halogen atoms such as fluorine, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy group, 2,6
-Benzoylamino group such as dichlorobenzoylamino group, 2,6-dimethoxybenzoylamino group, alkylsulfonyl group such as hexadecylsulfonyl, acylamino group such as acetylamino group, cyano group, nitro group, carboxyl group, amino group, Examples thereof include an alkoxycarbonyl group such as an ethoxycarbonyl group, an alkyl group such as a methyl group, an ethyl group, and an isopropyl group, but needless to say, a monovalent substituent other than the above may be used.

From the viewpoint of color developability and spectral absorption wavelength, it is preferable that at least one atom or group of R ³³ is a halogen atom or an alkoxy group.

Specific examples of the compound represented by the general formula [III] of the present invention are shown below, but the present invention is not limited thereto.

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

The compound represented by the general formula [III] (hereinafter, also referred to as magenta coupler represented by the general formula [III]) according to the present invention may be added to the photosensitive layer and is non-photosensitive. It may be added to the layer. In order to introduce the magenta coupler represented by the general formula [III] according to the present invention into a silver halide color photographic light-sensitive material, it can be added by dispersing it by various known dispersion methods described below, like the polyhydroxybenzene compound. Good, for example, known dibutyl phthalate,
A compound represented by the general formula [III] was dissolved alone or in combination in a mixed solution of a high boiling point solvent such as tricresyl phosphate and a low boiling point solvent such as butyl acetate and ethyl acetate, or a low boiling point solvent alone. After that, a method of mixing with an aqueous gelatin solution containing a surfactant, then emulsifying and dispersing using a high-speed rotary mixer, colloid mill or ultrasonic disperser, and directly adding to the silver halide emulsion can be adopted. Alternatively, the above emulsified dispersion may be set, shredded, washed with water, and then added to the silver halide emulsion.

The polyhydroxybenzene compounds represented by the general formulas [I] and [II] and the magenta coupler represented by the general formula [III] may be added to the same layer or different layers. The color sensitivities may be the same or different, but they are preferably added to the same color sensitive layer, and more preferably added to the same layer. When they are added to the same layer, they may be separately dispersed and added, or may be simultaneously mixed and dispersed and added.

When the compound represented by the general formula [III] is used in the present invention, by further using at least one compound represented by the following general formula [IV],
The object of the present invention can be achieved more efficiently.

[0065]

Embedded image

In the formula, R ⁴¹ and R ⁴² represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, and R ⁴³ , R ⁴⁴ and R ⁴⁵ represent a substituent.

R ⁴¹ and R ⁴² , R ⁴³ and R ⁴⁴ , and R ⁴⁴ and R ⁴⁵ may form a ring, respectively.

The groups represented by R ⁴¹ and R ⁴² in the general formula [IV] are, respectively, a hydrogen atom, an alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-
Octyl group, n-dodecyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg,
Propargyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), heterocyclic group (eg pyridyl group,
Thiazolyl group, oxazolyl group, imidazolyl group, furyl group, prolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.). These groups may themselves have a substituent.

In the general formula [IV], the substituent represented by R ⁴³ , R ⁴⁴ and R ⁴⁵ is an alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, t
tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-dodecyl group, etc., alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, , Propargyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, prolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl) Group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc.), halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyl group) Oxy group, n-pentyloxy group, cyclopentyloxy group, n Hexyloxy group, cyclohexyloxy group, n-octyloxy group, n-dodecyloxy group, etc., aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxy Carbonyl group, n-butyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyloxycarbonyl group, etc., aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (eg, , Methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group, n-hexylsulfonylamino group, cyclohexylsulfonylamino group, n-octylsulfonylamino group, n-dodecylsulfonylamino , Etc. phenylsulfonylamino group), a sulfamoyl group (e.g., aminosulfonyl group, methylaminosulfonyl group,
Dimethylaminosulfonyl group, n-butylaminosulfonyl group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylaminosulfonyl group, n-dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2- Pyridylaminosulfonyl group), ureido group (for example,
Methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, n-octylureido group, n-dodecylureido group, phenylureido group,
A naphthylureido group, a 2-pyridylaminoureido group, etc., an acyl group (for example, an acetyl group, an ethylcarbonyl group, a propylcarbonyl group, an n-pentylcarbonyl group, a cyclohexylcarbonyl group, an n-octylcarbonyl group, a 2-ethylhexylcarbonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc., carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, n-pentylaminocarbonyl group) , A cyclohexylaminocarbonyl group, an n-dodecylaminocarbonyl group, a phenylaminocarbonyl group, a naphthylaminocarbonyl group, a 2-pyridylaminocarbonyl group, etc., an amide group (for example, Acetamide group, an ethylcarbonyl group, a propyl carbonyl amino group, n- pentyl carbonylamino group, a cyclohexylcarbonyl group, a 2-ethylhexyl carbonylamino radical, n
-Octylcarbonylamino group, dodecylcarbonylamino group, benzoylamino group, naphthylcarbonylamino group, etc., sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group) , Dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group,
Dimethylamino group, n-butylamino group, cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, carboxyl group, hydroxyl Group, sulfo group, hydrogen atom and the like.
These groups can be substituted by the alkyl groups represented by R ⁴¹ and R ⁴² , and the same groups as the substituents of the alkyl group.

Examples of the ring formed by R ⁴¹ and R ⁴² include a piperidine ring, a pyrrolidine ring, a morpholine ring, a pyrrole ring, a piperazine ring and a thiomorpholine ring. The ring which can be formed by R ⁴³ and R ⁴⁴ and R ⁴⁴ and R ⁴⁵ is
For example, a benzene ring, a thiophene ring, a furan ring, a pyrrole ring and the like can be mentioned.

Specific examples of the compound represented by the general formula [IV] preferably used in the present invention are shown below, but the invention is not limited thereto.

[0072]

Embedded image

General formula [IV] preferably used in the present invention
The compound represented by the formula (1) is preferably added in the range of 1% by weight or more and 300% by weight or less with respect to the magenta coupler represented by the general formula [III]. More preferably 5% by weight or more 1
Add up to 50% by weight. The layer to be added has the general formula [II
It may be the same as or different from the layer to which the magenta coupler represented by I] is added, but it is preferably added to the same layer.

Like the magenta coupler represented by the general formula [III], the compound represented by the general formula [IV] can be introduced into the light-sensitive material by various known dispersion methods described later. The compound represented by the general formula [IV] may be mixed and dispersed at the same time as the magenta coupler represented by the general formula [III] and added to the photosensitive material, or may be separately dispersed and added from the magenta coupler. It is good, but it is desirable to mix and disperse them at the same time.

In the silver halide color photographic light-sensitive material of the present invention, the order of laminating each photosensitive layer is not particularly limited, and various laminating orders can be adopted according to the purpose. For example, a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer can be laminated in this order from the support side, and conversely, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer in order from the support side. Can be laminated.

The photosensitive layers having different color sensitivities may be sandwiched between two photosensitive layers having the same color sensitivities. Further, for the purpose of improving color reproduction, in addition to the three layers of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer, a fourth or more photosensitive layer having a color sensitivity can be provided. Regarding the layer constitution using a fourth or more color-sensitive photosensitive layer, JP-A-61-34541 and JP-A-61-201245 are available.
No. 61-198236, No. 62-160448 and the like, which can be referred to.

In this case, the fourth or more color-sensitive photosensitive layers may be arranged at any laminating position. The fourth or more color-sensitive photosensitive layer may be composed of a single layer or a plurality of layers.

Various non-photosensitive layers may be provided between the above-mentioned photosensitive layers and as the uppermost layer and the lowermost layer.

For these non-photosensitive layers, JP-A-61-43 is used.
748, 59-113438, 59-1134
Couplers, DIR compounds, and the like described in JP-A Nos. 40-61, 61-20037, and 61-20038 may be contained, and a color-mixing inhibitor may be contained as usually used. These non-photosensitive layers are RD3
08119, p. 1002, section VII-K, and may be an auxiliary layer such as a filter layer or an intermediate layer.

Examples of the layer structure that can be adopted in the light-sensitive material of the present invention include the forward layer, the reverse layer and the unit structure described in RD308119, page 1002, item VII-K.

When there are two light-sensitive layers having the same color sensitivity, these light-sensitive layers may be the same, or a high-sensitivity emulsion layer as described in West German Patent 923,045, It may have a two-layer structure of a low-sensitivity emulsion layer. In this case, it is usually preferable that the layers are arranged so that the sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the emulsion layers. Also, JP-A-57-112
No. 751, No. 62-200350, No. 62-2065
As described in JP-A Nos. 41 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support, the low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH)
/ High sensitivity green sensitive layer (GH) / Low sensitivity green sensitive layer (GL) /
Installed in the order of high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH Can be mentioned.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / from the side farthest from the support.
They can be arranged in the order of RH / GL / RL. Further, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer / G
They may be arranged in the order of L / RL / GH / RH.

Further, as described in JP-B-49-15495, three photosensitive layers having different sensitivities and having the same color sensitivity are provided.
Layers can be used. These three layers are arranged as a high-speed emulsion layer in the upper layer, a medium-speed emulsion layer in the middle layer, and a low-speed emulsion layer in the lower layer. Further, as described in JP-A-59-202264, a medium-speed emulsion layer, a high-speed emulsion layer, and a low-speed emulsion layer may be arranged in this order from the side away from the support.

When three layers having different sensitivities are formed, the order of laminating these three layers is arbitrary. For example, the laminating order includes a high sensitivity emulsion layer, a low sensitivity emulsion layer and an intermediate sensitivity emulsion layer. Order, or low-speed emulsion layer, medium-speed emulsion layer, high-speed emulsion layer and the like. Further, four or more photosensitive layers having the same color sensitivity can be provided, and in this case, the arrangement is arbitrary as described above.

As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The silver halide emulsion for use in the present invention is, for example, RD17643, pages 22 to 23 (December 1978).
"I. Emulsion preparationan
dtypes), pp. 18716, 648, Grafkides, Physics and Chemistry of Photography, published by Paul Montell (P.
Glafkids; Chemic et Physi
que Photographie, Paul M
Otel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photo.
optic Emulsion Chemist
RY, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al; Makin).
g and Coating Photographi
c Emulsion, FocalPress, 196
It can be prepared using the method described in 4). U.S. Pat. Nos. 3,574,628 and 3,663;
Monodisperse emulsions described in, for example, 5,394 and British Patent 1,413,748 are also preferable.

In the silver halide emulsion, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include the aforementioned RD17643, pp. 23-27, 1871.
6,648-651 and 308119,996 II
Various compounds described in sections IA to 1011, section XX-B can be used.

In order to prevent the deterioration of the photographic performance due to formaldehyde gas, the light-sensitive material is described in US Pat.
It is preferable to add a compound which can react with formaldehyde described in 1,987 or 4,435,503 and can be immobilized.

The silver halide emulsion used in the present invention preferably contains silver iodobromide having an average silver iodide content of 4 to 20 mol%, and an average silver iodide content of 5 to 15 mol%. It is particularly preferable to contain silver iodobromide containing Further, silver chloride may be contained as long as the object of the present invention is not hindered.

In the present invention, in the case of using a silver halide emulsion containing silver halide grains formed by deviating the development starting point to a specific site on the surface of the silver halide grain or in the vicinity thereof, the other silver halide emulsion is used. , Those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect or a composite form thereof.

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

The silver halide emulsion used in the present invention is
Research Disclosure (RD) 308
119 can be used. The places to be described are shown below.

[Item] [Page of RD308119] Iodine structure 993I-A Manufacturing method 〃 〃 and 994 E Crystal habit Normal crystal 〃 〃 Twin crystal 〃 Epitaxial〃〃 Halogen composition Uniform 993IB Not uniform 〃 〃 Halogen conversion 994I-C 〃 Substitution 〃 Metal 995I-D Monodispersion 995I-F Solvent addition 〃 Latent image forming position Surface 995I-G Inner surface 〃 Application Sensitive I-H negative 5 99 (Internal fog grains included) 〃 〃 Mixing emulsions 〃 I-J Desalting 〃 II-A In the present invention, the silver halide emulsion used is one that has been physically ripened, chemically ripened and spectrally sensitized. To do. The additives used in such a process are RD17643, 1871
6 and 308119.

The parts described below are shown.

[0096]

[Table 1]

Known photographic additives that can be used in the present invention are also described in the above RD. Below are the relevant locations.

[0098]

[Table 2]

Various color couplers can be used in the silver halide color photographic light-sensitive material of the present invention.

Examples of yellow couplers include US Pat. Nos. 3,933,051, 4,022,620, 4,326,024, 4,401,752 and 4,248,961. Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 4,314,023.
No. 4,511,649, European Patent 249,473
Those described in No. A and the like are preferable.

As the magenta coupler, a magenta coupler other than the magenta coupler represented by formula (III) of the present invention can be used in combination. As the magenta coupler used in combination, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 3,061,432
Nos. 3,725,067, 4,310,619
No. 4,351,897, European Patent 73,636.
Issue, Research Disclosure (hereinafter referred to as RD)
24220, 24230 (June 1984), JP-A-5
5-118034, 60-33552, 60-
No. 35730, No. 60-43659, No. 60-185.
951, 61-72238, U.S. Pat.
0,630, 4,540,654, 4,55
6,630, International Publication WO88 / 04795, etc.

Examples of cyan couplers include known phenol-type and naphthol-type couplers. Examples thereof include US Pat. Nos. 4,228,233, 4,296,200, 2,369,929 and 2,810. 171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173. , West German Patent Publication 3,329,729, European Patent 121,36
Nos. 5A and 249,453A; U.S. Pat.
No. 622, No. 4,333,999, No. 4,775,6
No.16, No.4,451,559, No.4,427,76
No. 7, 4,690,889, 4,254,212
No. 4,296,199, JP-A-61-42658.
Those described in No. 5 and the like are preferable.

For the purpose of correcting unnecessary absorption of color forming dye, a coupler for correcting unnecessary absorption of color forming dye by a fluorescent dye released at the time of coupling described in US Pat. No. 4,744,181, and US Pat. No. 4,777. It is also preferable to use a coupler having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group described in JP-A No.

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

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,080,
No. 211, No. 4,367,282, No. 4,409,3
No. 20, 4,576,910, British Patent 2,10
2, 173, etc.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. A DIR coupler releasing a development inhibitor is disclosed in
Nos. 7-151944, 57-154234, 60
Nos. 184248, 63-37346, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent 2,097,1 can be used.
Nos. 40 and 2,131,188, JP-A-59-157.
Nos. 638 and 59-170840 are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,472.
No. 4,338,393, and 4,310,618, multi-equivalent couplers described in JP-A-60-185950.
Compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound, or DIR redox compound described in JP-A-62-24252.
IR redox releasing redox compounds, EP 17
No. 3,302A, couplers capable of releasing a dye which becomes bicolor after release, RD11449, JP-A-24241, JP-A-61-61
Bleaching accelerator releasing couplers described in
Examples thereof include ligand releasing couplers described in U.S. Pat. No. 4,553,477 and the like, and couplers releasing a leuco dye described in JP-A-63-75747.

Further, various couplers can be used in the present invention, and specific examples thereof are RD17643 mentioned above.
VII-CF and RD308119, 1001-2
Page VII-DF.

The additive used in the present invention is RD3081.
19, XIV, etc. can be added.

As the support in the color light-sensitive material, any support can be used. In the case of a transparent support, a dye may be contained in the support for the purpose of preventing the light piping phenomenon (edge fog) that occurs when light enters the transparent support provided with the photographic emulsion layer from the edge. preferable. The dye to be blended for such a purpose is not particularly limited, but a dye having excellent heat resistance is preferable in the film forming process, and examples thereof include anthraquinone dye. Further, as the color tone of the transparent support, gray dyeing is preferred as seen in general light-sensitive materials, and one kind or a mixture of two or more kinds of dyes can be used. SUMIPL manufactured by Sumitomo Chemical Co., Ltd.
AST, Mitsubishi Kasei's Diaresin, Bayer
A dye such as MACROLEX manufactured by the company can be used alone or in an appropriate mixture.

The transparent support used in the present invention is, for example, a copolyester, or an antioxidant optionally blended with the copolyester, or a group consisting of sodium acetate, sodium hydroxide and tetraethylhydroxyammonium. An extruder controlled to a temperature range of 260 to 320 ° C. after sufficiently drying a copolyester composition containing at least one selected from the following:
Sheets are melt-extruded through a filter and a die, and the molten polymer is cooled and solidified on a rotating cooling drum to obtain an unstretched film. After that, the unstretched film is biaxially stretched in the machine direction and the transverse direction, and heat-set to produce the film.

The stretching conditions of the film cannot be uniformly specified because it varies depending on the copolymerization composition of the copolyester, but the stretching ratio is in the longitudinal direction in the temperature range of the glass transition temperature (Tg) to Tg + 100 ° C. of the copolyester. 2.5-6.0 times, Tg + 5 ° C to Tg + 50 ° C in the lateral direction
In the temperature range of, the draw ratio is in the range of 2.5 to 4.0 times.

The biaxially stretched film thus obtained is usually heat set at 150 to 240 ° C. and cooled. In this case, it may be relaxed in the vertical and / or horizontal direction if necessary.

The transparent support may be a single layer film or sheet formed by the above-mentioned method,
Further, it may have a multi-layer structure in which a film or sheet made of another material by a coextrusion method or a laminating method and a film or sheet formed by the above method are laminated.

The thickness of the transparent support thus obtained is not particularly limited, but is usually 120 μm or less, preferably 40 to 120 μm, more preferably 50 to
110 μm. Further, the local variation in the thickness of the transparent support is preferably within 5 μm, more preferably within 4 μm, and particularly preferably 3 μm or less.

When the thickness of the transparent support is set within the above range, the strength and curl characteristics of the film after coating the photographic constituent layers are not caused and the total thickness of the film can be kept within the desired range. You can Further, since the local variation in the thickness of the transparent support is within 5 μm, it is possible to prevent uneven coating and uneven drying when the photographic constituent layer is coated.

If necessary, a surface activation treatment such as corona discharge and / or a subbing layer is provided on the surface of the transparent support on the side where the photographic constituent layer is formed, prior to the formation of the photographic constituent layer. be able to.

As the undercoat layer, for example, JP-A-59-59
19941, 59-77439, 59-224
The undercoating layers described in JP-B No. 841 and JP-B-58-53029 can be mentioned as suitable examples. The undercoat layer provided on the surface of the transparent support opposite to the photographic component layer is also called a back layer.

When the color light-sensitive material of the present invention is used in the form of a roll, it is preferable that it is housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, the cartridges proposed in the following patents can also be used.

No. 58-67329 and 58-19.
5236, JP-A-58-181035, 58-1
82634, U.S. Pat. No. 4,221,479, JP-A Nos. 1-231045, 2-170156, and 2-1.
No. 99451, No. 2-124564, No. 2-2014
No. 41, No. 2-205843, No. 2-210346
No. 2, No. 2-211434, No. 2-214853, No. 2-264248, No. 3-37645, No. 3-37.
646, U.S. Pat. Nos. 4,846,418 and 4,84.
No. 8,693, No. 4,832,275.

Further, it can be applied to the "small photographic roll film cartridge and film camera" of JP-A-5-210201.

To obtain a dye image using the color light-sensitive material of the present invention, a generally known color development process is carried out after exposure. That is, the aforementioned RD17643, pages 28 to 29, R
D18716, pp. 647 and RD308119, 101
It can be developed by the usual method described on page 0, section XIX.

The light-sensitive material of the present invention includes, for example, the type and manufacturing number of the photographic light-sensitive material, the manufacturer's name, the emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. Magnetic recording for inputting various information required at the time, for example, various information obtained at the time of printing, such as the number of prints, selection of a filter, preference of a customer's color, size of a trimming frame, and other customer information. A layer may be provided.

In the present invention, the magnetic recording layer is preferably coated on the side of the support opposite to the photographic constituent layer. The undercoat layer, antistatic layer (conductive layer), It is preferable that the magnetic recording layer and the sliding layer are formed.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. . The method for producing these magnetic powders is known and can be produced according to a known method.

The optical density of the magnetic recording layer is preferably small considering the influence on the photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by Konica Sakura Densitometer P
Using DA-65, using a filter that transmits blue light, light having a wavelength of 436 nm is vertically incident on the coating film,
According to a method of calculating light absorption by the coating film.

The amount of magnetization of the magnetic recording layer per 1 m ² of the light-sensitive material is preferably 3 × 10 ^-2 emu or more. The amount of magnetization was measured by using an external magnetic field of 1000 in a coating direction of a coating film having a fixed volume using a sample vibration magnetometer (VSM-3) manufactured by Toei Industry.
The magnetic flux density (residual magnetic flux density) when the external magnetic field is reduced to 0 after saturation once with oe is measured, and this is converted into the volume of the transparent magnetic layer contained per 1 m ² of the photographic photosensitive material. You can ask. If the amount of magnetization per unit area of the transparent magnetic layer is smaller than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is 0.01 to 20 μm.
m is preferred, more preferably 0.05 to 15 μm, and still more preferably 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins, etc. are preferably used. It is also preferable to form the binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Furthermore, it is necessary to adjust the physical properties of these binders by curing with a curing agent, heat curing, electron beam curing, and the like. In particular, curing by adding a polyisocyanate type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add non-magnetic metal oxide particles, especially alumina fine particles.

Examples of the support for the photosensitive material include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film, cellulose diacetate film, polycarbonate film, polystyrene film, polyolefin film and the like. it can.
In particular, JP-A-1-244446 and JP-A-1-291248.
No. 1-298350 No. 2-89045 No. 2
No. 93641, No. 2-181749, No. 2-214
When a polyester having a high water content as shown in JP-A Nos. 852 and 2-291135 is used, even if the support is thinned, the curl recovery property after the development processing is excellent.

The supports preferably used in the present invention are PET and PEN. When these are used, the thickness is preferably 50 to 100 μm, particularly preferably 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ and T
iO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It is preferable to have a conductive layer containing metal oxide particles such as O, BaO, and MoO ₃ , wherein the metal oxide particles contain oxygen vacancies and foreign atoms that form donors for the metal oxide used. Is generally preferred because of its high conductivity, and the latter is particularly preferred because it does not give fog to the silver halide emulsion.

As the binder for the conductive layer and the undercoat layer, the same binder as used for the magnetic recording layer can be used.

Further, it is preferable to coat higher fatty acid ester, higher fatty acid amide, polyorganosiloxane, liquid paraffin, waxes, etc. on the magnetic recording layer as a sliding layer.

When the light-sensitive material of the present invention is used as a color light-sensitive material for roll-shaped photography, not only can a camera and a cartridge be miniaturized, but also resources can be saved, and a storage space for a developed negative film can be saved. Therefore, the film width is about 20 to 35 mm, preferably 20.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² , preferably 400 to 600 mm ² , it is possible to make a small format without deteriorating the image quality of the final photographic print, and a smaller patrone and a smaller camera than before can be achieved. In addition, the aspect ratio of the shooting screen is not limited, and is not limited to the conventional 12 aspect ratio.
6 sizes of 1: 1 and half sizes of 1: 1.4, 135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that it be housed in a cartridge. The most common cartridge is the current 135 format patrone. In addition, JP-A-58-67329, JP-A-58-195236, JP-A-58-181535, JP-A-58-182634,
U.S. Pat. No. 4,221,479, JP-A-1-23104
No. 5, 2-170156, 2-199451,
2-124564, 2-201441, 2-
No. 205843, No. 2-210346, No. 2-211
No. 443, No. 2-214853, No. 2-264248
Nos. 3-37645 and 3-37646; U.S. Pat. Nos. 4,846,418 and 4,848,693;
The cartridges proposed in JP-A-4,832,275 and the like can also be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

[0139]

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

Example 1 A multilayer color photographic light-sensitive material sample 101 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support having an undercoat layer.

Unless otherwise specified, the addition amount is the number of grams per 1 m ² . Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver.

First Layer: Antihalation Layer Black Colloidal Silver 0.16 Ultraviolet Absorber (UV-1) 0.20 High Boiling Organic Solvent (Oil-1) 0.12 Gelatin 1.53 Second Layer: Intermediate Layer Color Antifouling agent (SC-1) 0.06 High boiling point organic solvent (Oil-2) 0.08 Gelatin 0.80 Third layer: low sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, iodide) Silver iodide content 8.0 mol%) 0.43 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.15 Sensitizing dye (SD-1) 2. 8 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.9 × 1
0 ^-4 Sensitizing dye (SD-3) 1.9 × 10 -4 Sensitizing dye (SD-4) 1.0 × 10 -4 Cyan coupler (C-1) 0.56 Colored cyan coupler (CC-1 ) 0.021 DIR compound (D-1) 0.025 High boiling point solvent (Oil-1) 0.49 Gelatin 1.14 Fourth layer: medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm) , Silver iodide content 8.0 mol%) 0.89 silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.22 sensitizing dye (SD-1) 2.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.6 × 10 ⁻⁴ Cyan coupler (C-1) 0.45 Colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0.017 High boiling point solvent (Oil-1) 0.39 Gelatin 1.01 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^{− 4} Sensitizing dye (SD-2) 1.3 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.6 × 10 ⁻⁴ Cyan coupler (C-2) 0.20 Colored cyan coupler (CC-1) 0 0.034 DIR compound (D-3) 0.001 high boiling point solvent (Oil-1) 0.57 gelatin 1.10 sixth layer: intermediate layer color contamination inhibitor (SC-1) 0.075 high boiling point organic solvent ( Oil-2) 0.095 gelatin 1.00 Seventh layer: intermediate layer Gelatin 0.45 Eighth layer: low sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8. 0 mol%) 0.64 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.21 increase Sensitizing dye (SD-4) 7.4 × 10 ^-4 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.19 Magenta coupler (M-2) 0.49 Colored Magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.81 Gelatin 1.89 9th layer: Medium sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide) Content rate 8.0 mol%) 0.76 Sensitizing dye (SD-6) 1.5 × 10 ⁻⁴ Sensitizing dye (SD-7) 1.6 × 10 ⁻⁴ Sensitizing dye (SD-8) 1 0.5 × 10 ⁻⁴ Magenta coupler (M-1) 0.043 Magenta coupler (M-2) 0.10 Colored magenta coupler (CM-2) 0.039 DIR compound (D-2) 0.021 DIR compound ( D-3) 0.002 high boiling point solvent (Oil-2) 0.37 gelatin 0.7 10th layer: high sensitivity green-sensitive layer Silver iodobromide emulsion (average grain size 1.00 .mu.m, a silver iodide content of 8.0 mol%) 1.46 Sensitizing dye (SD-6) 0.93 × 10 - ⁴ Sensitizing dye (SD-7) 0.97 × 10 ⁻⁴ Sensitizing dye (SD-8) 0.93 × 10 ⁻⁴ Magenta coupler (M-1) 0.08 Magenta coupler (M-2) 0. 133 Colored magenta coupler (CM-2) 0.014 High boiling point solvent (Oil-1) 0.15 High boiling point solvent (Oil-2) 0.42 Gelatin 1.08 11th layer: Yellow filter layer Yellow colloidal silver 0. 07 Color Contamination Inhibitor (SC-1) 0.18 Formalin Scavenger (HS-1) 0.14 High Boiling Solvent (Oil-2) 0.21 Gelatin 0.73 12th Layer: Intermediate Layer Formalin Scavenger (HS-1) ) 0.18 gelatin 0 .60 thirteenth layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.073 Silver iodobromide emulsion (average grain size 0.38 μm) , Silver iodide content 3.0 mol%) 0.16 silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 sensitizing dye (SD-9) 2.1 × 10 ⁻⁴ Sensitizing dye (SD-10) 2.8 × 10 ⁻⁴ Yellow coupler (Y-1) 0.89 DIR compound (D-4) 0.008 High boiling point solvent (Oil-2) 0.37 Gelatin 1.51 14th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide content 8.0 mol%) 0.95 Sensitizing dye (SD-9 ) 7.3 × 10 ^-4 sensitizing dye (SD-10) 2.8 × 10 -4 yellow coupler (Y-1) 0.16 high boiling solvent (Oil-2) 0 Gelatin 0.80 Fifteenth layer: First protective layer Silver iodobromide emulsion (average grain size: 0.05 μm, silver iodide content: 3.0 mol%) 0.30 Ultraviolet absorber (UV-1) 094 UV absorber (UV-2) 0.10 Formalin scavenger (HS-1) 0.38 High boiling point solvent (Oil-1) 0.10 Gelatin 1.44 16th layer: 2nd protective layer Alkali-soluble matting agent PM -1 (Average particle size 2 μm) 0.15 Polymethylmethacrylate (Average particle size 3 μm) 0.04 Lubricant (WAX-1) 0.02 Gelatin 0.55 In addition to the above composition, a coating aid. SU-1, SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizer ST-1, dyes AI-1, AI-2, antifoggant AF-1, two types of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 100,000, a hard agent Membrane agents H-1, H-2 and preservative DI
-1 was added. The amount of DI-1 added was 9.4 mg / m ^2.
Met.

The structures of the compounds used in the above samples are shown below.

[0144]

[Chemical 21]

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

[0151]

Embedded image

[0152]

Embedded image

As shown in Tables 3, 4, and 5, M-1, M-2 of the eighth, ninth, and tenth layers of Sample 101 were replaced, and the compounds represented by the general formulas [I] and [II] were added. Samples 102 to 125 were prepared in the same manner as the sample 101 except for the above.

The amounts of the compounds of the general formulas [I] and [II] are shown in parentheses in Tables 3, 4 and 5 in millimoles per mol of silver halide, and the compounds of the general formula [III] are square meters. It is shown in millimoles per unit. If necessary, an amount of the compound IV corresponding to 30% by weight of the magenta coupler is used.
-5 was added to the eighth, ninth and tenth layers, respectively. The added samples are shown in Tables 3, 4 and 5.

For comparison, a sample in which the amount of antifoggant AF-1 was increased was also prepared and evaluated. AF-1 of each sample
The amounts used in Table 1 are also shown in Tables 3, 4 and 5 (unit: mmol / mol silver halide).

[0156]

[Table 3]

[0157]

[Table 4]

[0158]

[Table 5]

Samples 101 to 12 prepared as described above
5 was exposed to light according to the performance evaluation shown below, and the color development processing shown below was carried out to evaluate the performance.

A) Photographic sensitivity Gradient exposure to white light was applied to the sample, and the following color development processing was performed to find the minimum density +0.3 from the characteristic curve of the magenta color image.
The logarithm of the reciprocal of the exposure dose giving the density of
The difference (ΔS) was calculated based on 1. Where Δ
The larger the value of S is, the higher the sensitivity is.

B) Substantial fog, except that the developing agent was removed from the color developer,
Samples were processed as in a) photographic sensitivity determination. The difference between the green density of this sample and the green minimum density when the photographic sensitivity of a) was determined was determined as the actual fog of a magenta color image. The higher the value, the higher the actual fog.

C) Inter-image effect The sample was uniformly exposed with green light for 1 lux · sec and then with blue light for gradation exposure, and the following color development processing was performed.
The value obtained by subtracting the green density in the minimum density portion of the yellow color image from the green density at the exposure amount giving the density of the minimum density +1.0 of the blue density is the color turbidity value (Δ
It was evaluated as D _G ). The smaller the value, the greater the inter-image effect from the blue-sensitive layer to the green-sensitive layer and the better the color reproduction.

D) Granularity (RMS value) The portion which gives the green density of the minimum density +0.3 of the sample for which the photographic sensitivity was previously obtained was passed through a Ratten filter W-99 manufactured by Eastman Kodak Co., and an opening area of 1800 μm.
Scanning with a micro densitometer of ² (slit width 10 μm, slit length 180 μm), 1000 times the standard deviation of the fluctuation of the density value of the density measurement sampling number 1000 or more was obtained, and the relative value with the value of sample 101 as 100 Indicated by.

E) Raw storability The sample was conditioned for 6 hours at a temperature of 23 ° C. and a relative humidity of 65%, then sealed in a sealable bag and stored at 55 ° C. for one week. The raw preservation (substitute evaluation) sample thus obtained was exposed and processed in the same manner as the photographic sensitivity was determined in a) to determine the characteristic curve of a magenta color image. The difference (Δfog) between the minimum density value of this characteristic curve and the minimum density value when the photographic sensitivity was determined in a) was evaluated as the fog increase width during raw storage. The smaller the change, the better the raw preservability.

<< Color Development Processing >> (Processing Step) Process Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml Fixed 1 minute 30 Second 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Dry 60 seconds 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the light-sensitive material.

<Preparation of Processing Agent> (Color developer composition) Water 800 ml Potassium carbonate 30 g Sodium hydrogencarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added 1 Make up to 0.01 and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Color Development Replenisher Solution Composition) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make 1.0 l, and pH 1 was adjusted with potassium hydroxide or 20% sulfuric acid. Adjust to 0.18.

(Bleaching Solution Composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make a final volume of 1.0 l and aqueous ammonia was added. Alternatively, adjust the pH to 4.4 using glacial acetic acid.

(Bleaching Replenisher Solution Composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Water was added to make 1.0 l, and ammonia was added. Adjust to pH 4.4 with water or glacial acetic acid.

(Fixer Formulation) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water is added to make 1.0 l, and the pH is adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Fixing Replenisher Solution Formulation) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Water is added to make 1.0 l, and the pH is adjusted to 6.5 with aqueous ammonia or glacial acetic acid.

(Stabilizer and stable replenisher formulation) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 0. 1 g Siloxane (UC-L-77) 0.1 g Ammonia water 0.5 ml Water was added to make 1.0 l, and pH was adjusted to 8 with ammonia water or 50% sulfuric acid. Adjust to 5.

Table 6 shows the evaluation results obtained as described above.

[0174]

[Table 6]

As is clear from the results in Table 6, by using the compounds of the general formulas [I] and [II] in combination, the fog can be efficiently achieved without impairing the sensitivity. In addition, 3-anilino-5 represented by the general formula [III]
In a system using a pyrazolone magenta coupler, this effect is remarkable. Also, it can be seen that even if a high-speed coupler is used, high sensitivity can be achieved without impairing the inter-image effect, graininess and storability.

Further, from the results of Table 6, the compound represented by the general formula [II] was contained in the highest sensitivity layer, and the compound represented by the general formula [I] was contained in the same color-sensitive layer other than the highest sensitivity layer. It can be seen that the composition contained in can more effectively achieve the object of the present invention.

It is also understood that the combined use of the compound represented by the general formula [IV] is also a preferable direction for the manifestation of the effect.

[0178]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material capable of achieving high sensitivity while maintaining low fog, and further excellent in color reproducibility and graininess and long-term sensitization of the light-sensitive material. It was possible to provide a silver halide color photographic light-sensitive material excellent in storage stability with time.

Claims (3)

[Claims] 1. At least one light-sensitive emulsion on a support.
Layer having at least one non-photosensitive colloid layer
A silver genide color photographic light-sensitive material, the light-sensitive emulsion layer comprising:
A compound represented by the following general formula [I] in at least one layer of
And a compound represented by the following general formula [II]
Halogen containing at least one of
Silver halide color photographic light-sensitive material. [Chemical 1][In the formula, Z is -COOR¹¹, -CONR¹¹R¹², -SO
_TwoNR¹¹R¹², -SO_TwoR¹¹Or -COR¹¹Represents R
¹¹, R¹²Is a hydrogen atom, an alkyl group, an alkenyl
Group, alkynyl group, aryl group or heterocyclic group
You. [Chemical formula 2][In the formula, L₁, L_TwoEach represents a methylene chain, and A₁,
A_TwoIs -CO_Two-, -SO_Two-, -CONR
^{twenty four}-, -NR^{twenty four}CO-, -SO_TwoNR^{twenty four}-, -NR^{twenty four}S
O_Two-, -O-, -NR^{twenty four}CO_Two-Or-NR^{twenty four}CON
R^{twenty five}Represents-. R^{twenty one}, R ^{twenty two}, R^{twenty four}, R^{twenty five}Is hydrogen
Atom, alkyl group, alkenyl group, alkynyl group, ant
Group or heterocyclic group, R^{twenty three}Represents a substituent. x
₁, X_Two, Y₁, Y_TwoEach represents an integer of 0 to 20. ] 2. The photosensitive emulsion layer containing the compound represented by the general formula [I] and the compound represented by the general formula [II] is a green photosensitive emulsion layer. 1. The silver halide color photographic light-sensitive material described in 1. 3. The green photosensitive emulsion layer is represented by the following general formula [II
3. The silver halide color photographic light-sensitive material according to claim 2, containing at least one compound represented by I]. Embedded image [In the formula, R ³¹ represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. R ³² represents an aryl group. R ³³ represents a substituent n ₃
Represents an integer of 1 to 5. When n ₃ is 2 or more, R ³³ may be the same or different. ]