JP2001051382A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material superior in storage stability, production stability and processing stability, and high in sensitivity and image quality. SOLUTION: The silver halide photographic sensitive material has photographic constituent layers comprising at least each of red, green, and blue sensitive layers and nonphotosensitive layer, and at least one of the photographic constituent layers contains at least one kind of development inhibitor releasing(DIR) compound to be released from an active site of a coupler by a color development reaction, and after it has flow into color developing solution, it is decomposed into a compound substantially not affecting photographic performance, and at least one kind of magenta coupler represented by the formula is contained, at least one of the photographic constituent layers uses s deionized gelatin. In the formula, R21 is a group to be released by the reaction with the oxidation product of a color developing agent; R22 is an aryl group; R23 is a substituent; and n21 is 1, 2, 3, 4, or 5 and when n21 is >=2, R23 may be mutually the same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material (hereinafter, also referred to as a "photosensitive material"), and more particularly, to a silver halide photographic material having high sensitivity, excellent storage stability and improved production stability. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand for the development of silver halide photographic materials having high sensitivity, high image quality and excellent color reproducibility.

As one of effective means for obtaining high image quality, DI which reacts with an oxidized form of a color developing agent and releases a development inhibitor is used.
R compounds are known. It is well known that inclusion of a DIR compound in an emulsion improves sharpness by an edge effect and improves color reproducibility by an overlay effect. However, these DIR compounds are disadvantageous in that the development inhibitor released from the photosensitive material during color development is diffused and accumulated in the processing solution, and as a result, the processing solution exhibits a development inhibiting property. As a result, it is subject to restrictions on full use.

DIR compounds for solving the above-mentioned problems are disclosed in JP-A-57-151944 and JP-A-58-20515.
No. 0, No. 60-218644, No. 60-221750
No. 61-11743 and U.S. Pat.
No. 12 has been proposed.

When these DIR compounds are separated from the coupling position of the DIR compound, they exhibit development inhibiting properties,
After it has flowed into the processing solution, it has a leaving group having the property of decomposing into a compound that does not affect photographic properties.
R compound. Certainly, the use of this DIR compound significantly reduced the damage to the developing solution without causing development suppression even when a large amount of photosensitive material was continuously processed.

[0006] However, the photosensitive material is stored under various conditions for a long period of time until it is used after production. However, in the case of the photosensitive material containing the DIR compound, photographic characteristics vary during the long storage period. Further improvement is desired.

In a silver halide photographic light-sensitive material, yellow, magenta and cyan color images are formed by the reaction between an oxidized form of a color developing agent and a coupler. As the magenta dye-forming coupler, pyrazolone-based magenta couplers and as the cyan dye-forming coupler, phenol-based and naphthol-based cyan couplers are well known.
Although high sensitivity can be achieved by using a specific coupler having a high coupling speed, storage stability and production stability are deteriorated when used in combination with the above-mentioned DIR compound, which is not sufficient in practical use. Immediate improvement is desired without saying.

On the other hand, as a means for improving sensitivity and image quality, there is known a technique of arbitrarily using couplers having different coupling speeds in the same color-sensitive layer. For example, US Pat.
No. 26681 discloses a technique for improving granularity at a high sensitivity by using a coupler having a lower coupling speed than that of a high-sensitivity layer in a low-sensitivity layer, and Japanese Patent Application Laid-Open No. 59-60437 discloses a technique for coupling to a high-sensitivity layer. Including other fast couplers, the other layers have a slow coupling coupler and D
A technique for improving the granularity by using an IR compound is described. However, these prior arts have the problem that the load of sensitivity reduction due to the low-speed coupler is large and that the storage stability and production stability are impaired when used in combination with a specific DIR compound, and they have not been put to practical use. is the current situation.

In response to the demand for the development of high-sensitivity photographic materials, technical developments such as improvement of silver halide emulsions and speeding up of couplers have been carried out. In a low-sensitivity photographic material, an increase in the amount of silver is also used as a means for increasing the sensitivity. In this case, there is a disadvantage that bleaching failure occurs during the development processing. As a countermeasure, a coupler for releasing a bleaching accelerator has been proposed in order to improve the desilvering speed, but there are still problems in terms of storage stability and the like, which cannot be said to be sufficient from the viewpoint of practical use.

A silver halide photographic light-sensitive material is usually provided with a yellow filter layer in order to remove information in a spectral region unique to silver halide for the purpose of improving color reproducibility. Various compounds can be introduced into the yellow filter layer, but some necessary conditions such as absorption waveform, storage stability and residual color after treatment must be provided. Usually, colloidal silver has been generally used, but colloidal silver had a problem that fogging of an adjacent photosensitive layer occurs when the amount of colloidal silver is increased to improve cutability. Therefore, a technique of newly using a yellow dye for the filter layer is disclosed in, for example, JP-A-55-155350, JP-A-55-155351, and JP-A-5-155351.
Nos. 6-12639, 63-27838, 63-1
97943 and the like. However, although the use of these proposed dyes can prevent the fogging of the adjacent layer, the decolorization from the photosensitive material during the development processing is insufficient, and the fogging during storage has been adversely affected.

As described above, silver halide photographic materials generally have a color image-forming compound, a development inhibiting release compound, a bleach accelerator releasing compound,
Various photographic useful compounds such as yellow filter dyes have been used, but their storage stability or production stability are not sufficient. In particular, the characteristics are significantly impaired when combined with a specific DIR, and urgent improvement is required. ing.

As a result of intensive studies on this problem, it has been found that the above-mentioned properties are greatly affected by inorganic ions contained in photographic gelatin used as a hydrophilic binder. In particular, in the manufacturing process of high-sensitivity, high-quality silver halide photographic light-sensitive materials, the stability against slight fluctuations in manufacturing until coating is impaired due to the influence of inorganic ions on the photographic useful compound, and It turned out that it was the above restriction.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object a high sensitivity that meets various demands such as improvement of storage stability and production stability.
An object of the present invention is to provide a high-quality silver halide photographic material.

[0014]

The object of the present invention has been attained by the following.

1. A silver halide photographic material having at least one red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, and a photographic component layer composed of a non-photosensitive layer,
After at least one of the photographic constituent layers has been released from the active position of the coupler by a color development reaction, it becomes a compound exhibiting development inhibition properties, and after it has flowed into the color developer,
Contains at least one DIR compound having a group having a property of decomposing into a compound that does not substantially affect photographic properties at the coupling active site and at least one magenta coupler represented by the general formula (2) And a silver halide photographic material characterized in that deionized gelatin is used in at least one of the photographic constituent layers.

[0016]

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In the formula, R ²¹ represents a group capable of leaving by reaction with an oxidized form of a color developing agent, R ²² represents an aryl group, R ²³ represents a substituent, and n21 represents an integer of 1 to 5. Represent. n21 is 2 or more when R ²³ may be different even in the same.

2. A silver halide photographic material having at least one red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, and a photographic component layer composed of a non-photosensitive layer,
At least one of the photographic constituent layers contains at least one of the DIR compounds and at least one of the cyan couplers represented by the general formula (3), and deionized gelatin is used for at least one of the photographic constituent layers. A silver halide photographic light-sensitive material, characterized in that:

[0019]

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In the formula, R ³¹ represents an alkyl group or a cycloalkyl group, and R ³² represents a group that can be substituted on a benzene ring. n
31 represents an integer of 0 to 4. X ³¹ represents a group capable of leaving by reaction with an oxidized form of the color developing agent.

3. A silver halide photographic material having at least one red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, and a photographic component layer composed of a non-photosensitive layer,
At least one of the photographic constituent layers contains at least one of the DIR compounds and at least one of the cyan couplers represented by the general formula (4), and deionized gelatin is used for at least one of the photographic constituent layers. A silver halide photographic light-sensitive material, characterized in that:

[0022]

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In the formula, X represents a hydrogen atom or a group capable of leaving by coupling with an aromatic primary amine color developing agent. R ⁴¹ represents an aryl group or a heterocyclic group, and R ⁴² represents an aliphatic group or an aryl. Each group represented by R ⁴¹ or R ⁴² includes those having a substituent.

4. A silver halide photographic material having at least one red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, and a photographic component layer composed of a non-photosensitive layer,
At least one of the photographic constituent layers contains a high-speed coupler and a low-speed coupler in the same photosensitive layer as at least one of the DIR compounds, and deionized gelatin is used in at least one of the photographic constituent layers. Silver halide photographic light-sensitive material.

[5] A silver halide photographic material having at least one red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, and a photographic component layer composed of a non-photosensitive layer,
At least one of the photographic constituent layers contains at least one of the DIR compounds and at least one of the compounds represented by the general formula (5), and deionized gelatin is used for at least one of the photographic constituent layers. A silver halide photographic light-sensitive material comprising:

Formula (5) Cp- (T) m-S-Het In the formula, Cp represents a coupler residue, T represents a timing group, m represents 0 or 1, 2, and Het represents a substituent. Represents a saturated heterocyclic ring which may have However, the substituent substituted for Het never contains a carboxy group.

6. A silver halide photographic material having at least one red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, and a photographic component layer composed of a non-photosensitive layer,
At least one of the photographic constituent layers contains at least one of the DIR compounds and at least one of the yellow filter dyes represented by the general formulas (6) and (7). A silver halide photographic material characterized by using ionized gelatin.

[0028]

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In the formula, A represents an acidic nucleus, L ⁶¹ , L ⁶² and L ⁶³ represent a methine group, n61 represents 0, 1 or 2, and Z is bonded to the nitrogen atom shown in the formula. Represents a group of nonmetallic atoms necessary to form a heterocyclic residue, and Y is -C (R
⁶¹ ) represents a substituent or a heterocyclic residue represented by ( ^R62 ) ( ^R63 ). In the substituent represented by —C (R ⁶¹ ) (R ⁶² ) (R ⁶³ ), R ⁶¹ and R ⁶² represent a hydrogen atom or an alkyl group, which may be bonded to each other to form a ring. R ⁶³ has a hydrogen atom or a Hammett σp value of 0.3.
Represents three or more electron-withdrawing groups. However, R ⁶¹ , R ⁶² , R ⁶³
Does not simultaneously represent a hydrogen atom. Further, the dye represented by the general formula (6) has at least one carboxyl group or alkylsulfonamide group in an aromatic ring portion in its molecular structure.

[0030]

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In the formula, R ⁷¹ and R ⁷² each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
X is ^{-CN, -COOR 73, -CONR 73 R} 74, -SO
₂ NR ⁷³ R ⁷⁴ , -COR ⁷³ , -SO ₂ R ⁷³ or -CF ₃
And R ⁷³ and R ⁷⁴ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
L ⁷¹ , L ⁷² and L ⁷³ represent a methine group, and n represents an integer of 0, 1 or 2. 7. 7. An oil-in-water emulsion dispersion containing at least one hydrophobic photographically useful compound, wherein at least one layer contains a dispersion substantially free of a low-boiling solvent. 3. The silver halide photographic light-sensitive material described in 1. above.

8. The deionized gelatin has a chloride ion concentration of 500 ppm or less and a calcium ion concentration of 2 ppm.
The above-mentioned items 1 to 7, wherein the content is not more than 00 ppm.
6. The silver halide photographic light-sensitive material according to item 1.

Hereinafter, the present invention will be described in detail.

After the compound is dissociated from the active site of the coupler by the color development reaction according to the present invention, it becomes a compound having a development inhibiting property. After flowing out into the color developing solution, it substantially affects the photographic properties. As the DIR compound having a group having the property of decomposing into a compound that is not provided at the coupling active position, a compound represented by the following general formula (DIR-1) is preferable.

Formula (DIR-1) Cp- (T) mZ- (LY) n In the formula, Cp represents a coupler residue, T is bonded to the coupling position of the coupler, and the developing agent is oxidized. C by reaction with body
It represents a linking group in which the bond between T and Z is cut after the bond between p and T is cut off, and m represents 0, 1, or 2. Z represents a development inhibitor residue; L is a linking group containing a chemical bond in which the bond between L and Y is cleaved by a component in the developer after flowing out into the developer as Z- (LY) n. And Y represents a substituent. n represents 1 or 2, and when n represents 2, L and Y may be the same or different.

The coupler residue represented by Cp includes a yellow image forming coupler residue, a magenta image forming coupler residue, a cyan image forming coupler residue, and a coupler residue that does not substantially form an image forming color dye. Represent.

The yellow color image forming coupler represented by Cp includes acylacetanilide type (for example, pivaloylacetoanilide type, benzoylacetanilide type), malon diester type, malondiamide type, dibenzoylmethane type, and benzothia. Zolyl acetamide type, malon ester monoamide type, benzothiazolyl acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolylacetamide type or benzimidazolyl acetate type coupler residue, U.S. Pat. No. 880, the coupler residue derived from a heterocyclic-substituted acetamide or a heterocyclic-substituted acetate, or US Pat.
No. 0,446, British Patent No. 1,459,171, West German Patent No. 2,503,099, JP-A-50-13973.
No. 8 or Research Disclosure 15737
And the heterocyclic coupler residues described in U.S. Pat. No. 4,046,574.

Examples of the magenta color image forming coupler residue represented by Cp include a coupler residue having a 5-oxo-2-pyrazolin nucleus, a pyrazoloazole nucleus and a cyanoacetophenone type coupler residue.

Examples of the cyan image forming coupler residue represented by Cp include coupler residues having a phenol nucleus or an α-naphthol nucleus.

Further, after the coupler couples with the oxidized developing agent to release the development inhibitor, the effect as a DIR coupler is the same even if the image forming colorant is not substantially formed.

Examples of coupler residues of this type represented by Cp include, for example, US Pat. Nos. 4,052,213 and 4,052,213.
088,491, 3,632,345, 3,9
And coupler residues described in JP-A-58-9993 and JP-A-3,961,959. For example, a coupler residue that does not form a coloring dye or a coloring dye flows out of a light-sensitive material into a processing solution, so-called outflow property. So-called bleachable dye-forming coupler residues which are bleached by reacting with the dye-forming coupler residues and components in the processing solution.

Particularly preferably, Cp is a pivaloyl acetanilide type or benzoylacetanilide type yellow color image forming coupler residue, 5-oxo-2-virazoline nucleus magenta color image forming coupler residue, α-naphthol nucleus cyan color image forming residue. Α substituted with coupler residue and hydrophilic group
-An effluent dye-forming coupler residue of a naphthol nucleus.

Examples of the group represented by T include (1) a group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, and (2) a cleavage reaction that utilizes an intramolecular nucleophilic substitution reaction. , A group using a cleavage reaction of hemiacetal, (4) a group using a cleavage reaction of imino ketal, and (5) a group using a hydrolysis cleavage reaction of an ester.

The group (1) is described in, for example,
-114946, 57-154234, 57-
Nos. 188035, 58-98728, 58-16
No. 0954, No. 58-209736, No. 58-209
No. 737, No. 58-209736, No. 58-2097
No. 39, No. 58-209740, No. 62-86361
Nos. 6-87958 and 62-87958, for the group (2), for example, JP-A-57-56837 and U.S. Pat.
248,962, the group (3) is described in, for example, JP-A-60-249148 and JP-A-60-249149;
In U.S. Pat. No. 4,146,396, for the group (4), for example, in U.S. Pat. No. 4,546,073,
The group (5) is described in, for example, West German Published Patent No. 2,62.
No. 6,315.

Further, T may be such that after the bond between Cp and T is broken, the bond between T and Z is further broken by the reaction with the oxidized developing agent. And a redox component that undergoes a redox reaction with an oxidized developing agent.

When T is a coupler component, examples thereof include the respective coupler residues described in Cp.

When T is a redox component, examples thereof include hydroquinones, catechols, pyrogallols, aminophenols (for example, p-aminophenols, o-aminophenols), and naphthalene diols (for example, 1,2-naphthalene diols, 1,
4-naphthalenediols, 2,6-naphthalenediols) or aminonaphthols (for example, 1,2-aminonaphthols, 1,4-aminonaphthols, 2,2
6-aminonaphthols) and the like.

Among the groups represented by T, those shown below are preferred. In the structure, * 1 indicates a site binding to Cp, and * 2 indicates a site binding to Z.

[0049]

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R ₁ represents a substituent, R ₂ and R ₃ each represent a hydrogen atom or a substituent, 1 represents 0, 1 or 2, and when ₁ is 2, R ₁ may be the same or different; Further, R ₁ may form a condensed ring. p represents 0, 1 or 2.

Examples of the substituent represented by R ₁ include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamide group, Examples thereof include a sulfamoyl group, a carbamoyl group, an aryl group, a carboxyl group, a sulfo group, a cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl group, and an acyl group, and these include those further having a substituent. Examples of the substituent represented by R ₂ and R ₃ include an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group, and these include those further having a substituent.

L in the general formula (DIR-1) is a divalent linking group and contains a chemical bond which is cleaved by a component in the developer, for example, a nucleophile such as hydroxy ion or hydroxylamine. As such a chemical bond,
For example _{-COO -, - N (W 3} ) COO -, - SO 2 O
_{-, - OCH 2 CH 2 SO} 2 -, - OCOO -, - N
(W ₃₎ COCOO-. These chemical bonds are linked by intervening Z directly or alkylene group or / and phenylene group and the other is directly bonded to the Y. When linking to Z via an alkylene group or a phenylene group, an ether bond, an amide bond, a carbonyl group, a thioether bond, a sulfo group,
It may contain a sulfonamide bond and a urea bond.

W ₃ represents a hydrogen atom or a substituent. The substituent represents a halogen atom, a nitro group, an alkoxy group or an alkyl group.

As the linking group represented by L, for example, the following examples are preferable.

In the structure, * 3 represents a site binding to Z and * 4 represents a site binding to Y.

[0056]

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R ₄ and R ₅ each represent a hydrogen atom or an alkyl group or an aryl group which may have a substituent. Preferably, R ₄ is a hydrogen atom and R ₅ is an alkyl group having 1 to 4 carbon atoms.

W ₁ , W ₂ and W ₃ ′ represent a hydrogen atom or a substituent. d represents an integer of 0 to 10, preferably 0 to 5.

Examples of the substituent represented by W ₁ include a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkanamide group, an alkoxy group, an alkoxycarbonyl group, an alkane sulfonamide group and an alkylcarbamoyl. Group, aryloxycarbonyl group, aryl group, carbamoyl group, nitro group, cyano group, arylsulfonamide group, sulfamoyl group, imide group and the like.

[0060] The substituent represented by W _2, alkyl group, an aryl group or an alkenyl group and the like, W ₃ '
Has the same meaning as W ₃ , and the same substituents are exemplified.
Represents an integer of 6.

In the general formula (DIR-1), examples of the substituent represented by Y include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and a heterocyclic group. Further, those having a substituent are included.

The alkyl, cycloalkyl or alkenyl group represented by Y specifically represents a linear or branched alkyl, alkenyl or cycloalkyl group having 1 to 10, preferably 1 to 5 carbon atoms. And preferably has a substituent, and the substituent includes a halogen atom, a nitro group, an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an alkane sulfonyl group having 1 to 4 carbon atoms, Arylsulfonyl group having 6 to 10 carbon atoms, 2 carbon atoms
To 5 alkanamide group, anilino group, benzamide group, alkylcarbamoyl group having 2 to 6 carbon atoms, carbamoyl group, arylcarbamoyl group having 7 to 10 carbon atoms, alkylsulfonamide group having 1 to 4 carbon atoms, 6 carbon atoms ~ 1
0 arylsulfonamide group, C 1-4 alkylthio group, C 6-10 arylthio group, phthalimide group, succinimide group, imidazolyl group, 1,
2,4-triazolyl group, pyrazolyl group, benzotriazolyl group, furyl group, benzothiazolyl group, carbon number 1
4, alkylamino group having 2 to 4 carbon atoms, alkanoyl group having 2 to 4 carbon atoms, benzoyl group, alkanoyloxy group having 2 to 4 carbon atoms, benzoyloxy group, perfluoroalkyl group having 1 to 4 carbon atoms, cyano group, tetrazolyl group, hydroxyl Group, carboxyl group, mercapto group, sulfo group, amino group, alkylsulfamoyl group having 1 to 4 carbon atoms, arylsulfamoyl group having 6 to 10 carbon atoms, morpholino group,
C6-C10 aryl group, pyrrolidinyl group, ureido group, oxyamide group, C2-C6 alkoxycarbonyl group, C7-C10 aryloxycarbonyl group, imidazolidinyl group or C1-C6 alkylideneamino Selected from groups.

The aryl group represented by Y represents a phenyl group, a naphthyl group or the like, and these further include those having a substituent, and the substituent is the same as the above-mentioned alkyl group or alkenyl group. It is selected from 1-4 alkyl groups and the like.

The heterocyclic group represented by Y includes diazolyl group (such as 2-imidazolyl group and 4-pyrazolyl group), triazolyl group (such as 1,2,4-triazol-3-yl group), and thiazolyl group (such as -Benzothiazolyl group),
An oxazolyl group (e.g., a 1,3-oxazol-2-yl group), a pyrrolyl group, a pyridyl group, a diazinyl group (1,4
-Diazin-2-yl group), a triazinyl group (1,
2,4-triazin-5-yl group), furyl group, diazolinyl group (such as imidazolin-2-yl group), pyrrolinyl group and thienyl group.

Z in the general formula (DIR-1) includes, for example, a divalent nitrogen-containing heterocyclic group or a nitrogen-containing heterocyclic thio group. Examples of the heterocyclic thio group include a tetrazolylthio group and a benzothiazolylthio group. Group, benzimidazolylthio group, triazolylthio group, imidazolylthio group and the like.

Specific examples of Z in the general formula (DIR-1) are shown below.

In the structure, * 5 represents Cp- (T) m- and * 6
Represents a binding site to-(LY) n.

[0068]

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[0069]

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Wherein X represents a hydrogen atom or a substituent;
In the general formula (DIR-1), it is contained in the moiety Z, and examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkanamide group, an alkenamide group, an alkoxy group, a sulfonamide group, and an aryl group. Is mentioned.

The alkyl group or alkenyl group represented by X has the same meaning as the alkyl group or alkenyl group represented by Y in formula (DIR-1).

The alkanamide group, cycloalkaneamide group or alkenamide group represented by X is a straight-chain or branched-chain alkanamide group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, and a cycloalkaneamide group. Or represents an alkene amide group, and the alkoxy group or cycloalkoxy group represented by X specifically represents a straight-chain, branched-chain alkoxy group or cycloalkoxy group having 1 to 10, preferably 1 to 5 carbon atoms, These further include those having the same substituent as the substituent of the alkyl group or alkenyl group represented by Y in formula (DIR-1).

Among the DIR compounds represented by the general formula (DIR-1), preferred compounds are shown below.

[0074]

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[0075]

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R ₁ ′ is R ₁ , R ₂ ′ is R ₂ and R ₃ ′ is R ₃
And l ′ is the same as l, and X ′
Is synonymous with X.

Further, Cp, -LY is represented by the general formula (DIR-
It is synonymous with Cp and -LY in 1).

Among the DIR compounds represented by the general formula (DIR-1), a compound represented by the following general formula (1) is particularly preferred.

General formula (1) Cp- (T) m-TR- (LY) n In general formula (1), Cp and T, L, Y, m, n are each represented by the general formula (DIR-1) ) Cp and T, L, Y,
Synonymous with m and n. TR represents a monocyclic or condensed-ring triazole group bonded to (T) m with a nitrogen atom (m =
In the case of 0, TR binds directly to the coupling position of Cp).

The group represented by TR may have a substituent on the carbon atom, and TR is preferably a 1,2,3-triazolyl group or 1,2 which may have a substituent. , 4
-Triazolyl groups and benztriazolyl groups.

When TR binds to Cp or T, TR
It can be bonded at any nitrogen atom among the above three nitrogen atoms, and there are three isomers. When the DIR compound represented by the general formula (1) is contained in a silver halide color photographic light-sensitive material, these three isomers may be isolated and purified, and used alone, or the three isomers may be used alone. Or a mixture of any two of the three isomers.

In the general formula (1), TR is a 1,2,3-triazolyl group which may have a substituent, 1,2,4-
In the case of a triazolyl group, it is preferable that a thioether bond is included in the linking group represented by L, and in particular, a sulfur atom is directly linked to a 1,2,3-triazolyl group or 1,2,3.
It is preferred that a substituted thioether bond is included on the carbon atom of the 4-triazolyl group.

In formula (1), when Cp represents a yellow coupler residue or a magenta coupler residue,
m is preferably 0.

In the general formula (1), when Cp represents a cyan coupler residue, m is preferably 1, and in that case, T is preferably a group utilizing a cleavage reaction of hemiacetal.

Among the DIR compounds represented by the general formula (1), more preferred are the compounds represented by the following general formula (1A).

Formula (1A) Cp- (T) m-TR-S-J-CO ₂ R In Formula (1A), Cp represents a coupler residue;
T represents a timing group, and m represents 0, 1 or 2. T
R represents a 1,2,3-triazole group or a 1,2,4-triazole group bonded to (T) m with a nitrogen atom. TR-SJ-CO ₂ R represents an inhibitor residue released from Cp- (T) m by reaction with an oxidized developing agent. S represents a sulfur atom bonded to a carbon atom of TR. J represents an alkylene group, and R represents a substituted or unsubstituted alkyl group or aryl group.

In formula (1A), the groups represented by Cp and T have the same meanings as Cp and T in formula (DIR-1), and specifically, Cp and T in formula (DIR-1) T
And the like.

When TR binds to Cp or T, TR
It can be bonded at any of the above three nitrogen atoms and there are three isomers.

When the DIR compound represented by formula (1A) is contained in a silver halide photographic light-sensitive material, the
Each of the isomers may be isolated and purified and used alone, or a mixture of these three isomers or a mixture of any two of the three isomers may be used.

The alkylene group represented by J may be linear or branched, and may be cyclic. Also, J
The alkylene group represented by may have a substituent.
The alkylene group represented by J preferably has 1 to 6 carbon atoms interposed between S and CO ₂ R. Particularly preferably, the number of carbon atoms is one or two.
When the alkylene group represented by J is linear, R is preferably an unsubstituted alkyl group, and particularly preferably an alkyl group having 6 or more carbon atoms. When the alkylene group represented by J is branched, R is preferably a substituted alkyl, particularly preferably an aralkyl group or a substituted aryl group, particularly preferably a phenyl group substituted with an alkyl group at the O-position.

More preferably, the compound represented by formula (1A) is represented by the following formulas (1B), (1C) and (1C)
It is a compound represented by D).

[0092]

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In the general formula (1B), Y represents a yellow coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, and specifically, the yellow coupler residue exemplified in the general formula (DIR-1) is used. No.

TR represents a 1,2,3-triazolyl group or a 1,2,4-triazolyl group which may be substituted and which is bonded to the coupling position of Y with a nitrogen atom.

S represents a sulfur atom bonded on the carbon atom of TR.

R ₁ represents a hydrogen atom or an alkyl group or an aryl group which may have a substituent, and a hydrogen atom is particularly preferable. R ₂ represents an alkyl group or an aryl group which may have a substituent, and is preferably an unsubstituted alkyl group (particularly, a methyl group or an ethyl group).

R ₃ represents a group that can be substituted on the benzene ring. When m is 2 or more, the groups represented by R ₃ may be the same or different.

M represents an integer from 0 to 5.

(R ₃ ) m is preferably selected so that the sum of the Hammett σp values of m R ₃ is 0.2 or more and 0.7 or less. Particularly preferably, m is 1 and R ₃ is a chlorine atom, a bromine atom or an alkoxycarbonyl group.

[0100]

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In the general formula (1C), R _c1 represents an alkyl group which may have a substituent (for example, a methyl group, an i-propyl group, a t-butyl group, a trifluoromethyl group, etc.), a cycloalkyl group (for example, A cyclopropyl group, a 1-ethylcyclopropyl group, a cyclohexyl group, etc.) and an aryl group (for example, a phenyl group, a p-methoxyphenyl group, a naphthyl group, etc.). As R _c1 , a t-butyl group, a 1-ethylcyclopropyl group, a phenyl group and a p-methoxyphenyl group are preferred.

In the general formula (1C), R _c2 represents an alkyl group which may have a substituent (for example, t-octyl group, dodecyl group, tetradecyl group, 2-hexyldecyl group, etc.);
A cycloalkyl group (eg, cyclohexyl group, cyclododecyl group, etc.), an aryl group (eg, phenyl group, o-cyclohexylphenyl group, etc.), an acyl group (eg, octanoyl group, dodecanoyl group, trifluoroacetyl group,
Pivaloyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, cyclohexyloxycarbonyl group, n-dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, 2,4-
Di-t-amylphenoxycarbonyl group, 1-naphthyloxycarbonyl group, etc.). The total carbon number of the group represented by R _c2 is preferably 8 or more and 30 or less, particularly preferably 10 or more and 16 or less. R _c2 is 10 to 16 carbon atoms in total.
The alkyl group which may have a substituent is particularly preferable.

In the general formula (1C), R _c3 may be any group which can be substituted on the benzene ring, and k is 0, 1,
Represents 2, 3 or 4. When k represents 2, 3, and 4, R _c3
May be the same or different. k is 0,
1, 2 is preferred.

As R _c3 , a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, an oxycarbonyl group (eg, an alkoxycarbonyl group such as a methoxycarbonyl group, a cyclohexyloxycarbonyl group, an n-dodecyloxycarbonyl group, a phenoxycarbonyl group) Group, 2,4-
Di-t-amylphenoxycarbonyl group, aryloxycarbonyl group such as 1-naphthyloxycarbonyl group,
And a heterocyclic oxycarbonyl group such as 2-pyridyloxycarbonyl group, 1-phenylpyrazolyl-5-oxycarbonyl group, etc.), a sulfonylamino group (for example, methanesulfonylamino group, heptafluoropropanesulfonylamino group, n-hexadecylsulfonyl) An alkylsulfonylamino group such as an amino group, an arylsulfonylamino group such as a p-toluenesulfonyl group, and pentafluorobenzenesulfonylamino; an alkylcarbonylamino group such as an acetylamino group and a myristoylamino group; and an arylcarbonyl group such as a benzoylamino group Amino group) and the like. As R _c3 , a halogen atom is particularly preferred.

R _c4 is a hydrogen atom or an _optionally substituted alkyl (eg, methyl, ethyl, trifluoromethyl, etc.), a cycloalkyl group (eg, cyclopropyl, cyclohexyl, etc.), aryl A heterocyclic group (eg, a furyl group, a pyridyl group, etc.). As R _c4 , a hydrogen atom and a substituent having 6 or less carbon atoms are preferable.

In the general formula (1C), R _c5 represents a hydrogen atom, an alkyl group which may have a substituent (eg, methyl group, ethyl group, etc.), a cycloalkyl group (eg, cyclopropyl group, cyclobutyl group, etc.) ), An alkenyl group (eg, a vinyl group, an isopropenyl group, etc.), an alkynyl group (eg, an ethynyl group, a propynyl group, etc.), and an aryl group (eg, a phenyl group, a p-methoxyphenyl group, a naphthyl group, etc.). R _c5 is preferably a hydrogen atom or an alkyl group which may have a substituent having 4 or less carbon atoms.

In the general formula (1C), R _c6 represents an alkyl group which may have a substituent (for example, a methyl group, an ethyl group,
), A cycloalkyl group (eg, a cyclopropyl group, a cyclobutyl group, etc.), an alkenyl group (eg, a vinyl group, an isopropenyl group, etc.), an alkynyl group (eg, an ethynyl group, a propynyl group, etc.), an aryl group (eg, a phenyl group, p-methoxyphenyl group, naphthyl group, etc.).
As R _c6 , an alkyl group which may have a substituent having 4 or less carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable.

R _c7 represents a substituted alkyl group (eg, benzyl group, 1-hexyloxycarbonylethyl group, 2-phenoxyethyl group, etc.) or a substituted aryl group (eg, 2,6-dimethylphenyl group, 2-t-butylphenyl) Group). R _c7 is preferably a substituted benzyl group or a 2,6-disubstituted phenyl group, particularly preferably a p-chlorobenzyl group and a 2,6-dimethylphenyl group.

In the general formula (1C), a bond shown by throwing into a triazole ring indicates that the bond is bonded to any one of three nitrogen atoms on the triazole ring.

When the DIR compound represented by the general formula (1C) is contained in a silver halide color photographic light-sensitive material, the three isomers may be isolated and purified, and used alone. Or a mixture of any two of the three isomers.

Next, the compound represented by formula (1D) will be described.

[0112]

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In the general formula (1D), Ar ₁ and Ar ₂ each represent an aryl group or a heterocyclic group which may have a substituent.

As a substituent on Ar ₁ and Ar ₂ , a high-molecular weight substituent called a so-called ballast group is substituted with Ar ₁ or Ar ₂ for the purpose of making the DIR compound represented by the general formula (1D) resistant to diffusion. It is preferable that at least one is included in both or one of them. The ballast group has a total carbon number of 6 or more and 30 or less, preferably 10 or more and 20 or less.
The following groups are preferred:

As Ar ₁ and Ar ₂ , a phenyl group having a substituent is preferable. Examples of the substituent of the phenyl group include an oxycarbonyl group (for example, an alkoxycarbonyl group such as a cyclohexyloxycarbonyl group and an n-dodecyloxycarbonyl group, a 2,4-di-t-amylphenoxycarbonyl group, a 1-naphthyloxycarbonyl group, and the like) Aryloxycarbonyl group and heterocyclic oxycarbonyl group such as 2-pyridyloxycarbonyl group and 1-phenylpyrazolyl-5-oxycarbonyl group), carbamoyl group (for example, 4- (2,4-di-t-amyl) Phenoxy) an alkylcarbamoyl group such as a butylaminocarbonyl group, an arylcarbamoyl group such as a phenylcarbamoyl group and a 1-naphthylcarbamoyl group), a sulfamoyl group (for example, a dimethylsulfamoyl group, a 4- (2,4-
Di-t-amylphenoxy) alkylsulfamoyl group such as butylaminosulfonyl group, arylsulfamoyl group such as phenylsulfamoyl group, alkoxy group (eg, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy Group (for example, phenoxy group, 2,4-di-t
-Amylphenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group and the like), acylamino group (for example, alkylcarbonylamino group such as acetylamino group and myristoylamino group, arylcarbonylamino group such as benzoylamino group) and halogen atom ( For example, a chlorine atom, a bromine atom, etc.) are preferable.

Ar ₁ and Ar ₂ are each preferably a halogen atom, preferably a chlorine atom, or a phenyl group substituted by an alkoxy group, preferably a methoxy group, at the 2-position. The sum of carbon number is 6
The above substituted phenyl groups are preferred.

In formula (1D), R _d1 represents a hydrogen atom or an optionally substituted alkyl, cycloalkyl, aryl, or heterocyclic group. R _d2 and R _d3 each represent a hydrogen atom or an _optionally substituted alkyl group, cycloalkyl group, alkenyl group, alkynyl group,
Represents an aryl group. R _d4 represents an alkyl group or an aryl group which may have a substituent.

R_d1, R_d2And R_d3Specifically, each one
R in general formula (1C)_c4, R_c5And R_c6Same as exemplified in
The group of is mentioned. R_d4Is specifically represented by the general formula (1C)
R _c7The same groups and unsubstituted alkyl groups as exemplified in
(Eg, hexyl group, octyl group, etc.), aryl group (eg,
For example, a phenyl group).

In the general formula (1D), it is preferable that one of R _d2 and R _d3 is an alkyl group which may have a substituent, and it is particularly preferable that one of R _d2 and R _d3 is a hydrogen atom and the other is a carbon atom having 4 carbon atoms. The following alkyl groups are preferred.

Further, among the DIR compounds represented by the general formula (1), a compound represented by the following general formula (1E) is also preferable.

[0121]

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In the general formula (1E), Cp represents a coupler residue, T is bonded to a coupling position of Cp and a nitrogen atom on benztriazole, and Cp and T are reacted with an oxidized developing agent to form Cp and T. After the bond is broken, T represents a timing group at which the bond between T and the nitrogen atom on the benztriazole is broken, and m represents 0, 1, or 2. R ₄ and R ₅ each represent an aliphatic group or an aromatic group, and X represents a Hammett sp value of 0.3.
Represents a substituent of 0 or more, and n represents an integer of 1 to 4.

In formula (1E), the groups represented by Cp and T have the same meanings as Cp and T in formula (DIR-1), and specifically, Cp and T in formula (DIR-1) T
And the like.

R ₄ and R ₅ each represent a hydrogen atom, an aliphatic group or an aromatic group, and it is preferable that R ₄ is hydrogen and R ₅ is a hydrogen atom or an aliphatic group having 1 to 5 carbon atoms. preferable. R ₅ is particularly preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group.

X represents a substituent having a Hammett sp value of 0.30 or more, specifically, an oxycarbonyl group (eg, butoxycarbonyl group, pentyloxycarbonyl group, cyclohexyloxycarbonyl group, phenoxycarbonyl group, etc.), carbamoyl group Group (eg, dimethylcarbamoyl group, phenylcarbamoyl group, etc.), carbonyl group (eg, alkylcarbonyl group such as acetyl group, trifluoroacetyl group, pivaloyl group, etc., arylcarbonyl group such as benzoyl group, pentafluorobenzoyl group, etc.), cyano group And the like. Hammett's s of the group represented by X
The p value is preferably 0.35 or more and 0.7 or less.

Specific examples of preferred DIR compounds according to the present invention are shown below, but the present invention is not limited to these.

[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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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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The DIR compounds used in the present invention are described, for example, in JP-A-57-151944 and JP-A-58-205150.
No., No. 60-218644, No. 60-221750
And can be easily synthesized by the methods described in JP-A Nos. 60-233650 and 61-11743.

The DIR compound according to the present invention may be added to either a light-sensitive emulsion layer or a non-light-sensitive emulsion layer in a light-sensitive material. The addition amount is 1 × 10 ⁻⁴ to 1 × 10 ⁴ of the total coated silver amount.
^-1 mol% is preferred.

When the DIR compound according to the present invention is added to a light-sensitive material, an antihalation layer and an intermediate layer (different color-sensitive layers, the same color-sensitive layer, between a light-sensitive layer and a non-light-sensitive layer, etc.) May be added to any layer such as a light-sensitive silver halide emulsion layer, a non-light-sensitive silver halide emulsion layer, a yellow filter layer and a protective layer, or may be added to two or more layers.

Two or more of these compounds may be mixed in the light-sensitive material, and the total amount thereof may be from 1 × 10 ^{-5 to} 0.5 per mol of silver halide when incorporated in the emulsion layer.
Mole, preferably in the range of 1 × 10 ^{−3 to} 0.05 mole. When incorporated in the non-photosensitive hydrophilic colloid layer, the coating amount is preferably 10 ^-7 to 10
^-2 mol / m ² , more preferably 10 ^-6 to 10 ^-4 mol / m ²
It is.

Next, the compound represented by formula (2), which is the magenta coupler according to the present invention, will be described.

[0171]

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In the formula, R ²¹ represents a group capable of leaving by reaction with an oxidized form of a color developing agent, R ²² represents an aryl group, R ²³ represents a substituent, and n21 represents an integer of 1 to 5. Represent. n21 is 2 or more when R ²³ may be different even in the same.

In the general formula (2), R ²¹ represents a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent. R ²¹ is preferably a group which can be eliminated by a reaction with an oxidized form of an aromatic primary amine color developing agent, and more preferably an arylthio group, from the viewpoint of saving silver and improving resistance to harmful gases.

R ²² represents an aryl group, for example, phenyl, pentachlorophenyl, 2,4,6-trichlorophenyl, 2,5-dichlorophenyl, 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.

When the magenta coupler represented by the general formula (2) according to the present invention is used for a color negative film,
R ²² is preferably a pentachlorophenyl group, a 2,4,6-trichlorophenyl group, a 2,6-dichlorophenyl group, in that the spectral absorption wavelength of the color dye obtained by reacting with the oxidized form of the color developing agent is preferable.
Dichloro-4-methanesulfonylphenyl group, 2,6-
Dichloro-4-cyanophenyl group, 2,6-dichloro-
It is preferably a 4-morpholinosulfonylphenyl group, particularly preferably a pentachlorophenyl group and a 2,4,6-trichlorophenyl group.

R ²³ represents a substituent, for example, chlorine, bromine,
Halogen atoms such as fluorine, alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy groups, 2,6
-Dichlorobenzoylamino group, 2,6-dimethoxybenzoylamino group, benzoylamino group such as hexadecylsulfonyl group, alkylsulfonyl group such as hexadecylsulfonyl group, acylamino group such as acetylamino group,
Examples thereof include an alkoxycarbonyl group such as a cyano group, a nitro group, a carboxyl group, an amino group, and an ethoxycarbonyl group; and an alkyl group such as a methyl group, an ethyl group, and an isopropyl group. You may.

From the viewpoints of color development and spectral absorption wavelength, at least one of R ²³ is preferably a halogen atom or an alkoxy group.

Specific examples of the magenta coupler represented by the general formula (2) according to the present invention are shown below, but the present invention is not limited thereto.

[0179]

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[0180]

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[0181]

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[0182]

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[0183]

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The magenta coupler represented by the general formula (2) according to the present invention may be used in two or more kinds, or may be used in combination with other magenta couplers.

The magenta coupler represented by the general formula (2) according to the present invention is used for a silver halide emulsion layer.
It is preferably used for a green-sensitive layer.

The amount of the magenta coupler represented by the general formula (2) according to the present invention is preferably 0.1 to 2.0 g / m ^2, more preferably 0.3 to 1.0 g / m ² . is there.

Next, the compound represented by the general formula (3), which is the cyan coupler according to the present invention, will be described.

[0188]

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In the formula, the alkyl group represented by R ³¹ includes, for example, iso-propyl, butyl, iso-butyl, sec-butyl, tert-butyl, octyl,
-Ethylhexyl, 2-hexyldecyl, tetradecyl and the like. Examples of the cycloalkyl group represented by R ³¹ include groups such as cyclopentyl, cyclohexyl, and adamantyl. Of the substituents represented by R ^31, branched alkyl groups are preferred. The substituent groups on the benzene ring represented by R ^32, for example, alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamido, alkylthio, arylthio, halogen atom, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl , Sulfamoyl, cyano,
Groups such as alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, carboxy, etc. Is mentioned. Of these, alkyl and alkoxy groups are preferred.

N31 is preferably 0 or 1. In R ³² is an alkyl or alkoxy group, particularly preferred is a case n31 is 1.

The leaving group represented by X ³¹ includes, for example, aryloxy, carbamoyloxy, alkoxy, acyloxy, sulfonamide, succinimide and the like in which a halogen, an oxygen atom or a nitrogen atom is directly bonded to the coupling position. The group of is mentioned. Of these, alkoxy and aryloxy groups are preferred, and carboxyl, hydroxyl, and sulfonamide groups are preferred as the substituents.

Specific examples of the cyan coupler represented by the general formula (3) according to the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0193]

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[0194]

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The cyan coupler represented by the general formula (3) according to the present invention may be used in combination of two or more, or may be used together with other cyan couplers.

The cyan coupler represented by the general formula (3) according to the present invention is used for a silver halide emulsion layer, but is preferably used for a red-sensitive layer.

[0197] The amount of the cyan coupler represented by formula (3) according to the present invention is preferably from 0.01 to 1.0 g / m ^2, more preferably at 0.1 to 0.8 g / m ² is there.

Next, the compound represented by the general formula (4), which is the ureido cyan coupler according to the present invention, will be described.

[0199]

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In the formula, X represents a hydrogen atom or a group capable of leaving by coupling with an aromatic primary amine color developing agent. R ⁴¹ represents an aryl group or a heterocyclic group, R ⁴² represents an aliphatic group or an aryl group, each group represented by R ⁴¹ or R ⁴² include those having a substituent, the R ⁴¹ or R ⁴² R ⁴¹ and R include those which form multimers of dimers or more
Reference numeral ⁴² , alone or in combination, has a shape or size necessary for imparting diffusion resistance to the coupler represented by formula (4) and a dye formed from the coupler.

At least one of R ⁴¹ and R ⁴² has a total of 10 or more carbon atoms in a linear or branched alkyl group, or is bonded to a polymer chain.

The aryl group represented by R ⁴¹ or R ⁴² includes, for example, a phenyl group and a naphthyl group.

Examples of the substituent for the group represented by R ⁴¹ or R ⁴² include a halogen atom and nitro, cyano, alkyl, aryl, amino, hydroxyl, acyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, Each group includes alkoxysulfonyl, aryloxysulfonyl, carbamoyl, sulfamoyl, acyloxy, carbonamide, and sulfonamide. The number of the substituents is preferably 1 to 5, and when it is 2 or more, each substituent may be the same or different. Is also good.

Preferred as the substituent for R ⁴¹ are a halogen atom, an alkylsulfonyl group and a cyano group.

R ⁴² is preferably represented by the following formula (4)
-2).

[0206]

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In the formula, J represents an oxygen atom or a sulfur atom.
k is an integer of 0 to 4, l is 0 or 1, and when k is 2 or more, two or more ^R44s may be the same or different. R ⁴³ represents an alkylene group, and R ⁴⁴ represents a substituent.

As the substituent represented by R ⁴⁴ , for example,
Examples include groups such as alkyl, aryl, alkoxy, aryloxy, hydroxyl, acyloxy, alkylcarbonyloxy, arylcarbonyloxy, carboxyl, alkoxycarbonyl, aryloxycarbonyl, alkylthio, acyl, acylamino, sulfonamido, carbamoyl, and sulfamoyl.

Examples of the leaving group represented by X include an aryloxy group, an alkoxy group, an acyloxy group, an arylthio group and an alkylthio group in which a halogen atom, an oxygen atom, a sulfur atom or a nitrogen atom is directly bonded to the coupling position. , A sulfonamide group, an acid imide group, and the like. Further, specific examples include U.S. Pat.
Nos. 563 and 3,749,735, and JP-A-47-37.
No. 425, JP-B-48-36894, JP-A-50-1
No. 0135, No. 50-117422, No. 50-130
No. 441, No. 51-108841, No. 50-1203
No. 34, No. 52-18315, No. 53-105226
And those described in each gazette.

The specific examples of the ureido cyan coupler represented by the general formula (4) according to the present invention are shown below, but the present invention is not limited thereto.

[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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[0222]

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[0223]

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[0224]

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When two or more types of magenta couplers represented by the general formula (2) and cyan couplers represented by the general formulas (3) and (4) are used, a cup with an oxidized color developing agent is used. It is preferable to use two or more couplers having different ring speeds in the same layer. A method for measuring the coupling speed of a coupler and specific examples of a coupler having a high coupling speed and a coupler having a low coupling speed are described in
No. 307375, but is not limited thereto.

The coupling speeds of the couplers represented by formulas (2) to (4) of the present invention are classified as follows.

A coupler having a high coupling speed; 2-
1, 2-3, 2-4, 2-6 to 14, 3-1 to 8 couplers having a low coupling speed; 2-2, 2-5, 4
-1 to 50 Next, the compound represented by formula (5) according to the present invention will be described.

Formula (5) Cp- (T) m-S-Het In the formula, Cp represents a coupler residue, T represents a timing group, m represents 0 or 1, 2, and Het represents a substituent. Represents a saturated heterocyclic ring which may have However, the substituent substituted for Het is not a carboxy group.

In formula (5), the groups represented by Cp and T have the same meanings as Cp and T in formula (DIR-1), and specifically, Cp and T in formula (DIR-1) Examples of the group include those exemplified for T. m represents 0 or 1, 2; The group represented by Het is preferably 3 selected from an oxygen atom, a nitrogen atom and a sulfur atom as a hetero atom.
It is a membered to 8-membered saturated heterocyclic group, preferably a 4- to 8-membered saturated heterocyclic group. Further, the ring-constituting atomic group may include a carbonyl group.

Representative examples of the saturated heterocyclic ring represented by Het include a sulfolane ring, a tetrahydrothiophene ring, an aziridine ring, an azetidine ring, a pyrrolidine ring, a piperidine ring, an oxirane ring, a tetrahydrofuran ring, a morpholine ring, a piperazine ring, and an imidazo ring. A lysine ring, a pyrazolidine ring, a thiazolidine ring, a γ-butyrolactone ring, a pyrrolidone ring and a succinimide ring. As the saturated heterocyclic group represented by Het, a sulfolane ring, a pyrrolidone ring and a succinimide ring are preferable.

The group represented by Het may have a substituent. Examples of the substituent for the group represented by Het include an aliphatic group, a hydroxy group, an alkoxycarbonyl group, an alkoxy group, an acylamino group, an acyloxy group,
Examples include a sulfonamide group, a sulfamoyl group, a carbamoyl group, a halogen atom, an amino group, a sulfo group, an acyl group, an alkoxycarbonylamino group, a ureido group, and an alkylthio group. These substituents that substitute for the group represented by Het may further have a substituent. Where H
The substituent substituted for et does not contain a carboxy group. As a substituent for Het, a group having a total carbon number of 4 or less is preferable.

Next, typical compounds represented by the general formula (5) used in the present invention are shown, but the present invention is not limited thereto.

[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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The hydrophobic photographic useful compounds represented by formulas (1) to (5) according to the present invention described above can be introduced into a silver halide photographic material by a known dispersion method.

For example, the hydrophobic photographically useful compound is dissolved together with a high-boiling organic solvent using a low-boiling organic solvent such as ethyl acetate, butyl acetate, or butyl propionate as an auxiliary solvent, and then gelatin containing a surfactant is dissolved. After mixing with an aqueous solution, the mixture is emulsified using an emulsifying and dispersing apparatus, for example, a high-speed rotary mixer, a colloid mill or an ultrasonic dispersing machine, to prepare an oil-in-water type emulsified dispersion, and then added to the silver halide emulsion. be able to. Further, after the above-mentioned emulsified dispersion is cooled and set, it may be shredded, washed with water, and then added to the silver halide emulsion.

As the low boiling organic solvent, an organic solvent having a boiling point of about 30 to 150 ° C. is usually used. Examples of the low boiling organic solvent include lower alkyl acetate (ethyl acetate, butyl acetate, etc.), methanol and methanol. Examples include ethanol, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, and cyclohexane.
The low-boiling point organic solvent is removed during or after emulsification and dispersion by a degassing method or an ultrafiltration method, whereby an emulsified dispersion substantially containing no low-boiling point organic solvent can be obtained.

The term "substantially free of a low-boiling organic solvent" as used in the present invention means that no low-boiling organic solvent is contained, and at the same time, an oil phase solution comprising a hydrophobic photographically useful compound and a high-boiling organic solvent. It also means that a low-boiling organic solvent up to 1.0% by weight is contained therein.

Next, the compound represented by formula (6) according to the present invention will be described.

[0243]

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In the formula, A represents an acidic nucleus, L ⁶¹ , L ⁶² and L ⁶³ represent a methine group, n61 represents 0, 1 or 2, and Z represents a bond to a nitrogen atom shown in the formula. Represents a group of nonmetallic atoms necessary to form a heterocyclic residue, and Y is -C (R
⁶¹ ) represents a substituent or a heterocyclic residue represented by ( ^R62 ) ( ^R63 ). In the substituent represented by —C (R ⁶¹ ) (R ⁶² ) (R ⁶³ ), R ⁶¹ and R ⁶² represent a hydrogen atom or an alkyl group, which may be bonded to each other to form a ring. R ⁶³ has a hydrogen atom or a Hammett σp value of 0.3.
Represents three or more electron-withdrawing groups. However, R ⁶¹ , R ⁶² , R ⁶³
Does not simultaneously represent a hydrogen atom. Further, the dye represented by the general formula (6) has at least one carboxyl group or alkylsulfonamide group in an aromatic ring portion in its molecular structure.

In the general formula (6), examples of the acidic nucleus represented by A include 2-pyrazolin-5-one, pyrazolidinedione, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone. , Isoxazolone, indandione, hydroxypyridone, pyrazolopyridone and the like.
-Pyrazolin-5-one. These acidic nuclei may have a substituent. Examples of the substituent include an alkyl group (eg, a methyl group, an ethyl group, a hexyl group, etc.), a cycloalkyl group (eg, a cyclohexyl group, Cyclopentyl group, etc.), aryl group (eg, phenyl group, tolyl group, 4-hydroxyphenyl group, 4-carboxyphenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), alkoxy group (eg, methoxy group) Ethoxy group, tert-butoxy group, etc.), aryloxy group (eg, phenoxy group, 4-methylphenoxy group, etc.), heterocyclic group (eg, pyridyl group, furyl group, thienyl group, etc.), substituted or unsubstituted Amino group (eg, dimethylamino group, diethylamino group, anilino group, etc.), alkylthio group (eg, methylthio group, etc.) An acyl group (e.g., acetyl group, pivaloyl group,
Benzoyl group etc.), alkoxycarbonyl group (for example,
Methoxycarbonyl group, ethoxycarbonyl group, 2-hydroxyethoxycarbonyl group, etc., carbamoyl group (for example, carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, 2-hydroxyethylcarbamoyl group, dimethylcarbamoyl group, 4-carboxyphenylcarbamoyl group) Etc.), a cyano group and the like.

[0246] If combined with L ⁶¹ in the general formula (6) acidic nucleus in any position, is either a compound represented by the general formula (6) has a function as a dye, known to those skilled in the art And can also be confirmed by experiment.

Further, L ⁶¹ , L ⁶² and L of the general formula (6)
^The methine group represented by ⁶³ includes those having a substituent,
Examples of the substituent are the same as those described above as the substituent of the acidic nucleus A.

In the general formula (6), examples of the heterocyclic ring formed by Z together with a nitrogen atom include pyrrole, pyrazole, imidazole, triazole and tetrazole. The heterocyclic ring may be condensed with a benzene ring, and examples of such a heterocyclic ring include indole, indazole, and benzimidazole. The heterocyclic ring includes those having a substituent, and examples of the substituent include a halogen atom in addition to those described above as the substituent of the acidic nucleus A.

In the general formula (6), Y represents —C (R ⁶¹ )
(R ⁶² ) represents a substituent or a heterocyclic residue represented by (R ⁶³ ). As the heterocyclic residue, pyrrole, imidazole, pyrazole, pyridine, pyrimidine, thiophene,
Quinoline, benzimidazole, indole, benzthiazole, sulfolane, thiacyclohexane-1,1-
Heterocyclic residues derived from dioxide, butyrolactone, pyran, morpholine, piperidine and the like can be mentioned. The heterocyclic residue includes those having a substituent, and examples of the substituent include a halogen atom in addition to those described above as the substituent of the acidic nucleus A.

R ⁶¹ and R ⁶² represent an alkyl group, examples of which include a methyl group, an ethyl group, an isopropyl group, a butyl group, a neopentyl group and an octyl group, preferably a methyl group and an ethyl group. R ⁶¹ and R ⁶² may combine with each other to form a ring, and examples thereof include cyclohexane, cyclopentane, cyclohexene, and cyclohexanone. The alkyl group and the ring formed include those having a substituent, and examples of the substituent include a halogen atom in addition to those described above as the substituent of the acidic nucleus A.

R ⁶³ is a hydrogen atom or a substituent constant Hamm
sigma _p value of ett (Toshio Fujita, ed., "Chemistry region extra number 122
No. Structure-activity relationship of drugs ", pp. 96-103 (197
9) It is described in Nankodo etc. ) Represents a group of 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl group) Group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (for example, carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl group, dimethylcarbamoyl group, phenylcarbamoyl group, 4-carboxyphenylcarbamoyl group, etc.), acyl group ( For example, a methylcarbonyl group, an ethylcarbonyl group, a butylcarbonyl group, a phenylcarbonyl group, a 4-ethylsulfonamidophenylcarbonyl group, and the like, an alkylsulfonyl group (for example, methylsulfonyl) , An ethylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, etc.), an arylsulfonyl group (eg, a phenylsulfonyl group, 4-chlorosulfonyl group, etc.), preferably an alkoxycarbonyl group, an alkylsulfonylamino group, trifluoro Examples include a methyl group and a cyano group.

The dye represented by the general formula (6) has at least one carboxyl group or alkylsulfonylamino group in the aromatic ring portion in the molecule as described above, and examples of the alkylsulfonylamino group include methyl Examples include a sulfonylamino group and an ethylsulfonylamino group. It is preferably a carboxyl group or a methylsulfonylamino group, and particularly preferably a carboxyl group.

Hereinafter, specific examples of the dye represented by the general formula (6) are shown, but the invention is not limited thereto.

[0254]

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[0255]

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[0256]

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[0257]

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[0258]

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[0259]

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[0260]

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[0261]

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[0262]

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Next, the compound represented by formula (7) according to the present invention will be described.

[0264]

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In the formula, R ⁷¹ and R ⁷² each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
X is ^{-CN, -COOR 73, -CONR 73 R} 74, -SO
₂ NR ⁷³ R ⁷⁴ , -COR ⁷³ , -SO ₂ R ⁷³ or -CF ₃
And R ⁷³ and R ⁷⁴ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.
L ⁷¹ , L ⁷² and L ⁷³ represent a methine group, and n represents an integer of 0, 1 or 2.

In the general formula (7), R ⁷¹ , R ⁷² and R ⁷³
And the alkyl group represented by R ⁷⁴ include, for example, methyl, ethyl, propyl, i-propyl, butyl, t-
Examples include butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl and the like. These alkyl groups further include a halogen atom (eg, chlorine, bromine, fluorine, etc.), an alkoxy group (eg, a group such as methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy), an aryloxy group (eg, For example, phenoxy, naphthyloxy, etc.), an aryl group (eg, phenyl, naphthyl, etc.),
Alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl, etc.) aryloxycarbonyl group (eg, phenoxycarbonyl, naphthyloxycarbonyl, etc.), alkenyl group (eg, vinyl, allyl, etc.), heterocyclic ring Groups (eg, 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, pyrimidyl, pyrazolyl, furyl, etc.), alkynyl groups (eg, propargyl), amino groups (eg, amino, N, N-dimethyl) Amino, anilino, etc.), hydroxyl group, cyano group, sulfo group, carboxyl group, sulfonamide group (for example, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, It may be replaced by Le sulfonylamino etc.) and the like.

The alkenyl groups represented by R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ include, for example, vinyl, allyl and the like.

Examples of the alkynyl group represented by R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ include, for example, propargyl.

The aryl group represented by R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ includes, for example, phenyl, naphthyl and the like.

Examples of the heterocyclic group represented by R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ include a pyridyl group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl and the like), a thiazolyl group, an oxazolyl group , Imidazolyl group, furyl group, phenyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group,
Examples include a pyridazinyl group, a selenazolyl group, a sulfolanyl group, a piperidinyl group, a pyrazolyl group, and a tetrazolyl group.

The alkenyl group, alkynyl group, aryl group and heterocyclic group are all the same as the alkyl groups represented by R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ and the substituents of the alkyl groups. Can be substituted by a group.

Hereinafter, specific examples of the dye represented by Formula (7) are shown, but the present invention is not limited thereto.

[0273]

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[0274]

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[0275]

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[0276]

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[0277]

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The silver halide photographic light-sensitive material according to the present invention is characterized in that the binder forming at least one of the light-sensitive layer and the non-light-sensitive layer contains gelatin as a main component, and the gelatin is deionized gelatin. Preferably, chlorine and calcium ions are reduced by the deionization step. For example,
Calcium in gelatin is derived from raw materials. To obtain gelatin having the calcium content of the present invention, selection of raw materials, selection of production conditions, ion exchange treatment, etc. may be appropriately combined. As the ion exchange treatment, gelatin may be extracted from raw materials such as beef bone and pig skin, and then subjected to ion exchange using an ion exchange resin (for example, IRA type manufactured by Rohm and Haas Company). Quantification of calcium ion content after ion exchange treatment is based on the gelatin test method for photographs (abbreviated Pagii method) established by the Joint Council for Gelatin Test Methods,
The method may be performed according to the method described in the sixth edition.

In the present invention, the chloride ion concentration is 500
ppm or less, preferably 300 ppm or less, more preferably 100 ppm or less, and the calcium ion concentration is 200 ppm or less, preferably 100 ppm or less, and more preferably 50 ppm or less.

The gelatin according to the present invention is preferably subjected to a peroxide treatment at the time of production. It is preferable to use a method of adding a primary or secondary amine having no dissociable group for the purpose of shortening the extraction time in the lime treatment step during the production of gelatin. These compounds are preferably added to the lime suspension to a concentration of 0.01% to 0.1%. As the compound, a compound having a relatively small molecular weight is preferable, and a compound having 5 or less carbon atoms is particularly preferably used. Examples of the compound include methylamine, dimethylamine, ethylamine, n-propylamine, ethylmethylamine, n-butylamine, guanidine, ethylenediamine, hydrazine, hydroxylamine, or cyclic compounds such as piperidine and piperazine. Particularly preferred is gelatin extracted after addition of piperazine.

In the present invention, the ultraviolet absorber described in JP-A-8-69087 can be used.

In the present invention, Japanese Patent Application Laid-Open No. 8-160575
The color stain inhibitor represented by the general formula (A) described in (1) can be used.

In the present invention, when the magenta coupler represented by the general formula (2) is used, a method disclosed in JP-A-9-120 is used.
126 can be used.

In the present invention, Research Disclosure No. 1 may be used as the silver halide emulsion. 308119
(Hereinafter abbreviated as RD308119) can be used.

[0285] The following shows the places to be described.

[Item] [Page of RD308119] Iodine composition 993 IA Section Production method 993 IA and 994 E Crystal wall Normal crystal 999 IA Twin crystal 999 IA Section Epitaxial 933 I- Section A Halogen composition uniform 993 IB Section Not uniform 993 IB Section Halogen conversion 994 IC Halogen substitution 994 IC Section Metal content 994 ID Monodispersion 990 IF Section Solvent addition 996 Item IF Latent image formation position Surface 995 I-G Inside 995 I-G Applicable photosensitive material negative 995 I-H Positive (including internal fog particles) 995 I-H Item Emulsion mixed 995 I- Section I Desalting 995 II-A In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. Additives used in such a process are described in Research Disclosure No. 17643, no. 18716 and no. Three
08119 (hereinafter RD17643, RD18, respectively)
716 and RD308119). The places to be described are shown below.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-AA, B, C, D, 23 to 24 648 to 649 H, I, J section Supersensitizer 996 IV-AE, J section 23 to 24 648 to 649 Antifoggant 998 VI 24 to 25 649 Stabilizer 998 VI 24 to 25 649 Known methods usable in the present invention Are also described in Research Disclosure, supra. The relevant sections are described below.

[Items] [Page RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Brightener 998 V 24 Ultraviolet absorber 1003 VIII-I, XIII -C section 25-26 Light absorber 1003VIII 25-26 Light scattering agent 1003VIII Filter dye 1003VIII 25-26 Binder 1003IX 26 651 Static inhibitor 1006XIII 27 650 Hardener 1004X 26 651 Plasticizer 1006XII 27 650 Lubricant 1006XII 27650 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in the light-sensitive material) Item 1001 XXB Various couplers can be used in the present invention, and specific examples thereof are described in the above Research Disclosure. It is described in the catcher over. The relevant sections are described below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D Section VIIC to G Magenta coupler 1001 VII-D VIIC to G Cyan coupler 1001 VII-D VIIC to G Colored coupler 1002 VII-G Section VIIG DIR coupler 1001 VII-F Section VIIF BAR coupler 1002 VII-F Other useful residue release 1001 VII-F Coupler Alkali-soluble coupler 1001 VII-E The additives used in the present invention are described in RD308119XIV It can be added by a dispersion method or the like.

In the present invention, the aforementioned RD17643
Page 28, RD18716 pages 647 to 648, and RD3
The support described in XIX of 08119 can be used.

The light-sensitive material of the present invention includes RD3081 described above.
An auxiliary layer such as a filter layer or an intermediate layer described in the section 19VII-K can be provided.

The light-sensitive material of the present invention can be obtained by using the aforementioned RD30811
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

To develop the silver halide color light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (T
he Theory of The Photograph
ic Process Forth Edition)
Pages 291-334 and Journal of the American Chemical Society (Journal of the American Chemical Society)
the American Chemical So
publicly known developers described in Vol. 73, page 3, 100 (1951), and RD17643 pages 28 to 29, R.
The development can be carried out by a usual method described in D18716, page 615 and RD308119XIX.

[0294]

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

Example 1 On a cellulose triacetate film support provided with an undercoat layer, each layer having the following composition was sequentially applied from the support side to prepare Sample 101 of a silver halide multilayer color photographic light-sensitive material. .

[0296] The addition amount is the number of grams per 1 m ^2, unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes (shown by SD) are shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.05 CC-1 0.03 OIL-1 0.10 Gelatin 1.80 Second Layer (Low Sensitivity red-sensitive layer) Silver iodobromide emulsion b 0.36 Silver iodobromide emulsion c 0.12 SD-1 2.2 × 10 ^-5 SD-2 3.0 × 10 ^-5 SD-3 0 × 10 ^-4 SD-4 1.0 × 10 ^-4 SD-5 2.0 × 10 ^-4 C-1 0.35 CC-1 0.025 OIL-2 0.22 AS-2 0.001 Gelatin 0.80 Third layer (medium-speed red-sensitive layer) Silver iodobromide emulsion a 0.39 Silver iodobromide emulsion b 0.39 Silver iodobromide emulsion d 0.53 SD-1 1.7 × 10 ^-4 SD-4 2.5 × 10 ^-4 SD-5 3.0 × 10 ^-4 C-1 1.00 CC-1 0.08 DI-4 0.10 OIL-2 0.80 AS −2 0.005 Gelatin 2.30 Fourth layer (high-sensitivity red-sensitive layer) Silver iodobromide emulsion c 0.07 Silver iodobromide emulsion d 1.34 SD-1 1.5 × 10 ⁻⁵ SD -2 6.5 × 10 ^-5 SD-4 2.8 × 10 ^-4 SD-5 2.5 × 10 ^-5 C-1 0.28 CC-1 0.03 DI-4 0.03 OIL-2 0.28 AS-2 0.005 gelatin 1.10 Fifth layer (intermediate layer) F-1 0.01 Y-1 0.09 OIL-1 0.40 AS-1 0.30 gelatin 1.00 sixth Layer (low-sensitivity green color-sensitive layer) Silver iodobromide emulsion b 0.25 Silver iodobromide emulsion c 0.13 SD-6 6.0 × 10 ^-5 SD-7 5.5 × 10 ^-4 M- 1 0.22 CM-1 0.040 DI-3 0.007 OIL-1 0.24 AS-2 0.005 AS-3 0.05 Gelatin 0.75 7th layer (medium speed green Color-layer) Silver iodobromide emulsion e 1.09 SD-6 3.5 × 10 -5 SD-7 1.7 × 10 -4 SD-8 2.0 × 10 -4 SD-9 1.5 × 10 ^-4 SD-10 2.5 × 10 ^-5 M-1 0.26 CM-1 0.07 CM-2 0.03 DI-2 0.06 OIL-1 0.50 AS-3 0.02 AS -2 0.02 Gelatin 1.10 Eighth layer (highly sensitive green color-sensitive layer) Silver iodobromide emulsion c 0.06 Silver iodobromide emulsion f 1.20 SD-6 3.0 × 10 ^-5 SD -8 3.0 × 10 ^-4 SD-9 3.0 × 10 ^-5 SD-10 3.5 × 10 ^-5 M-1 0.070 CM-2 0.010 DI-2 0.01 OIL-1 0.30 AS-3 0.030 AS-2 0.010 Gelatin 1.00 Ninth layer (yellow filter layer) Yellow colloidal silver 0.10 OIL-1 0.20 AS-10 .20 X-1 0.06 Gelatin 0.85 Tenth layer (low-sensitivity blue-sensitive layer) Silver iodobromide emulsion g 0.23 Silver iodobromide emulsion h 0.29 Silver iodobromide emulsion i 0. 13 SD-11 2.5 × 10 ^-4 SD-12 5.5 × 10 ^-4 SD-13 1.5 × 10 ^-5 Y-1 0.96 DI-4 0.022 OIL-1 0.29 AS -2 0.005 X-1 0.08 Gelatin 1.80 Eleventh layer (highly sensitive blue-sensitive layer) Silver iodobromide emulsion j 0.60 Silver iodobromide emulsion h 0.26 SD-11 0 × 10 ^-5 SD-12 1.0 × 10 ^-4 SD-13 5.0 × 10 ^-5 Y-1 0.31 DI-1 0.01 OIL-1 0.10 AS-2 0.005 X -1 0.07 Gelatin 0.80 12th layer (first protective layer) Silver iodobromide emulsion k 0.30 UV-1 0.10 UV-2 0.06 Liquid paraffin 0.50 X-1 0.15 gelatin 1.50 13th layer (second protective layer) PM-1 0.15 PM-2 0.05 WAX-1 0.02 gelatin 0.56 The characteristics of the silver bromide emulsion are shown below (the average particle size is one side length of a cube having the same volume).

Emulsion No. Average particle size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide emulsion a 0.56 2.4 5.5 Silver iodobromide emulsion b 0.38 8.0 Octahedral twin iodine Silver iodide emulsion c 0.27 2.0 1.0 Silver iodobromide emulsion d 0.70 2.4 6.4 Silver iodobromide emulsion e 0.65 8.0 6.5 Silver iodobromide emulsion f0 .85 2.9 6.4 Silver iodobromide emulsion g 0.74 3.5 6.2 Silver iodobromide emulsion h 0.44 4.2 6.1 Silver iodobromide emulsion i 0.30 1.9 5.5 Silver iodobromide emulsion j 1.00 8.0 2.0 Silver bromoiodide emulsion k 0.03 2.0 1.0 The above sensitizing dyes were added to each of the above emulsions and ripened. Triphosphine selenide, sodium thiosulfate, chloroauric acid, potassium thiocyanate are added and chemically sensitized according to the usual method to optimize fog and sensitivity. Was.

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1, AF-2, inhibitors AF-3, AF-4, AF-
5. Hardeners H-1, H-2 and preservative Ase-1 were added. In addition, gelatin is subjected to a peroxide treatment during manufacture,
Gelatin extracted after adding piperazine during lime treatment was used (Ca ion concentration: 500 ppm / g gelatin, chloride ion concentration: 1,000 ppm / g gelatin).

The structure of the compound used for preparing the above sample is shown below.

[0301]

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[0302]

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[0303]

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[0304]

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[0305]

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[0306]

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[0307]

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[0309]

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[0310]

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[0311]

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[0312]

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<Preparation of Coating Solution for Eighth Layer> A hydrophobic photographically useful compound (M-
1, CM-2, DI-2, AS-3, AS-2)
Heat dissolved in ethyl acetate three times the total weight of IL-1 and the hydrophobic photographically useful compound, added to a 10% aqueous gelatin solution containing SU-4 in advance, and emulsified and dispersed using a high-speed rotary mixer. Thereafter, the mixture was mixed with a silver halide emulsion to prepare a coating solution.

A coating solution for the seventh layer was prepared in the same manner.

The coating solutions of the eighth layer and the seventh layer obtained were each 2
The sample was divided into two parts, one of which was stirred at 40 ° C. for 2 hours and then applied, and was coated with a sample 101a (the coating liquid condition a). The other was stirred at 40 ° C. for 30 hours and coated with a sample 101b (the coating liquid condition b). ).

Next, the M-layers of the eighth and seventh layers of the sample 101
Samples 102a, b-115a, b were prepared in the same manner except that DI, DI-2 and gelatin were changed as shown in Tables 1 and 2.
Was prepared. The compound of the general formula (1) is referred to as DI-2
With three times the number of moles.

Samples 116 and 117 were prepared in the same manner except that the ethyl acetate contained in the emulsified dispersion of the hydrophobic photographically useful compound used in Samples 107 and 109 was removed by a degassing method.

[0318]

[Table 1]

[0319]

[Table 2]

The sample obtained as described above was subjected to wedge exposure with white light, and subjected to the following color development processing,
The density of the green photosensitive layer was measured to obtain a characteristic curve.

<< Reference Color Development Processing >> Processing Step Processing Time Processing Temperature Replenishment Quantity * Color Development 3 min 15 sec 38 ± 0.3 ° C. 780 ml Bleaching 45 sec 38 ± 2.0 ° C. 150 ml Fixing 1 min 30 sec 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishment amount is shown per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter, and potassium hydroxide or 20% sulfuric acid was added. And adjust the pH to 0.06.

Color developing replenisher Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Add water to make 1 liter, and adjust the pH to 0.18 using potassium hydroxide or 20% sulfuric acid.

Bleaching solution 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 Add water to make 1 liter, and use aqueous ammonia or glacial acetic acid. Adjust the pH to 4.4.

Bleach replenisher Water 700 ml 1,3-Diaminopropanetetraacetate iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.4 using aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0.1 g Siloxane (L-77 manufactured by UCC) 0.1 g Ammonia water 0.5 ml After adding water to make 1 liter, the pH is adjusted to 8.5 with ammonia water or 50% sulfuric acid.

Fog, sensitivity, storage stability and production stability were evaluated from the characteristic curves of the obtained samples, and the results are summarized in Table 3.

For the measurement of fog, the minimum density (fog) was determined from the characteristic curve of the sample under the coating solution condition a. The sensitivity is represented by the reciprocal of the exposure amount that gives a density of minimum density + 0.3, and is shown as a relative value with the value of sample 101 being 100.

[0332] The evaluation of the storage stability was carried out by using four samples of the coating solution condition a.
After storing for 7 days in an environment of 0 ° C. and a relative humidity of 80%, exposure and color development were performed in the same manner, and the sensitivity of the green photosensitive layer was determined from the measured characteristic curve.
Are shown as relative values with the sensitivity of 100 as 100. The smaller the difference in sensitivity from the sample that is not subjected to the preservation treatment, the smaller the fluctuation during preservation and the more preferable.

Evaluation of production stability due to stagnation of coating liquid
From the characteristic curves obtained from the samples under the coating conditions a and b,
The sensitivities of the respective green photosensitive layers were measured, and the sensitivities were indicated as relative values with the sensitivity difference between Sample 101a and Sample 101b being 100. The smaller the value, the smaller the sensitivity fluctuation due to the stagnation of the coating liquid.

[0334]

[Table 3]

As is clear from the results in Table 3, the samples using the general formulas (1) and (2) and the deionized gelatin according to the present invention have low fog, high sensitivity, and little fluctuation during storage. It can be seen that the production stability is good. In addition, the level at which ethyl acetate contained in the emulsified dispersion was removed, sample 11
6, 117 show that the production stability is further excellent.

Example 2 As shown in Table 4, the seventh layer of the sample 107 of Example 1 was changed in the same manner as in Table 1 except that the kind of gelatin and the magenta coupler described in JP-A-10-30737 were changed. The samples 201a, b to 206 are obtained by the methods (a) and (b).
a and b were prepared.

The obtained sample was exposed and developed in the same manner as in Example 1, the characteristic curve of the green photosensitive layer was determined, and fog, sensitivity, granularity and production stability were evaluated.
Sensitivity and production stability were determined for sample 104 without storage treatment.
Is shown as a relative value with 100 as a reference. The results obtained are summarized in Table 4.

The granularity was evaluated by RMS granularity.

The magenta image at the image density point of fog of the characteristic curve of the green photosensitive layer + 0.5 was obtained by opening an area of 1800 μm.
The sample 104 was scanned with a microdensitometer having a m ² (slit width of 10 μm and a slit length of 180 μm) to obtain 1,000 times the standard deviation of the variation of the density value of 1,000 or more density measurement samplings. The relative values are shown below. The smaller the value, the better the granularity.

[0340]

[Table 4]

As is apparent from Table 4, the compound of the general formula (2) is used in the combination of the present invention, and the DIR compound of the general formula (1) according to the present invention and deionized gelatin are used. Thus, a silver halide photographic material excellent in fog, sensitivity, graininess and production stability was obtained.

Example 3 The third and fourth layers C-1 and DI of the sample 101 of Example 1 were obtained.
Samples 301a, b to 317a, b having different coating solution conditions were prepared in the same manner except that Compound-4 and gelatin were changed to the compounds according to the present invention as shown in Table 5. Incidentally, the compound according to the general formula (1) was replaced with twice the amount of moles of DI-4. Samples 318 and 318 were prepared in the same manner except that the ethyl acetate contained in the emulsified dispersion of the hydrophobic photographically useful compound used in Samples 309 and 313 was removed by a degassing method.
319 was produced.

[0343]

[Table 5]

The samples obtained as described above were exposed and developed in the same manner as in Example 1, and the characteristic curves of the red-sensitive layer of each sample were determined to evaluate fog, sensitivity, storage stability and production stability. The properties were evaluated, and the obtained results are summarized in Table 6.

The results are shown for Sample 10 not subjected to the preservation processing.
It is shown as a relative value where 1 is 100.

[0346]

[Table 6]

As is clear from Table 6, the silver halide photographic materials according to the present invention are excellent in fog, sensitivity, storage stability and production stability.

Further, from the results of Samples 318 and 319, it is understood that the production stability is further improved by removing the ethyl acetate contained in the emulsified dispersion.

Example 4 As shown in Table 8, the coating conditions of the third layer of the sample 302 described in Example 3 were changed in the same manner except that the kind of gelatin and the cyan coupler described in JP-A-10-30737 were changed. The samples 401a, b to 406 are obtained by the methods (a) and (b).
a and b were prepared.

The obtained sample was subjected to exposure and color development in the same manner as in Example 1 to determine the characteristic curve of the red photosensitive layer, and the fogging, sensitivity, granularity and production of the sample under the coating condition (a) were determined. The stability was evaluated, and the obtained results are shown in Table 7 as relative values with Sample 302 being 100.

[0351]

[Table 7]

As is clear from Table 7, the silver halide photographic light-sensitive material according to the present invention is excellent in fog, sensitivity, graininess and production stability.

Example 5 As shown in Table 8, the compound represented by the general formula (5) according to the present invention was added to the second layer of the sample 307 described in Example 3 in an amount of 0.0
Samples 501a, b-5 of coating solution conditions (a) and (b) were similarly prepared except that 15 g / m ^{2 was} added and gelatin was changed.
07a and 07b were prepared, and the obtained samples were evaluated for fog, sensitivity, storage stability, desilvering performance and production stability in the same manner as in Example 3. The results obtained are shown in Table 8 as relative values with the sample 101 not subjected to the preservation processing being taken as 100.

The evaluation of the desilverability was performed by the following method.

(Development condition 1: standard processing) Exposure and color development were performed in the same manner as in Example 3, and the amount of residual silver in the portion giving the maximum density of the red photosensitive layer was measured by a fluorescent X-ray silver amount analyzer. The quantification was performed.

(Developing condition 2: Fatigue bleaching solution treatment) Example 3
After performing exposure in the same manner as above, of the color development processing step, after performing the color development processing in the same manner except that the bleaching solution composition and the bleaching processing time of the bleaching step were changed, the maximum color development was performed in the same manner as above. The amount of residual silver in the density portion was determined.

The bleaching solution was changed as follows. 550 ml of the bleaching solution shown in Example 1 and 220 m of the color developing solution
Water was added to 1 l to make 1 liter, and the pH was adjusted to 4.4 with ammonia water or glacial acetic acid to prepare a fatigue bleaching solution. The bleaching time was 35 seconds.

With respect to the obtained results, the difference between the residual silver amount under the developing condition 2 and the residual silver amount under the developing condition 1 was shown as a relative value with the value of the sample 101 being 100. The smaller the value, the smaller the amount of residual silver and the better the desilverability.

[0359]

[Table 8]

As is clear from the results shown in Table 8, the silver halide photographic light-sensitive material according to the present invention is excellent in fog, sensitivity, storage stability, production stability and desilverability.

Example 6 In the sample 101 of Example 1, as shown in Table 9, DI-8 in the eighth layer was changed to the compound represented by the general formula (1) according to the present invention, and The coating conditions were the same except that the yellow filter dye represented by formulas (6) and (7) according to the present invention was added in an amount of 150 mg / m ² instead of the yellow colloidal silver used in the layer. (A),
Samples 601a, b to 614a, b of (b) were prepared.
In addition, the compound of the general formula (1) is 3 moles of DI-2.
Replaced by double amount.

The yellow filter dye is disclosed in World Patent 88/0
Solid dispersion is performed according to the method described in No. 4794,
It was added to the coating solution as a solid dispersion. That is, 1
100 g of the dye powder and the surfactant Triton X-200 (manufactured by Rohm & Haas) are added to 1 liter of water to a solid concentration of 10 g, and after pre-dispersion, a diameter of 0.1 g is obtained using Mitsubishi Diamond Fine Mill MD-2M. After dispersing for 20 hours using 5 mm zirconia beads, the zirconia beads were obtained by filtering off the zirconium oxide beads.

[0363]

[Table 9]

The samples thus obtained were exposed and developed in the same manner as in Example 1, and the characteristic curves of the green color-sensitive layer of each sample were determined. Fog, sensitivity, storage stability, production stability Was evaluated. Table 10 summarizes the obtained results.

[0365]

[Table 10]

As is clear from the results shown in Table 10, the silver halide photographic light-sensitive material according to the present invention is excellent in fog, sensitivity, storage stability and production stability.

[0367]

According to the present invention, a high-sensitivity, high-quality silver halide photographic material having excellent storage stability, production stability, and processing stability can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/388 G03C 7/388

Claims (8)

[Claims] 1. at least one red-sensitive layer,
In a silver halide photographic material having a photographic constituent layer composed of a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer, at least one of the photographic constituent layers is released from the active position of the coupler by a color development reaction. Thereafter, a compound having a development inhibiting property is formed, and after flowing out into the color developing solution, a DIR having a group having a property of being decomposed into a compound which does not substantially affect photographic properties at a coupling active position. A silver halide photographic light-sensitive material comprising at least one compound and at least one magenta coupler represented by the formula (2), wherein deionized gelatin is used in at least one of the photographic constituent layers. . Embedded image In the formula, R ²¹ represents a group capable of leaving by reaction with an oxidized form of a color developing agent, R ²² represents an aryl group, R ²³ represents a substituent, and n21 represents an integer of 1 to 5. n21 is 2 or more when R ²³ may be different even in the same. 2. at least one red-sensitive layer each;
In a silver halide photographic light-sensitive material having a photographic constituent layer composed of a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, at least one of the photographic constituent layers has at least one of the DIR compounds and a compound represented by the general formula (3) A silver halide photographic light-sensitive material comprising at least one cyan coupler represented by formula (I), wherein deionized gelatin is used in at least one of the photographic constituent layers. Embedded image In the formula, R ³¹ represents an alkyl group or a cycloalkyl group;
³² represents a group that can be substituted on a benzene ring. n31 is 0 to 4
Represents an integer. X ³¹ represents a group capable of leaving by reaction with an oxidized form of the color developing agent. 3. at least one red-sensitive layer each;
In a silver halide photographic light-sensitive material having a photographic layer composed of a green light-sensitive layer, a blue light-sensitive layer, and a non-light-sensitive layer, at least one of the photographic layers has at least one of the DIR compounds and a compound represented by the general formula (4) A silver halide photographic light-sensitive material comprising at least one cyan coupler represented by formula (I), wherein deionized gelatin is used in at least one of the photographic constituent layers. Embedded image In the formula, X represents a hydrogen atom or a group capable of leaving by coupling with an aromatic primary amine color developing agent. R ⁴¹ represents an aryl group or a heterocyclic group, and R ⁴² represents an aliphatic group or an aryl. Each group represented by R ⁴¹ or R ⁴² includes those having a substituent. 4. at least one red-sensitive layer,
In a silver halide photographic light-sensitive material having a photographic constituent layer composed of a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer, at least one of the photographic constituent layers is the same light-sensitive layer as at least one of the DIR compounds. A silver halide photographic light-sensitive material comprising a high-speed coupler and a low-speed coupler therein, and using deionized gelatin for at least one of the photographic constituent layers. 5. Each of at least one red-sensitive layer,
In a silver halide photographic light-sensitive material having a photographic layer composed of a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer, at least one of the photographic layers has at least one of the DIR compounds and a compound represented by the general formula (5) A silver halide photographic material comprising at least one of the compounds represented by the formula (I), wherein deionized gelatin is used in at least one of the photographic constituent layers. Formula (5) Cp- (T) m-S-Het In the formula, Cp represents a coupler residue, T represents a timing group, m represents 0 or 1, 2, and Het has a substituent. Represents a saturated heterocyclic ring which may be substituted. However, the substituent substituted for Het never contains a carboxy group. 6. at least one red-sensitive layer each;
In a silver halide photographic light-sensitive material having a photographic constituent layer composed of a green light-sensitive layer, a blue light-sensitive layer and a non-light-sensitive layer, at least one of the photographic constituent layers comprises at least one of the DIR compounds and a compound represented by the general formula (6) A silver halide photographic light-sensitive material comprising at least one of the yellow filter dyes represented by (7) to (7), wherein deionized gelatin is used in at least one of the photographic constituent layers. Embedded image In the formula, A represents an acidic nucleus, L ⁶¹ , L ⁶² and L ⁶³ represent a methine group, n61 represents 0, 1 or 2, and Z is bonded to the nitrogen atom shown in the formula to form a heterocyclic residue. Y represents -C (R ⁶¹ ) (R ⁶² ), which represents a group of non-metallic atoms necessary for forming a group;
And a substituent or a heterocyclic residue represented by (R ⁶³ ). −
In the substituent represented by C (R ⁶¹ ) (R ⁶² ) (R ⁶³ ), R ⁶¹ and R ⁶² represent a hydrogen atom or an alkyl group, and these may be bonded to each other to form a ring. R ⁶³
Represents a hydrogen atom or an electron-withdrawing group having a Hammett σp value of 0.3 or more. However, R ⁶¹ , R ⁶² and R ⁶³ do not simultaneously represent a hydrogen atom. Further, the dye represented by the general formula (6) has at least one carboxyl group or alkylsulfonamide group in an aromatic ring portion in its molecular structure. Embedded image In the formula, R ⁷¹ and R ⁷² each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. X is -CN,
-COOR ⁷³ , -CONR ⁷³ R ⁷⁴ , -SO ₂ NR
⁷³ R ⁷⁴ , —COR ⁷³ , —SO ₂ R ⁷³ or —CF ₃ , wherein R ⁷³ and R ⁷⁴ are each a hydrogen atom, an alkyl group,
Represents an alkenyl group, an aryl group or a heterocyclic group.
L ⁷¹ , L ⁷² and L ⁷³ represent a methine group, and n represents an integer of 0, 1 or 2. 7. An oil-in-water emulsion dispersion containing at least one hydrophobic photographically useful compound, wherein at least one layer contains a dispersion substantially free of a low-boiling-point solvent. Item 7. The silver halide photographic light-sensitive material according to any one of Items 1 to 6. 8. The deionized gelatin having a chloride ion concentration of 500 ppm or less and a calcium ion concentration of 20 ppm or less.
8. The silver halide photographic material according to claim 1, wherein the content is 0 ppm or less.