JPH1195385A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material enhanced in prevention of occurrence of muddy colors and reduction of minimum density without deteriorating image storage stability of a color-developed image and also superior in prevention of rise of fog due to storage with the lapse of time and deterioration of sensitivity by incorporating a specified reducing agent for color development and a specified dye-forming coupler and a specified compound in one of photographic constituent layers. SOLUTION: One of the photographic constituent layers contains the reducing agent for color development represented by formula I and the dye-forming coupler and further the compound represented by formula II or the like, and in formulae I and II, R<1> is an aryl or heterocyclic group or the like; R<2> is an alkyl or alkenyl or heterocyclic group or the like; X is a -SO2 -, -CO-, or -COCO- group or the like; and each of R<41> -R<46> is an H or halogen atom or a hydroxy, cyano, sulfo, or alkyl group or the like, but at least one of R<41> and R<43> and at least one of R<44> and R<46> are a hydroxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method, and more particularly, to a silver halide color photographic light-sensitive material incorporating (containing) a color-forming reducing agent and a dye-forming coupler and a color. The present invention relates to an image forming method.

[0002]

2. Description of the Related Art Silver halide photographic materials have excellent characteristics such as high sensitivity, excellent gradation and large-scale processing. Used. With this feature, further processing speed,
Simplification and reduction of the amount of waste liquid are desired.

[0003] In ordinary silver halide color photography, a dye image is formed by a coupling reaction between an oxidized aromatic primary amine and a coupler corresponding to the development of silver halide. As commonly used couplers, open-chain ketomethylene compounds, pyrazolone compounds, pyrazoloazole compounds, phenol compounds, naphthol compounds and the like are known. The formation reaction of the dye image is achieved by immersing the exposed silver halide color photographic material in a developer containing an aromatic primary amine at a predetermined temperature for a predetermined time. Is harmful to the human body, and the treatment of a used developer containing such a harmful substance is also a serious problem.
In addition, in order to obtain a stable quality color image, it is necessary to strictly control the temperature, concentration, and degree of fatigue of the developer.

As one means for solving such a problem, there is a method of incorporating an aromatic primary amine developing agent or a precursor thereof into a silver halide color photographic light-sensitive material. Examples of the main drug include U.S. Pat. Nos. 803,783, 3,342,597, 3,719,492, 4,060,418, British Patent 1,069,061, West German Patent 1, and the like. 159,75
No.8, Japanese Patent Publication No. 58-14671 and No. 58-14672
And compounds described in JP-A-57-76543 and JP-A-59-81643. However, silver halide color photographic light-sensitive materials containing these aromatic primary amine developing agents or their precursors have the problem of poor color developability. Apart from this, a method of incorporating a sulfonylhydrazine type developing agent in a silver halide color photographic light-sensitive material has been disclosed as a means not using an aromatic primary amine which is a harmful substance. No. 491, 565, 165, 572, 0
No. 54, 593, 110, JP-A-7-134355
And the compounds described in JP-A-8-227131 and the like. However, even with these developing agents, long-term development at a high temperature is required to obtain a sufficient color density. In order to further improve the color developing property, a carbamoylhydrazine type developing agent described in JP-A-8-286340,
Although carbonyl hydrazone type developing agents described in JP-A-234390 have been proposed, although the color developability is improved, the stability of the formed dye image against heat and light is insufficient.
In addition, there is a problem that storage stability over time is low.

Auxiliary developing agents and precursors thereof are preferably used in a silver halide color photographic light-sensitive material containing (containing) a color-forming reducing agent and a dye-forming coupler.
The use of an auxiliary developing agent or the like is a very effective means for obtaining a high color density, but the auxiliary developing agent and its oxidized form easily diffuse between layers, causing a problem of causing color turbidity in the obtained color image. is there. Therefore, when an auxiliary developing agent or the like is used, the non-photosensitive layer (intermediate layer) located between silver halide emulsion layers having different color sensitivity is thickened.
Alternatively, a compound (reducing agent) capable of deactivating the oxidized form of the auxiliary developing agent needs to be contained in the intermediate layer.

Further, such a reducing agent can deactivate the oxidized form of the auxiliary developing agent that is unnecessarily generated, and thus is effective in lowering the minimum density. For such a purpose, it is effective to include such a reducing agent in the photosensitive silver halide emulsion layer.

As a reducing agent (a compound capable of deactivating an oxidized form of an auxiliary developing agent) used for such a purpose, a hydroquinone derivative having a ballast group substituted at the 2-position or 5-position has been used. Although this compound is effective from the viewpoint of preventing color turbidity and reducing the minimum density as described above, it has a disadvantage in that the image storability of the processed sample is deteriorated.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to prevent color turbidity and reduce the minimum density without deteriorating the image storability of a color image, and to store (raw) aging before development. An object of the present invention is to provide a silver halide color photographic light-sensitive material and a color image forming method which incorporate (contain) a color-forming reducing agent and a dye-forming coupler, which are excellent in prevention of increase in fog and reduction in sensitivity due to the above.

[0009]

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

[0010] 1. In a silver halide color photographic light-sensitive material having a photographic layer containing at least one light-sensitive silver halide emulsion layer on a support, at least one of the following general formulas (I) And at least one kind of a dye-forming coupler represented by the formula: wherein at least one compound represented by the following general formula [1] or [2] is contained in any one of the photographic constituent layers. A silver halide color photographic light-sensitive material comprising:

[0011]

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[Wherein, R ¹ represents an aryl group or a heterocyclic group, and R ² represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, or —OM (M represents a hydrogen atom or a metal atom). . X is _{-SO 2 -, - CO -,} - COCO
-, - COO -, - CON (R 3) -, - COCOO
^{-, - COCON (R 3)} - or -SO ₂ N (R ³⁾ - represents a. Here, R ³ represents a hydrogen atom or a group having the same meaning as R ² . ]

[0013]

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Wherein R ^{41 to} R ⁴⁶ each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group; Group, sulfonyl group, acyl group, arylcarbonyl group,
Represents an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acyloxy group, or an arylcarbonyloxy group. However, R ⁴¹ and R ⁴³
And at least one of R ⁴⁴ and R ⁴⁶ represents a hydroxyl group. R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ ,
R ⁴⁴ and R ⁴⁵ , and R ⁴⁵ and R ⁴⁶ may combine with each other to form a ring. X represents a divalent linking group, and n represents 1 or 0. ]

[0015]

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[Wherein R ⁴⁷ and R ⁴⁸ are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, an acyl group, an arylcarbonyl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Represents an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acyloxy group, or an arylcarbonyloxy group, and R ⁴⁷ and R ⁴⁸ may combine with each other to form a ring. Y is -CO- or -SO ₂ - represents a. R ⁴⁹ represents a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, or amino group. ] 2. 2. The silver halide color photographic light-sensitive material according to 1, wherein the color-forming reducing agent represented by the general formula (I) is a color-forming reducing agent represented by the following general formula (II) or (III). material.

[0017]

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[In the formula, Z ¹ and Z ² each represent an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each represent hydrogen. Represents an atom or a substituent. However,
The Hammett's substituent constant σp value of R ¹¹ , R ¹³ and R ¹⁵ and R
The sum of Hammett's substituent constant σm values of ¹² and R ¹⁴ is 0.8
0 to 3.80. R ²⁰ represents a heterocyclic group. ] 3. The halogenation according to 2, wherein the color-forming reducing agent represented by the general formula (II) or (III) is a color-forming reducing agent represented by the following general formula (IV) or (V). Silver color photographic light-sensitive material.

[0019]

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[In the formula, R ¹⁶ and R ¹⁷ each represent a hydrogen atom or a substituent, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ^15
20 has the same meaning as in formulas (II) and (III), respectively. ] 4. The halogenation according to 3, wherein the color-forming reducing agent represented by the general formula (IV) or (V) is a color-forming reducing agent represented by the following general formula (VI) or (VII). Silver color photographic light-sensitive material.

[0021]

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[In the formula, R ²⁶ and R ²⁷ each represent a hydrogen atom or a substituent, and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group. Group, sulfamoyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group,
Represents a trifluoromethyl group, a halogen atom, an acyloxy group or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of R ²¹ , R ²³ and R ²⁵ and the Hammett's substituent constant σm value of R ²² and R ²⁴ is 1.20 to 3.80. Q
Represents a nonmetallic atomic group necessary for forming a 5- to 8-membered nitrogen-containing heterocyclic ring together with C. ] 5. 5. The silver halide color photographic light-sensitive material according to any one of items 1 to 4, wherein the compound represented by formula (1) or (2) has an I / O value of 1.5 or less. .

6. 6. The compound according to any one of 1 to 5, wherein the compound represented by the general formula [1] or [2] is contained in a layer different from the layer containing the photosensitive silver halide. Silver halide color photographic light-sensitive material.

[7] The compound represented by the general formula [1] or [2] is contained in a layer which is located in the middle of the photosensitive silver halide emulsion layers having different color sensitivity and does not contain the photosensitive silver halide. 7. The silver halide color photographic light-sensitive material as described in any one of items 1 to 6, above.

8. The reaction is carried out in the presence of a color-forming reducing agent represented by the general formula (I) and at least one dye-forming coupler, and at least one compound represented by the general formula [1] or [2]. Color image forming method.

Hereinafter, the present invention will be described in detail.

The color-forming reducing agent represented by the general formula (I) will be described.

The color-forming reducing agent represented by the general formula (I) used in the present invention reacts directly with the exposed silver halide in an alkaline solution or is oxidized, or is oxidized by the exposed silver halide. And a compound which is oxidized by an oxidation-reduction reaction with the developed auxiliary developing agent, and whose oxidized product reacts with a dye-forming coupler to form a dye. Hereinafter, the structure of the color-forming reducing agent represented by the general formula (I) will be described in more detail.

In the general formula (I), R ¹ represents an aryl group or a heterocyclic group which may have a substituent. The aryl group represented by R ¹ preferably has 6 to 14 carbon atoms,
Examples include phenyl and naphthyl.

The heterocyclic group represented by R ¹ is preferably a saturated or unsaturated 5- to 7-membered ring containing at least one of nitrogen, oxygen, sulfur and selenium. These may be condensed with a benzene ring or a heterocyclic ring. Specific examples of the heterocyclic group include furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl, pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, and quinazolinyl. Prinyl, pteridinyl, azepinyl, benzoxepinyl and the like.

Examples of the substituent which the aryl group or the heterocyclic group may have include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group and an alkylthio group. An arylthio group, a heterocyclic thio group, an acyloxy group, an acylthio group,
Alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group, arylamino group, amide group,
Alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylcarbamoyl group, carbamoylcarbamoyl group, sulfonylcarbamoyl group , Sulfamoylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfamoyl group, acylsulfamoyl group, carbamoylsulfamoyl group, halogen atom, Examples include a nitro group, a cyano group, a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, a mercapto group, an imide group, and an azo group.

R ² is an alkyl group which may have a substituent,
Represents an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. The alkyl group preferably has 1 to 1 carbon atoms.
6, linear, branched or cyclic, for example, methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl,
Cyclopentyl, cyclooctyl and the like can be mentioned.

The alkenyl group is preferably a chain or cyclic one having 2 to 16 carbon atoms, for example, vinyl, 1-
Octenyl and cyclohexenyl.

The alkynyl group preferably has 2 to 16 carbon atoms, such as 1-butynyl and phenylethynyl.

The aryl group and the heterocyclic group represented by R ² include those described for R ¹ above.

Examples of the substituent which the alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group may have include those described above for the substituent of R ¹ .

X is -SO _2- , -CO-, -CO
CO -, - COO -, - CON (R 3) -, - COCO
O—, —COCON (R ³ ) — or —SO ₂ N (R ³ ) —
Is mentioned. Here, R ³ is a hydrogen atom or a group described for R ² . Among these groups, -CO-, -CONH
(R ³ ) — and —COO— are preferable, and —CONH (R ³ ) — is particularly preferable in that color developing properties are excellent.

Among the compounds represented by the general formula (I), the compounds represented by the general formulas (II) and (III) are preferable.
The compounds represented by the general formulas (IV) and (V) are more preferable, and the compounds represented by the general formulas (VI) and (VII) are further preferable. Hereinafter, the compounds represented by formulas (II) to (VII) will be described in detail.

In the general formulas (II) and (III), Z ¹ and Z ² each represent an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. The acyl group preferably has 1 to 50 carbon atoms, and more preferably has 2 to 40 carbon atoms. Specific examples include acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, octanoyl,
-Hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4-dodecyloxybenzoyl, 2-hydroxymethylbenzoyl,
3- (N-hydroxy-N-methylaminocarbonyl)
And propanoyl. The case where Z ¹ and Z ² are carbamoyl groups will be described in detail in the general formulas (VI) to (VII).

The alkoxycarbonyl group and the aryloxy group are preferably carbonyl groups having 2 to 50 carbon atoms, more preferably 2 to 40 carbon atoms. Specific examples include methoxycarbonyl, ethoxycarbonyl, i-butyloxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, 4-octyloxyphenoxycarbonyl, 2-hydroxymethylphenoxycarbonyl, and 2-dodecyl And groups such as oxyphenoxycarbonyl.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or a substituent. Examples of the substituent include those having 1 to 5 carbon atoms.
0 linear or branched, chain or cyclic alkyl group (trifluoromethyl, methyl, ethyl, propyl, heptafluoropropyl, i-propyl, butyl, t-butyl, t-butyl)
-Pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), having 2 to 5 carbon atoms
0 linear or branched, chain or cyclic alkenyl group (vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), alkynyl group having 2 to 50 carbon atoms (ethynyl, 1-
Propynyl, etc.), aryl group having 6 to 50 carbon atoms (phenyl, naphthyl, anthryl, etc.), acyloxy group having 1 to 50 carbon atoms (acetoxy, tetradecanoyloxy, benzoyloxy, etc.), carbamoyloxy having 1 to 50 carbon atoms Group (N, N-dimethylcarbamoyloxy and the like), a carbonamide group having 1 to 50 carbon atoms (formamide, N-
Methylacetamide, acetamide, N-methylformamide, benzamide, etc.), a sulfonamide group having 1 to 50 carbon atoms (methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.), Carbamoyl groups (N-methylcarbamoyl, N, N-diethylcarbamoyl, N
-Mesylcarbamoyl, etc.), a sulfamoyl group having 0 to 50 carbon atoms (N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl, etc.), and a carbon number of 1 To 50 alkoxy groups (methoxy, propoxy, i-propoxy, octyloxy, t-octyloxy, dodecyloxy, 2
-(2,4-di-t-pentylphenoxy) ethoxy and the like), an aryloxy group having 6 to 50 carbon atoms (phenoxy, 4-methoxyphenoxy, naphthoxy and the like), and an aryloxycarbonyl group having 7 to 50 carbon atoms (phenoxy) Carbonyl, naphthoxycarbonyl, etc.), having 2 to 50 carbon atoms
An alkoxycarbonyl group (methoxycarbonyl, t-
Butoxycarbonyl), an acylsulfamoyl group having 1 to 50 carbon atoms (N-tetradecanoylsulfamoyl,
N-benzoylsulfamoyl and the like, an alkylsulfonyl group having 1 to 50 carbon atoms (such as methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl and 2-hexyldecylsulfonyl), and an arylsulfonyl group having 6 to 50 carbon atoms (benzene) Sulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl and the like), an alkoxycarbonylamino group having 2 to 50 carbon atoms (such as ethoxycarbonylamino), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (phenoxycarbonylamino and naphtho) Xycarbonylamino, etc.), carbon number 0
-50 amino groups (amino, methylamino, diethylamino, di-i-propylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, mercapto group, 1-50 carbon atoms Alkylsulfinyl group (methanesulfinyl, octanesulfinyl, etc.), arylsulfinyl group having 6 to 50 carbon atoms (benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl, etc.), carbon number 1
To 50 alkylthio groups (methylthio, octylthio,
Cyclohexylthio, etc.), an arylthio group having 6 to 50 carbon atoms (phenylthio, naphthylthio, etc.), 1 to 5 carbon atoms
Ureide group (3-methylureide, 3,3-dimethylureide, 1,3-diphenylureide, etc.), carbon number 2
To 50 heterocyclic groups (including at least one or more nitrogen, oxygen and sulfur as a hetero atom, a 3- to 12-membered monocyclic or condensed ring, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), carbon number 1
To 50 acyl groups (acetyl, benzoyl, trifluoroacetyl, etc.), a sulfamoylamino group having 0 to 50 carbon atoms (N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), and a carbon number of 3 to 50 silyl groups (such as trimethylsilyl, dimethyl-t-butylsilyl, and triphenylsilyl), and halogen atoms (such as fluorine, chlorine, and bromine).

The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be bonded to each other to form a condensed ring.

The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 34 or less.
It is as follows. Further, it is preferably at least one.

In the general formula (II), R ¹¹ , R ¹² , R ¹³ ,
Regarding R ¹⁴ and R ¹⁵ , the Hammett's substituent constant σp value of R ¹¹ , R ¹³ and R ^{15 and} the Hammett's substituent constant σ of R ¹² and R ¹⁴
It is preferable that the sum of m values is 0.80 to 3.80.

Further, R ²¹ , R ²² , R in the general formula (VI)
²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group , An acylthio group or a heterocyclic group, which may further have a substituent and may combine with each other to form a condensed ring. These specific examples are the same as those described for R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ . However, in the general formula (VI), R ²¹ , R ²³ , R
The sum of the Hammett's substituent constant σp value of ^{25 and} the Hammett's substituent constant σm value of R ²² and R ²⁴ is preferably 1.20 to 3.80, more preferably 1.50 to 3.80,
More preferably, it is 1.70 to 3.80.

The Hammett's substituent constants σp and σm are described, for example, in Naoki Inamoto, “Hammet Rule—Structure and Reactivity—” (Maruzen); Reaction V ", p. 2605 (Maruzen), Tadao Nakaya," Explanation of Theoretical Organic Chemistry ", p.
Chemical Review, 91, pp. 165-195 (19
(1991) and other detailed books.

In the general formulas (IV) and (V), R ¹⁶ ,
R ^17, formula (VI), each R ^{2 6,} R ²⁷ in (VII), represents a hydrogen atom or a substituent, specific examples of the substituent, the same as those described for the R ¹¹ to R ¹⁵ Meaning is preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted hetero group having 1 to 50 carbon atoms. A cyclic group, more preferably R ¹⁶ , R
^At least one of ¹⁷ and at least one of R ²⁶ and R ²⁷ are a hydrogen atom.

R ²⁰ in formulas (III) and (V) represents a heterocyclic group. Preferred heterocyclic groups are heterocyclic groups having 1 to 50 carbon atoms. The heteroatom contains at least one nitrogen, oxygen, sulfur atom or the like, and is a saturated or unsaturated 3- to 12-membered ring (preferably 3 to 12). -8-membered ring) or a condensed ring, specific examples of which are furan, pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole , Pyrrole, oxazole, thiazole, quinazoline, isothiazole, pyridazine, indole, pyrazole, triazole, quinoxaline and the like.

These heterocyclic groups may have a substituent, and preferably have at least one electron-withdrawing group. Here, the electron-withdrawing group means a group having a positive Hammett σp value.

When the color-forming reducing agent of the present invention is incorporated in a light-sensitive material, Z ¹ , Z ² , R of the general formulas (II) to (VII) are used.
^{11 ~R 15, R 16, R} 17, R 21 ~R 25, R 26, preferably has a ballast group in at least one group of R ^27. Examples of the heterocycle completed by Q are specific compound examples (1
0) to (41).

The following are typical examples of the compound represented by formula (I) used in the present invention, but the invention is not limited thereto.

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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In addition to the color-forming reducing agents of the general formulas (II) to (VII), compounds represented by the following general formula (VIII) are also preferably used.

[0066]

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In the formula, each of R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ represents a hydrogen atom, a halogen atom or a monovalent substituent,
M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a nitrogen-containing organic base. n is 1
Or 2 is represented.

Examples of the substituent represented by R ^{31 to} R ³⁵ include the same substituents as R ^{11 to} R ¹⁵ described in the formula (II).

The alkali metal atom represented by M includes potassium, sodium, lithium and the like, the alkaline earth metal atom includes calcium and barium, and the nitrogen-containing organic base includes pyridine, piperazine and triethylamine. Can be

The following formula (VIII) used in the present invention
Specific examples of the compound are shown below, but it should not be construed that the invention is limited thereto.

[0071]

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[0072]

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[0073]

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[0074]

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Next, the compound represented by formula (1) or (2) will be described.

In the present invention, the compound represented by the general formula [1] or [2] is a hydroquinone derivative known in the art. First, the compound represented by the general formula [1] is a compound disclosed in JP-A-2-32338 as a reducing agent used in combination with a reducible dye-providing compound. In the general formula [1], R ^{41 to} R ⁴⁶ each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a sulfo group, a carboxyl group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, Sulfamoyl group, sulfonyl group, acyl group, arylcarbonyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, acyloxy group,
Or an arylcarbonyloxy group. Specific examples of these substituents are described in JP-A-2-32338,
On page 3 in detail. Among them, at least one of R ⁴¹ and R ⁴³ and at least one of R ⁴⁴ and R ⁴⁶ represent a hydroxyl group. R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R
⁴⁴ and R ⁴⁵ , and R ⁴⁵ and R ⁴⁶ may combine with each other to form a ring. X represents a divalent linking group, and n represents 1 or 0
Represents

The compound represented by the general formula [2] is
As a reducing agent used as a color mixture inhibitor, JP-A No. 2-6
No. 4633. In the general formula [2], R ⁴⁷ and R ⁴⁸ each represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, an acyl group, an arylcarbonyl group, and an alkoxy group. Represents an aryloxy group, an alkylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acyloxy group, or an arylcarbonyloxy group;
⁴⁷ and R ⁴⁸ may combine with each other to form a ring. Y is-
CO- or -SO ₂ - represents a. R ⁴⁹ represents a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, or amino group. Specific examples of these substituents are described in detail in page 3 of JP-A-2-64633.

In the present invention, the compound represented by the general formula [1] or [2] is preferably a compound which hardly moves between coating layers during both coating and development. Therefore, it is preferable that these compounds are ballasted with a long-chain alkyl group or the like.
The inventor has found that an I / O value is a good index, especially as a parameter of the difficulty of migration of these compounds between layers. The I / O value is a concept described in detail in “Organic Conceptual Diagram” (by Yoshio Koda, published by Sankyo), and is often cited in the art as an index indicating the organic and inorganic properties of organic compounds. In the present invention, the general formula [1]
Alternatively, as the compound represented by [2], a highly organic compound having an I / O value of 1.5 or less, preferably 1 or less is selected and used.

As a layer to which the compound represented by the general formula [1] or [2] is added, a layer containing no silver halide emulsion is selected. Such layers include an undercoat layer, an intermediate layer,
Although there is a protective layer and the like, any layer may be selected. In order to further enhance the effect of the present invention, it is preferable not to make the layer containing the compound represented by the general formula [1] or [2] adjacent to the layer containing the silver halide emulsion.

The addition amount of the compound represented by the general formula [1] or [2] has a wide range, but is preferably 0.001 to 10 times, more preferably 0.01 to 1 times, the mole of the dye-donating compound. It is molar times. Specific examples of the compound represented by the general formula [1] or [2] are shown below, but the compound of the present invention is not limited to the following specific examples.

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[0082]

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In the present invention, an auxiliary developing agent can be preferably used. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons to silver halide, and the auxiliary developing agent in the present invention is preferably represented by the general formula (B-1) or the general formula (B-2). Is an electron-emitting compound according to the Kendall-Peltz rule represented by Among them, those represented by (B-1) are particularly preferred.

[0086]

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In the general formulas (B-1) and (B-2),
R ^{51 to} R ⁵⁹ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

R ^{55 to} R ⁵⁹ are a hydrogen atom, a halogen atom, a cyano atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic oxy group. Group, silyloxy group, acyloxy group, amino group, anilino group, heterocyclic amino group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, hydroxyl group,
Nitro group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group,
Cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group,
Represents a sulfamoylamino group, an alkylsulfinyl group, an arenesulfinyl group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, a sulfo group, a phosphinoyl group, and a phosphinoylamino group.

Q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different from each other. R ⁶⁰ represents an alkyl group or an aryl group.

Specific examples of the compound represented by formula (B-1) or (B-2) are shown below, but the auxiliary developing agent used in the present invention is not limited to these specific examples.

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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Next, the dye-forming coupler (hereinafter, also referred to as a coupler) used in the present invention will be described.

As the coupler used in the silver halide photographic light-sensitive material of the present invention, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Although any compound obtained can be used, particularly typical ones are a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500 to 6
Representatively, a magenta dye-forming coupler having a spectral absorption maximum wavelength at 00 nm and a cyan dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm are representative.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include those represented by the general formulas (C-I) and (C-I) described in JP-A-4-114154, page 5, lower left column. Couplers represented by II) can be mentioned. Specific compounds are listed in the lower right column of page 5 to lower left column of page 6 in the same publication, CC-1 to CC-9.
Can be mentioned.

The magenta couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention include those represented by the general formulas (MI) and (M-I) described in JP-A-4-114154, page 4, upper right column. Couplers represented by II) can be mentioned. Specific compounds are listed in the lower left column of page 4 to the upper right column of page 5 in the same publication, MC-1 to MC-.
11 can be mentioned.
More preferred among the above magenta couplers are couplers represented by the general formula (MI) described in the upper right column on page 4 of the specification of the same gazette.
The coupler of I) in which the RM is a tertiary alkyl group is particularly preferred because of its excellent light resistance. MC-8 to MC-11 described in the upper column on page 5 of the publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail depiction power, and thus are preferable.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (YI) described in the upper right column of page 3 of JP-A-4-114154. Couplers can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Above all, a coupler in which RY1 of the general formula [Y-1] of the same publication is an alkoxy group or a coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone. preferable. Among these, particularly preferred examples of the compounds are described in YC-8 and YC-9 described in the lower left column of page 4 of JP-A-4-114154, and in JP-A-6-67388, pages 13-14. No
Compounds represented by (1) to (47) can be mentioned. Further, the most preferred compound is described in JP-A-4-81847.
It is a compound represented by the general formula [Y-1] described in the specification of Japanese Patent Application Laid-Open No. 1-page and the specification of Japanese Patent Application Laid-Open No. 11-17.

Dye-forming couplers used in the present invention include dye-forming couplers described in JP-A-9-152691, pages 28 to 46, and the like.

The couplers used in the present invention can be used alone or in combination of two or more, and can be used in combination with other types of couplers.

The color-forming reducing agent used in the present invention is used in an amount of 0.01 to 1 per color-forming layer in order to obtain a sufficient color-forming density.
It is preferable to use 0 mmol / m ² . A more preferred amount is 0.05 to 5 mmol / m ² , and a particularly preferred amount is 0.1 to 1 mmol / m ² . This range is preferred in that a sufficient color density can be obtained. The preferred amount of the coupler in the coloring layer in which the color-forming reducing agent of the present invention is used is 0.0
It is 5 to 20 times, more preferably 0.1 to 10 times, particularly preferably 0.2 to 5 times. This range is preferred in that a sufficient color density can be obtained.

The color light-sensitive material of the present invention is basically formed by coating a support with a photographic constituent layer comprising at least one hydrophilic colloid layer. , A coupler for forming a dye, and a reducing agent for forming a color. In the most typical embodiment, the dye-forming coupler and the color-forming reducing agent used in the present invention are added to the same layer. These components are preferably added to a silver halide emulsion layer or a layer adjacent to the silver halide emulsion layer in the light-sensitive material, and particularly preferably added to a silver halide emulsion layer.

In order to incorporate the color-forming reducing agent represented by the general formula (I) and the coupler of the present invention, a conventional method, for example, a method using a known solvent such as dibutyl phthalate or tricresyl phosphate and a high boiling point solvent such as acetic acid is used. After dissolving in a mixture of low-boiling solvents such as butyl and ethyl acetate, or a solvent containing only low-boiling solvents, mix with a gelatin aqueous solution containing a surfactant, and then use a high-speed rotary mixer or colloid mill or ultrasonic disperser. After emulsifying and dispersing by using the method described above, a method of directly adding the emulsion to the emulsion can be adopted. Alternatively, the emulsified dispersion may be set, then cut into pieces, washed with water, and then added to the emulsion.

In the present invention, the coupler may be separately dispersed in the high-boiling solvent and the above-mentioned dispersion method and added to the silver halide emulsion. Alternatively, both compounds may be dissolved simultaneously, dispersed and added to the emulsion. Is preferred.

The amount of the high boiling point solvent to be added is preferably 0.01 to 10 g, more preferably 0.1 to 5.0 g, per 1 g of the coupler represented by formula (C) of the present invention.
Range.

The silver halide emulsion used for the light-sensitive material of the present invention is generally subjected to physical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643, no. 187
16 and No. 308119 (hereinafter referred to as RD17
643, abbreviated as RD18716 and RD308119)
It is described in.

[0111] The places to be described are shown below.

[Item] [Page RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A section 23 648 Spectral sensitizer 996 IV-A, B, C, D, 23-24 648-9H , I, J Section Supersensitizer 996 IV-AE, J Section 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Chemical sensitization of emulsion used in the present invention More specifically, the sensitization may be, for example, a chemical containing sulfur capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, or gold. A noble metal sensitization method using another noble metal compound or the like can be used alone or in combination.

In the present invention, for example, a chalcogen sensitizer can be used as the chemical sensitizer, and among them, a sulfur sensitizer and a selenium sensitizer are preferable.

Examples of the sulfur sensitizer include thiosulfate,
Allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, p-trienethiosulfonate, rhodanine and the like can be mentioned.

Others are described in US Pat. Nos. 1,574,944, 2,410,689, and 2,2,211.
Nos. 78,947, 2,728,668, 3,501,313, and 3,653.
No. 6,955, West German Application Publication (OLS) 1,42
2,869, JP-A-56-24937,
Sulfur sensitizers described in JP-A-55-45016 and the like can also be used.

The amount of the sulfur sensitizer to be added varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains.
It is preferably about 10 ^-7 mol to about 10 ^-1 mol per mol.

As the selenium sensitizer, aliphatic isocyanates such as allyl isoselenocyanate, selenoureas, seleno selenides, selenides such as diethyl selenide and the like can be used. Specific examples thereof are described in US Pat. Nos. 1,574,944 and 1,602,
No. 592 and No. 1,623,499. Further, reduction sensitization can be used in combination.

Examples of the reduction sensitizer include stannous chloride, thiourea dioxide, hydrazine, polyamine and the like.
Also, a noble metal compound other than gold, for example, a palladium compound or the like can be used in combination.

The silver halide grains of the emulsion used in the present invention are preferably chemically sensitized by a gold compound.

The gold compound preferably used in the present invention may have a gold oxidation number of +1 or +3, and various gold compounds are used.

Representative examples include potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, and gold selenide. .

The amount of the gold compound to be added varies depending on various conditions. As a guide, the amount is from 10 ^-8 mol to 10 ^-1 mol, preferably from 10 ^-7 mol to 10 ^-1 mol, per mol of silver halide.
^-2 .

These compounds may be added at any time during the formation of silver halide grains, during physical ripening, during chemical ripening, and after the completion of chemical ripening.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion. The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer.

Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, and a coupling reaction with a colored coupler, a competing coupler, and an oxidized form of a developing agent having a color correcting effect. Compounds that release photographically useful fragments such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

In the light-sensitive material of the present invention, an image stabilizer and an ultraviolet absorber can be used for the purpose of preventing the deterioration of the dye image.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound that can be fixed by reacting with formaldehyde described in the specification of JP-A No. 7 or 4,735,503 to the photosensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used. The support usually has a thickness of 50 to 200 μm.

When the light-sensitive material of the present invention is used in the form of a roll film, it is preferable that the light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format cartridge. Other cartridges proposed in the following patents can also be used (Japanese Utility Model Laid-Open No. 58-67329, Japanese Patent Laid-Open No. 58-181).
No. 035, No. 58-182634, Shokai 5
8-195236, U.S. Pat. No. 4,221,47
No. 9, Japanese Patent Application No. 63-57785 and No. 63-57785.
JP 183344, JP 63-325638, Japanese Patent Application No. 1-21862, JP 1-25362,
Nos. 1-30246, 1-20222, 1-221863, 1-37181, 1
-33108, 1-85198, 1-
Nos. 172595 and 1-172594, 1
No. 172593, U.S. Pat. No. 4,846,418
No. 4,848,693, No. 4,848,693
832, 275).

[0130]

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 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by weight was laminated to produce a reflective support. After the reflective support was subjected to corona discharge treatment, a gelatin undercoat layer was provided thereon, and each layer having the following constitution was further provided thereon to prepare a silver halide photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 5.68 g of yellow coupler (EY-1), 6.68 g of color developing agent (10), and high boiling organic solvent (DBP)
To 33 g and 1.67 g of a high boiling point organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution was added to 220 ml of a 10% gelatin aqueous solution containing 7 ml of a 20% surfactant (SU-1) using an ultrasonic homogenizer. The mixture was emulsified and dispersed to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

Further, (H-1) and (H-2) as hardening agents
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension.
Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² .

[0135]

[Table 1]

[0136]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2 -Sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) 102.7 g of sodium chloride 102.7 g of K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
As in the case of -1, the average particle size is 0.64 μm, and the variation coefficient is 0.
07, a monodispersed cubic emulsion EMP-1B having a silver chloride content of 99.5 mol% was obtained.

The above EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

Next, a monodisperse cubic emulsion EMP-2B having an average particle size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally chemically sensitized at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

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[0152]

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The light-sensitive material prepared as described above was used for Sample 1
01.

Next, in the preparation of Sample 101, the anti-stain agents (HQ-2, HQ-3, HQ-3) contained in the second layer were used.
-4, HQ-5), a stain inhibitor (HQ-5) contained in the fourth layer, a stain inhibitor (HQ) contained in the sixth layer
Specimen 1 except that -5) was changed as shown in Table 3 below.
Samples 102 to 106 were prepared in exactly the same manner as in Sample No. 01.

[0155]

[Table 3]

After exposing these samples to light wedges with green light by a conventional method, development processing was performed in the following processing steps.

<< Development Processing >> Processing Step Processing Temperature Time Color development 40.0 ± 0.3 ° C. 30 seconds Bleaching and fixing 40.0 ± 0.5 ° C. 45 seconds Rinse room temperature 30 seconds Alkaline processing room temperature 30 seconds Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-disulfonic acid (30%) 4 ml Add water 1000 ml pH (25 ° C./potassium hydroxide) 12 Bleach-fix solution Water 600 ml Ammonium thiosulfate ( 93 ml Ammonium iron (III) ethylenediaminetetraacetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g pH (at 25 ° C./acetic acid and ammonium water) 5.8 Rinse solution 0.02 g chlorinated sodium isocyanurate Deionized water (dielectric constant: 5 μm / cm or less) 1000 ml pH 6.5 Alkaline treatment liquid 800 ml Potassium carbonate 30 g Water was added to 1000 ml pH (with 1N sulfuric acid or 1N potassium hydroxide) 10 The obtained sample was PDA-65. concentration (Konica Co., Ltd.)
Was used to measure the reflection density. The following methods were used to evaluate color turbidity, light stain, and moisture resistance.

<Color turbidity> The blue density and red density at the point where the green density gave 1.5 were measured and used as a scale of the color turbidity.

<Light Stain> The treated sample was irradiated with light using a xenon fade meter (70,000 lux) for 14 days, and the blue density Dmin (B) of the unexposed portion was measured. The difference from Dmin (B) before light irradiation is ΔDmin
(B).

<Moisture resistance>
After storage under 0% condition for 21 days, the green density D (G) was measured. D in the portion where D (G) is 1.0 immediately after processing
The change in (G) was defined as the residual ratio of the dye image density.

Table 4 shows the above results.

[0163]

[Table 4]

As is clear from Tables 3 and 4, the sample No. When 102 to 105 are used, it is possible to obtain a color image in which color turbidity is small, generation of light stain is suppressed, and dye image deterioration due to humidity is small.

Example 2 In Samples 101 to 106 of Example 1, the blue-sensitive silver halide emulsion of the first layer was 0.026 g / m ² , and the green-sensitive silver halide emulsion of the third layer was 0.014 g. / M ² , 5th
Sample ² was prepared in exactly the same manner as Samples 101 to 106 except that the red-sensitive silver halide emulsion in the layer was changed to 0.021 g / m 2.
01 to 206 were created.

After exposing these samples in the same manner as in Example 1, the samples were treated with the following processing solutions using the following processing solutions.

Processing Step Processing Temperature Amplification Developer (CDA-1) 33.0 ± 0.5 ° C. 60 seconds Bleaching / Fixing Solution (BF-1) 35.0 ± 0.5 ° C. 20 seconds Stabilization Liquid 30 to 34 ° C for 60 seconds Drying 60 to 80 ° C for 30 seconds The composition of the treatment liquid is shown below.

Amplification developer (CDA-1) Pure water 800 ml Potassium bromide 0.001 g Potassium chloride 0.35 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4 0.0 g N, N-diethylhydroxylamine 4.7 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 1-hydroxyethylidene-1,1'-diphosphonic acid 0.35 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative 2.0 g Potassium carbonate 20 g Hydrogen peroxide (30%) 5.0 g Add water to make the total volume 1 liter, and adjust to pH = 10.3.

Bleach-fix solution (BF-1) Pure water 700 ml Diethylenetriaminepentaacetate ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4 -Thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution Pure water 800 ml o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1 0.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP (polyvinylpyrrolidone) 1.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or ammonia water. .

Using the treated sample, color turbidity, light stain and moisture resistance were evaluated in the same manner as in Example 1.

Table 5 shows the results.

[0173]

[Table 5]

As is clear from Table 5, the sample N of the present invention
o. When 202 to 205 are used, it is possible to obtain a color image in which color turbidity is small, generation of light stain is suppressed, and excellent storage stability of the dye image is obtained. In particular, when the amplification and development processing is performed, the compound according to the present invention is preferably used, since color turbidity and image storability after processing tend to deteriorate.

Example 3 Preparation of Magnetic Recording Medium << Preparation of Support >> 0.1 part by weight of calcium acetate hydrate as a transesterification catalyst was added to 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol. After the addition, a transesterification reaction was carried out according to a conventional method.
To the obtained product, 0.05 parts by weight of antimony trioxide,
0.03 parts by weight of trimethyl phosphate was added.
Then, gradually raise the temperature and reduce the pressure, 290 ° C, 0.05 mm
Polymerization was performed under the conditions of Hg to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.

This was vacuum-dried at 150 ° C. for 8 hours, melt-extruded in a layer form from a T-die at 300 ° C., adhered to a cooling drum at 50 ° C. while applying static electricity, cooled and solidified, and the unstretched sheet was cooled. Obtained. This unstretched sheet was stretched 3.3 times in the machine direction at 135 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 155 ° C. at a total transverse stretching ratio of 3. The film was stretched three times. Then 10
Heat treated at 0 ° C for 2 seconds, and further heat-fixed zone 200 ° C
For 5 seconds and a second heat setting zone at 240 ° C. for 15 seconds. Next, the film was gradually cooled to room temperature over 30 seconds while relaxing in a transverse direction by 5% to obtain a polyethylene naphthalate film having a thickness of 85 μm.

This is wound around a stainless steel core, and
A heat treatment (annealing treatment) was performed at 10 ° C. for 48 hours to form a support.

On both sides of this support, 12 W / m ² / min
Of the undercoating coating solution B-1
Is applied to a dry film thickness of 0.4 μm, and 1
A 2 W / m ² / min corona discharge treatment was applied, and the undercoat coating solution B-2 was applied so as to have a dry film thickness of 0.06 μm.

On the other surface subjected to the corona discharge treatment at 12 W / m ² / min, the undercoating coating solution B-3 was dried to a thickness of 0.
2 μm, and 12 W / m ² / m
An in-corona discharge treatment was performed, and a coating solution B-4 was applied so as to have a dry film thickness of 0.2 μm.

Each of the layers was dried at 90 ° C. for 10 seconds after coating, and after the four layers were coated, heat-treated at 110 ° C. for 2 minutes, and then cooled at 50 ° C. for 30 seconds.

<Undercoat Coating Solution B-1> A copolymer latex liquid of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate (solid content: 30% 125 g Compound (UL-1) 0.4 g Hexamethylene-1,6-bis (ethylene urea) 0.05 g Finish with water 1000 ml <Subbing coating solution B-2> Hydroxidation of styrene-maleic anhydride copolymer Sodium aqueous solution (solid content 6%) 50 g Compound (UL-1) 0.6 g Compound (UL-2) 0.09 g Silica particles (average particle size 3 μ) 0.2 g Finish with water 1000 ml <Coating solution B-3> Butyl 30% by weight of acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25 of 2-hydroxyacrylate % By weight copolymer latex liquid (solid content 30%) 50 g Compound (UL-1) 0.3 g Hexamethylene-1,6-bis (ethylene urea) 1.1 g Finish with water 1000 ml

[0183]

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<Coating Solution B-4> 60 mol% of dimethyl terephthalate, 30 mol% of dimethyl isophthalate, 10 mol% of a sodium salt of dimethyl 5-sulfoisophthalate, 50 mol% of ethylene glycol as a glycol component, 50 mol% of diethylene glycol was copolymerized by a conventional method. The copolymer was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A.

Water dispersion of tin oxide-antimony oxide composite fine particles (average particle size: 0.2 μm) (solid content: 40% by weight) 109 g Water dispersion A 67 g Finished with water 1000 ml << Coating of magnetic recording layer >> Sublayer U- for processing support
4 On the layer coated with the coating solution, a magnetic recording layer coating solution having the following composition was dried with a precision extrusion coater to a dry film thickness of 0.
The coating was applied so as to have a thickness of 8 μm, and at the same time as drying, the magnetic substance was oriented in the application direction in an orientation magnetic field while the coating film was not dried, thereby achieving high output during magnetic recording and reproduction.

[Composition and Preparation of Magnetic Recording Layer Coating Solution M-1] Cobalt-containing gamma iron oxide (average major axis length 0.12 μm, minor axis length 0.015 μm, Fe ² + / Fe ³ + = 0.2, Specific surface area 40 m ² / g, Hc = 750 Oe) 10 parts by weight Alumina (α-Al ₂ O ₃ , average particle size 0.2 μm) 3 parts by weight Diacetyl cellulose (manufactured by Teijin Limited) 150 parts by weight Polyurethane (N3132, Japan Polyurethane Co., Ltd. 15 parts by weight Stearic acid 2 parts by weight Cyclohexanone 920 parts by weight Acetone 920 parts by weight After thoroughly mixing and dispersing the above, and then dispersing with a sand mill, Coronate-3041 of polyisocyanate (manufactured by Nippon Polyurethane Co., Ltd., solid (50% by weight) was added, and the mixture was sufficiently stirred and mixed to obtain a magnetic coating material M-1.

<< Coating of Lubricating Layer >> A lubricant coating solution (wax liquid described below) was prepared by dispersing a carnauba wax in a water / methanol mixed solution so as to contain 0.1% of carnauba wax on the magnetic recording layer. Was applied so that the coating weight of was 15 mg / m ² . The raw material after the wax application was passed through a heat treatment zone at 100 ° C. for 5 minutes to dry, and then left in an oven at 40 ° C. for 5 days to sufficiently perform a crosslinking reaction of isocyanate.

(Preparation of Wax Liquid) Polyoxyethylene lauryl ether 4 was added to 100 parts by weight of water heated to 90 ° C.
Parts by weight, and 40 parts by weight of carnauba wax separately melted at 90 ° C. were added thereto, followed by sufficiently stirring using a high-speed stirring homogenizer to prepare a dispersion of carnauba wax (WAX1). .

Next, 995 parts by weight of water, 900 parts by weight of methanol and propylene glycol monomethyl ether 10
0 parts by weight, and 5 parts by weight of WAX1 was added thereto.
By stirring, a wax liquid was prepared.

After providing the undercoating layer with the undercoating coating solutions B-1 and B-2 under the same conditions on the side of the magnetic recording medium opposite to the magnetic recording layer side, the undercoat layer having the following composition was prepared. A sample 301 was provided with a photographic component layer. The addition amount is expressed in grams per 1 m ^2. However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 OIL-1 0.044 Gelatin 1.33 Second Layer (Intermediate Layer) Polyethylacrylate Latex 0.20 Gelatin 1. 40 third layer (low-sensitivity red-sensitive layer) silver iodobromide a 0.12 silver iodobromide b 0.50 SD-1 3.0 × 10 ^-5 SD-4 1.5 × 10 ^-4 SD -3 3.0 × 10 ^-4 SD-6 3.0 × 10 ^-6 C-1 0.51 Color developing agent (10) 0.54 OIL-2 0.45 Gelatin 1.40 Fourth layer (medium sensitivity) Red-sensitive layer) Silver iodobromide c 0.64 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-2 0.22 Color developing agent (10) 0.28 OIL-2 0.21 Gelatin 0.87 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0 13 silver iodobromide d 1.14 SD-1 3.0 × 10 -5 SD-2 1.5 × 10 -4 SD-3 3.0 × 10 -4 C-1 0.085 C-2 0. 084 Color developing agent (10) 0.20 OIL-2 0.23 Gelatin 1.23 6th layer (intermediate layer) Polyethyl acrylate latex 0.23 Gelatin 1.00 7th layer (Low sensitivity green color sensitive layer) Silver iodobromide a 0.245 Silver iodobromide b 0.105 SD-6 5.0 × 10 ^-4 SD-5 5.0 × 10 ^-4 M-1 0.21 Color developing agent (10) 23 OIL-1 0.25 Gelatin 0.98 Eighth layer (Medium speed green-sensitive layer) Silver iodobromide e 0.87 SD-7 3.0 × 10 ^-4 SD-8 6.0 × 10 ^{− 5 SD-9 4.0 × 10 -5} M-2 0.17 color developing agent (10) 0.20 OIL-1 0.29 gelatin 1.43 9-layer (high sensitivity green-sensitive layer) Silver iodobromide f 1.19 SD-7 4.0 × 10 -4 SD-8 8.0 × 10 -5 SD-9 5.0 × 10 -5 M -1 0.09 Color developing agent (10) 0.12 OIL-1 0.11 Gelatin 0.78 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Polyethyl acrylate latex 0.20 Gelatin 1.00 11 layers (low-sensitivity blue-sensitive layer) Silver iodobromide g 0.29 Silver iodobromide h 0.19 SD-10 8.0 × 10 ^-4 SD-11 3.1 × 10 ^-4 Y-1 0.91 Color developing agent (10) 0.90 OIL-1 0.37 Gelatin 1.29 12th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.13 Silver iodobromide i 1.00 ^{SD-10 4.4 × 10 -4 SD} -11 1.5 × 10 -4 Y-2 0.48 color developing agent (10) 0.4 OIL-1 0.21 gelatin 1.55 thirteenth layer (first protective layer) silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.63 gelatin 1.32 14 layers (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 gelatin 0.55 In addition to the above composition, a coating aid SU -1, SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizers ST-1, ST-2, antifoggant AF-1, weight average molecular weight: 10,000 and weight average molecular weight: 1,
100,000 two types of polyvinylpyrrolidone (AF-
2), inhibitors AF-3, AF-4, AF-5, hardener H
-1 and H-2 were added.

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

Table 6 shows the features of the silver iodobromide.

[0194]

[Table 6]

[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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As a preferred example of forming silver halide grains of the present invention, a production example of silver iodobromide d and f is shown below.

Preparation of Seed Emulsion-1 A seed crystal emulsion was prepared as follows.

JP-B-58-58288, 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side ratio of 1.0% or more of 90% or more of the total projected area of the silver halide grains.
~ 2.0 hexagonal tabular grains.
This emulsion is referred to as seed emulsion-1.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) ₁₉ . ₈ (CH ₂ CH ₂ O) _n H (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 0.06 mol of iodine While vigorously stirring 5 liters of a 6.0% by weight aqueous gelatin solution containing potassium iodide, 7.06
2 liters of an aqueous silver nitrate solution and 2 liters of a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are prepared, the pH is adjusted using an aqueous sodium carbonate solution.
Was adjusted to 5.0. The average particle size of the obtained silver iodide fine particles was 0.05 μm. This emulsion is designated as SMC-1.

Preparation of silver iodobromide d: 0.178 mol of seed crystal emulsion-1 and HO (CH ₂ CH ₂
O) _m (CH (CH ₃ ) CH ₂ O) ₁₉ . ₈ (CH ₂ CH ₂ O)
_{n H (m + n = 9.77} ) 10% ethanol solution 0.
4.5% by weight of an inert gelatin aqueous solution containing 5 ml 7
The solution was kept at 75 ° C., the pAg was 8.4, and the pH was 5.
After adjusting to 0, particles were formed by the simultaneous mixing method with vigorous stirring according to the following procedure.

1) A 2.1 mol silver nitrate aqueous solution and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g while maintaining the pH at 8.4 and the pH at 5.0.

2) Subsequently, the temperature of the solution was lowered to 60 ° C., and pAg
Was adjusted to 9.8. Then, 0.071 mol of SMC
-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

3) 0.959 mol of silver nitrate aqueous solution and
03 mol of SMC-1 and an aqueous solution of potassium bromide were added to p
Ag was added at 9.8 and the pH was maintained at 5.0.

[0211] Throughout the formation of particles, each solution was added at an optimum rate so as to prevent the formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The resulting emulsion had a particle size (cubic 1 of the same volume).
The emulsion was composed of tabular grains having a halogen composition of 0.75 μm in side length, an average aspect ratio of 5.0, and a halogen composition of 2 / 8.5 / X / 3 mol% (X is a dislocation line introduction position) from the inside of the grains. . When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 6.7 mol%.

Preparation of silver iodobromide f In the preparation of silver iodobromide d, pAg was adjusted to 8. in step 1).
8, and silver iodobromide f was prepared in exactly the same manner as silver iodobromide d except that the amount of silver nitrate added in step 3) was 0.92 mol and the amount of SMC-1 was 0.069 mol. .

The obtained emulsion had a particle size (cubic 1 of the same volume).
An emulsion comprising tabular grains having a halogen composition of 0.65 μm, an average aspect ratio of 6.5, and a halogen composition of 2 / 8.5 / X / 7 mol% (X is a dislocation line introduction position) from the inside of the grains. . When this emulsion was observed with an electron microscope, five or more dislocation lines were observed both in the fringe portion and in the inside of the grain in 60% or more of the total projected area of the grain in the emulsion. The surface silver iodide content was 11.9 mol%.

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added, and the fogging and sensitivity were optimized according to a conventional method. Chemical sensitization was applied to obtain.

Silver iodobromide a, b, c, e, g, h, i, j
Was also subjected to spectral sensitization and chemical sensitization according to d and f above.

Next, Sample 301 was prepared in exactly the same manner as Sample 301 except that AS-1 of the sixth layer and AS-5 of the ninth layer were changed to the compounds and addition amounts shown in Table 7 below. To prepare Samples 302 to 305.

[0218]

[Table 7]

These samples were exposed to light wedges with green light by a conventional method, and then subjected to development processing using the following developing solution in the following processing steps.

<< Development Processing >> (Processing Step) Step Processing Time Processing Temperature Color Development 120 seconds 38 ° C. Bleaching 90 seconds 38 ° C. Fixing 120 seconds 38 ° C. Stable (1) 30 seconds 38 ° C. Stable (2) 30 seconds 38 C. Stability (3) 30 seconds 38.degree. C. Drying 90 seconds 60.degree. C. * Stabilization was performed in the countercurrent method from (3) to (1).

The composition of the processing liquid is shown below.

(Color developing solution) Tripotassium phosphate 30 g 5-Nitrobenzotriazole 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 3.3 g Potassium chloride 10 g Hydroxyethylidene-1,1-diphosphone Acid (30% solution) 4 ml 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g Add water 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 12.00 (bleach Liquid) Ammonium ferric 1,3-diaminopropanetetraacetate-hydroxide 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 80 g Ammonium nitrate 15 g Hydroxyacetic acid 25 g Acetic acid (98%) 40 g Add water 1.0 L pH (adjusted with aqueous ammonia and acetic acid) 4.3 (Fixing solution ) Ethylenediaminetetraacetic acid disodium salt 15 g Ammonium sulfite 19 g Imidazole 15 g Ammonium thiosulfate (70 wt%) 280 ml Add water 1.0 liter pH (adjusted with aqueous ammonia and acetic acid) 7.4 (Stabilized solution) p-toluenesulfin Sodium acrylate 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 g Ethylenediaminetetraacetic acid disodium salt 0.05 g 1,2,4-triazole 1.3 g 1,4-bis ( 1,2,4-triazol-1-ylmethyl) piperazine 0.75 g Water was added and 1.0 liter pH (adjusted with ammonia water and acetic acid) 9.5 The obtained sample was subjected to PDA-65 densitometer (Konica ( Co., Ltd.)
Was used to measure the transmission density. The sensitivity was defined as the reciprocal of the exposure amount that gave a transmission density of fog +0.3.

The same treatment and evaluation were performed on a sample stored at 50 ° C. and 80% RH for 7 days. Table 8 shows the change ΔDmin (G) of the minimum green density with storage over time. Table 8 shows the sensitivity after storage over time (relative sensitivity) when the sensitivity before storage over time was set to 100.

[0224]

[Table 8]

As is clear from Table 8, the use of the compounds represented by the general formulas [1] and [2] according to the present invention suppresses an increase in fog and a decrease in sensitivity due to storage over time. Became possible.

[0226]

According to the present invention, excellent prevention of color turbidity and reduction of the minimum density without deteriorating the image storability of a color image, prevention of increase in fog due to (raw) storage over time before development processing, and sensitivity. A silver halide color photographic light-sensitive material and a color image forming method which incorporate (contain) a color-forming reducing agent and a dye-forming coupler, which are excellent in preventing a decrease in color, can be provided.

Claims (8)

[Claims] 1. A silver halide color photographic material having a photographic layer comprising at least one photosensitive silver halide emulsion layer on a support, wherein at least one type of It contains a color-forming reducing agent represented by the general formula (I) and at least one dye-forming coupler, and is further represented by the following general formula [1] or [2] in one of the photographic constituent layers. Silver halide color photographic light-sensitive material comprising at least one compound selected from the group consisting of: Embedded image [In the formula, R ¹ represents an aryl group or a heterocyclic group, and R ² represents an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, or —OM (M represents a hydrogen atom or a metal atom). X
Represents —SO ₂ —, —CO—, —COCO—, —COO—,
-CON (R ³ )-, -COCO-, -COCON
(R ³ ) — or —SO ₂ N (R ³ ) —. Here, R ³ represents a hydrogen atom or a group having the same meaning as R ² . [Chemical formula 2] Wherein R ^{41 to} R ⁴⁶ each represent a hydrogen atom, a halogen atom,
Hydroxyl group, cyano group, sulfo group, carboxyl group, substituted or unsubstituted alkyl group, aryl group, heterocyclic group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, arylcarbonyl group, alkoxy group, aryloxy group, Represents an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acyloxy group, or an arylcarbonyloxy group. However, at least one of R ⁴¹ and R ⁴³ and at least one of R ⁴⁴ and R ⁴⁶ represent a hydroxyl group. R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴⁴ and R ⁴⁵ , and R ⁴⁵ and R ⁴⁶ may be bonded to each other to form a ring. X represents a divalent linking group, and n represents 1 or 0. [Chemical formula 3] Wherein R ⁴⁷ and R ⁴⁸ are each a hydrogen atom, a halogen atom,
A substituted or unsubstituted alkyl group, aryl group, heterocyclic group, carbamoyl group, sulfamoyl group, acyl group,
Represents an arylcarbonyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, an acyloxy group, or an arylcarbonyloxy group, and R ⁴⁷ and R ⁴⁸ are bonded to each other; To form a ring. Y is -CO- or -SO ₂ - represents a. R ⁴⁹ represents a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, or amino group. ] 2. The method according to claim 1, wherein the color-forming reducing agent represented by the general formula (I) is a color-forming reducing agent represented by the following general formula (II) or (III). Silver halide color photographic material. Embedded image [Wherein, Z ¹ and Z ² each represent an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each represent a hydrogen atom or a substituted Represents a group. However, the sum of the Hammett's substituent constant σp value of R ¹¹ , R ¹³ and R ¹⁵ and the Hammett's substituent constant σm value of R ¹² and R ¹⁴ is 0.80 to 3.80.
It is. R ²⁰ represents a heterocyclic group. ] 3. The color-forming reducing agent represented by the general formula (II) or (III) is a color-forming reducing agent represented by the following general formula (IV) or (V). Item 6. A silver halide color photographic light-sensitive material according to item 2. Embedded image [Wherein, R ¹⁶ and R ¹⁷ each represent a hydrogen atom or a substituent, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ²⁰ represent the above-mentioned general formulas (II) and (III), respectively. Is synonymous with ] 4. The color-forming reducing agent represented by the general formula (IV) or (V) is a color-forming reducing agent represented by the following general formula (VI) or (VII). Item 6. A silver halide color photographic light-sensitive material according to item 3. Embedded image [Wherein, R ²⁶ and R ²⁷ each represent a hydrogen atom or a substituent, and R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group. A carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of R ²¹ , R ²³ and R ²⁵ and the Hammett's substituent constant σm value of R ²² and R ²⁴ is 1.20 to 3.80. Q represents a group of nonmetallic atoms necessary for forming a 5- to 8-membered nitrogen-containing heterocyclic ring together with C. ] 5. The compound according to claim 1, wherein the compound represented by the general formula [1] or [2] has an I / O value of 1.5 or less. Silver halide color photographic material. 6. The compound according to claim 1, wherein the compound represented by the general formula [1] or [2] is contained in a layer different from the layer containing the photosensitive silver halide. The silver halide color photographic light-sensitive material according to any one of the above items. 7. A layer wherein the compound represented by the above general formula [1] or [2] is located in the middle of a photosensitive silver halide emulsion layer having different color sensitivity and does not contain a photosensitive silver halide. The silver halide color photographic light-sensitive material according to any one of claims 1 to 6, wherein 8. In the presence of a color-forming reducing agent represented by formula (I) and at least one dye-forming coupler, and at least one compound represented by formula (1) or (2). A method for forming a color image.