JPH1195364A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic sensitive material capable of being easily and rapidly processed and small in fluctuation of toe gradation during storage with the lapse of time by incorporating a specified compound and a specified noncolor-developing water-insoluble compound in at least one of photosensitive layers and nonphotosensitive layers formed on a support. SOLUTION: At least one of the photosensitive layers and the nonphotosensitive layers formed on the support contains the compound represented by formula I: R<1> -NHNH-X-R<2> and at least one of them contains the noncolordeveloping and water-insoluble compound represented by formula II, and in formulae I and II, R<1> is an aryl or heterocyclic group; R<2> is an alkyl or alkenyl or alkynyl or heterocyclic group or the like; L is a -SO2 -, -CO-, or -COCO- group or the like; X is an electron withdrawing group having a Hammett's substituent constant σp, of >=0.25; Y is an alkylene group having 1-4C in the main chain; and Z is a nonmetallic atomic group necessary to form a 5-7-membered nonaromatic hetero ring together with the N atom.

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 and a method for forming an image which can be processed quickly and easily and have little variation in leg gradation during storage over time.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (hereinafter, also referred to as light-sensitive materials) have excellent characteristics such as high sensitivity and excellent gradation, and are widely used today. ing. The photosensitive material has excellent characteristics, and furthermore, it is desired to speed up processing and reduce the amount of waste liquid.

[0003] Various means have been proposed as these improving means. For example, a method has been proposed in which an aromatic primary amine or a precursor thereof is incorporated in a hydrophilic colloid layer in a photosensitive material, but there is a problem that storage stability of the photosensitive material is poor. In addition, there is a problem that stain is generated by light or heat after image formation.

[0004] Furthermore, European Patent Nos. 0545491A1 and 0565165A1 disclose simple and rapid processing methods.
No. 5,720,054 A1 and JP-A-8-202002.
Discloses a method of adding a sulfonylhydrazine compound to a hydrophilic layer. However, the above-mentioned photosensitive material has a problem that the gradation of the leg portion is apt to fluctuate when stored over time.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material and an image forming method which can perform simple and rapid processing and have less fluctuation of the leg gradation during storage over time. It is in. Another object of the present invention is to provide a silver halide photographic light-sensitive material having less fog.

[0006]

As a result of various studies, the inventor of the present invention has found that by performing a specific method, it is possible to carry out simple and rapid processing, and to reduce fluctuations in leg gradation during storage of a photosensitive material over time. They have found that they can do less, leading to the present invention.
At the same time, an image with little fog was obtained.

That is, the above object of the present invention has been achieved by the following constitutions.

(1) On the support, at least one
At least one layer of a silver halide photographic material having a light-sensitive layer and a non-light-sensitive layer contains a compound represented by the following general formula (I) and at least one layer represented by the following general formula (II) Silver halide photographic material containing a non-color-forming and water-insoluble compound.

[0009] Formula (I) in R ¹ -NHNH-L-R ² formula, R ¹ represents an aryl group or a heterocyclic group, 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). L is _{-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 .

[0010]

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In the formula, X represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.25 or more, Y represents an alkylene group having 1 to 4 carbon atoms in the main chain, and Z represents a nitrogen atom together with a nitrogen atom. 5
Represents a group of non-metallic atoms necessary to form a 7-membered non-aromatic heterocyclic ring, and when there is a substitutable nitrogen atom in Z,
The nitrogen atom is substituted by (-Y'-X '), X' represents a group having the same meaning as X, and Y 'represents a group having the same meaning as Y;
X and X 'and Y and Y' may be the same or different. However,

[0012]

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There is no basic amino group other than the basic skeleton of the non-aromatic heterocyclic ring represented by the formula, and the total number of carbon atoms in the molecule is 14 or more.

(2) On the support, at least one
At least one layer of a silver halide photographic material having a light-sensitive layer and a non-light-sensitive layer, containing the compound represented by the formula (I), and between the light-sensitive layer closest to the support and the support; A silver halide photographic material having a non-photosensitive hydrophilic colloid layer on its surface.

(3) On the support, at least one
A silver halide photographic material having at least one light-sensitive layer and a non-light-sensitive layer, wherein at least one layer contains a compound represented by the above general formula (I) and a compound represented by the following general formula (III): Silver photographic photosensitive material.

[0016]

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Wherein R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each
Hydrogen atom, halogen atom, alkyl group, alkenyl group,
Aryl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group , An alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group or an arylacyloxy group.

(4) On the support, at least one
At least one layer of a silver halide photographic material having a light-sensitive layer and a non-light-sensitive layer contains the compound represented by the formula (I), and at least one layer has an oil pH fluctuation value (ΔpH). A silver halide photographic light-sensitive material containing a compound of +0.11 or more.

(5) On the support, at least one
At least one of the silver halide photographic materials having a light-sensitive layer and a light-insensitive layer contains the compound represented by the formula (I), and at least one light-insensitive layer has an oxidation potential of 0. A silver halide photographic light-sensitive material containing a compound of 95 V or more.

(6) On the support, at least one
At least one layer of a silver halide photographic material having a light-sensitive layer and a non-light-sensitive layer contains the compound represented by the formula (I) and is contained in at least one non-light-sensitive layer. The average molecular weight of the hydroquinone derivative is 460
The above is a silver halide photographic light-sensitive material.

(7) On the support, at least one
At least one of the silver halide photographic materials having a light-sensitive layer and a non-light-sensitive layer contains the compound represented by the formula (I), and at least one coupler-containing layer contains the compound represented by the formula (III) A silver halide photographic material containing the compound represented by formula (1) in an amount of 0.001 to 2 mol% based on the coupler.

(8) An image forming method according to any one of (1) to (7), wherein the color development time is 5 to 14 seconds in the processing of the silver halide photographic material.

Hereinafter, the present invention will be described in more detail.

First, the compound represented by the formula (I) (referred to as color-forming reducing agent -HCD-) will be described.

In the formula (I), R ¹ -NHNH-L-R ² , 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). L is _{-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 .

The compound represented by the general formula (I) is preferably represented by the following general formula (I-2) or (I-3).

[0027]

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Formula (I-3) R ¹⁰ -NHNH-Z ^{2 wherein} Z ¹ and Z ² are each an acyl group, a carbamoyl group,
Represents 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 substituent. Provided that R ¹¹ , R ¹³ and R ¹⁵
The sum of the Hammett's substituent constant σp value and the Hammett's substituent constant σm value of R ¹² and R ¹⁴ is 0.80 to 3.80. R ¹⁰ represents a heterocyclic group.

The compound represented by the general formula (I-2) or (I-3) is represented by the following general formula (I-4) or (I-
More preferably, it is represented by 5).

[0030]

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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 and R ¹⁵ each have the same meaning as in the above formula (I-2). And R
²⁰ has the same meaning as R ¹⁰ in formula (I-3).

The compound represented by formula (I-4) or (I-5) is more preferably a compound represented by the following formula (I-
6) or (I-7).

[0033]

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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. , A sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an 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.

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 and 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 above for R ¹ .

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 .

L 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 (I-2) and (I-3) are preferable, and the compounds represented by the general formulas (I-4) and (I-5) Compounds represented by formulas (I-6) and (I-7) are more preferred. The general formula (I-
The compounds represented by 2) to (I-7) will be described in detail.

In the general formulas (I-2) and (I-3), 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, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, 4-dodecyloxybenzoyl, 2-hydroxymethylbenzoyl, and 3-hydroxymethylbenzoyl. (N-hydroxy-N-methylaminocarbonyl) propanoyl and the like. The case where Z ¹ and Z ² are carbamoyl groups will be described in detail in the general formulas (VI) to (VII).

As the alkoxycarbonyl group and the aryloxy group carbonyl group, an alkoxycarbonyl group and an aryloxycarbonyl group having 2 to 50 carbon atoms are preferable, and those having 2 to 40 carbon atoms are more preferable. 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 substituents, and examples of the substituents include the substituents mentioned here.

Further, 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.

R ¹¹ , R ¹² and R in the general formula (I-2)
^13, with respect to R ^14, R ¹⁵ is the sum of R ^11, R ^13, Hammett's substituent constant σp value of R ¹⁵ and R ^12, Hammett substituent constant σm values of R ¹⁴ is from 0.80 to 3.80 It is preferred that

In addition, R ²¹ in the general formula (I-6),
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, an acylthio group or a heterocyclic group, which further represent 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
The sum of the Hammett's substituent constant σp value of ²³ and R ^{25 and} the Hammett's substituent constant σm value of R ²² and R ²⁴ is 1.20 to 3.80.
Is preferably 1.50 to 3.80, and more preferably 1.70 to 3.80.

The Hammett's substituent constants σp and σm are described in, for example, “Hammet's Rule-Structure and Reactivity-” by Naoki Inamoto (Maruzen), “New Experimental Chemistry Course 14, edited by The Chemical Society of Japan. Reaction V ", p. 2605 (Maruzen), Tadao Nakaya," Explanation of Theoretical Organic Chemistry ", p. 217 (Tokyo Kagaku Dojin),
Chemical Review, 91, pp. 165-195 (19
(1991) and other detailed books.

R in the general formulas (I-4) and (I-5)
¹⁶ , R ¹⁷ , R in general formulas (I-6) and (I-7I)
²⁶ and R ²⁷ each represent a hydrogen atom or a substituent, and specific examples of the substituent have the same meanings as those described for R ^{11 to} R ¹⁵ , but are preferably a hydrogen atom or a carbon atom having 1 to ¹⁵ carbon atoms.
50 substituted or unsubstituted alkyl groups, 6 to 5 carbon atoms
0 substituted or unsubstituted aryl group, 1 to 50 carbon atoms
Or more preferably, at least one of R ¹⁶ and R ¹⁷ and at least one of R ²⁶ and R ²⁷ are a hydrogen atom.

R ¹⁰ and R ²⁰ in formulas (I-3) and (I-5) represent a heterocyclic group. Preferred heterocyclic groups are heterocyclic groups having 1 to 50 carbon atoms, and the heteroatom contains at least one nitrogen, oxygen, sulfur atom, or the like,
It is a saturated or unsaturated 3- to 12-membered ring (preferably a 3- to 8-membered ring) monocyclic or condensed ring, and specific examples include furan,
Pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole, pyridazine, indole,
Rings such as pyrazole, triazole, quinoxaline and the like can be mentioned.

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 ^{11 to} R ¹⁵ , R ¹⁶ , R ¹⁷ , R ^{21 to} R ²⁵ , R ²⁶ , R
It is preferable that at least one of the groups ²⁷ has a ballast group. Examples of the heterocycle completed by Q are shown in specific compound examples (10) to (41).

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

[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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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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In addition to the color-forming reducing agents represented by formulas (I-2) to (I-7), compounds represented by the following formula (I-8) are also preferably used.

[0073]

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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 (I-2).

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, triethylamine and the like. Can be

Hereinafter, typical examples of the compound represented by formula (I-8) will be given.

[0078]

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[0079]

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[0080]

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[0081]

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Next, the general formula (I) according to the first invention of the present invention
The compound represented by I) will be described.

[0083]

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In the formula, X represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.25 or more, Y represents an alkylene group having 1 to 4 carbon atoms in the main chain, and Z represents a nitrogen atom together with a nitrogen atom. 5
Represents a group of non-metallic atoms necessary to form a 7-membered non-aromatic heterocyclic ring, and when there is a substitutable nitrogen atom in Z,
The nitrogen atom is substituted by (-Y'-X '), X' represents a group having the same meaning as X, and Y 'represents a group having the same meaning as Y;
X and X 'and Y and Y' may be the same or different. However,

[0085]

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There is no basic amino group other than the basic skeleton of the non-aromatic heterocyclic ring represented by the following formula, and the total number of carbon atoms of the molecule is 14 or more.

Among the compounds represented by the general formula (II), preferred compounds are those represented by the following general formulas (IIa), (IIb) and (II)
c) and (IId), more preferably the following general formulas (IIa-1), (IId-1) and (IId-
The compound represented by 2), most preferably the compound represented by formula (IIa-2).

[0088]

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In the formula, X represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.25 or more; Y represents an alkylene group having 1 to 4 carbon atoms in the main chain; , Y 'is Y
And X and X 'and Y and Y' may be the same or different, and R _a , R _b , R _c , R _d ,
R _e , R _f , R _g , R _h , R _i and R _j represent a hydrogen atom or an alkyl group, and the total number of carbon atoms in the molecule is 14 or more.

[0090]

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In the formula, X and Y are each represented by the general formula (II)
Wherein A represents an oxygen atom, a sulfur atom, a methylene group or a bond, and R _a , R _b , R _c , R _d , R _e ,
R _f , R _g and R _h represent a hydrogen atom or an alkyl group, and the total number of carbon atoms in the molecule is 14 or more.

[0092]

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In the formula, X has the same meaning as in general formula (II), Y ₁ represents an alkylene group having 1 to 3 carbon atoms in the main chain, and R _a , R _b , R _c , R _d , R _e , R _f , R _g and R _h each represent a hydrogen atom or an alkyl group, and the total number of carbon atoms of X and Y ₁ is 12 or more.

[0094]

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In the formula, X has the same meaning as in general formula (II), Y ₁ has the same meaning as in general formula (IIa-1), and R _a , R _b , R _c , R _d , R _e , R _f , R _g and R _h each represent a hydrogen atom or an alkyl group, and the total number of carbon atoms of X and Y ₁ is 12 or more.

[0096]

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In the formula, X has the same meaning as in general formula (II), Y ₂ has the same meaning as in general formula (IIa-1), and R _a ', R _b ', R _c 'and R _d '. Represents an alkyl group, R ₁ represents an acyloxy group, an acylamino group, a hydroxyl group or an alkyl group, and X, Y ₂ , R ₁ , R _a ′, R _b ′, R
The sum of carbon numbers of _c ′ and R _d ′ is 12 or more.

[0098]

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In the formula, R _a and R _b represent a hydrogen atom or an alkyl group, R _a ″, R _b ″, R _c ″ and R _d ″ represent a hydrogen atom or an alkyl group, and Z represents —O— or -N (R ₃₎ - represents, R ₂ represents an alkyl group, an alkenyl group or an aryl group, R ₃ represents a hydrogen atom, an alkyl group or an aryl group, n represents 0 or 1, R _a, R _b , R _a ″, R _b ″,
The sum of the carbon numbers of R _c ″, R _d ″, R ₂ and R ₃ is 20 or more.

Hereinafter, the present invention will be described in more detail.

Formulas (II), (IIa) to (IId), (II
a-1), (IIa-2), (IId-1) and (IId-
In 2), examples of the electron-withdrawing group having a Hammett's substituent constant σp value of 0.25 or more represented by X and X ′ include, for example, “Chemical Region Extra Edition”, No. 122, pp. 96-103,
1979 (Nankodo), J.M. A. "Lang" edited by Dean
e's Handbook of Chemistr
y "12th edition, 1979 (Mc Graw-Hil
l), Chemical Reviews, 91, 1
Among those described in detail on pages 65 to 195 (1991), those having a σp value of 0.25 or more are mentioned. Representative examples thereof include a nitro group (0.78) and a cyano group (0.6
6), carboxyl group (0.45), acetyl group (0.
50), trifluoromethyl (0.54), trichloromethyl (0.33), benzoyl group (0.43), acetyloxy group (0.31), methanesulfonyl group (0.
72), methanesulfinyl group (0.49), benzenesulfonyl group (0.70), carbamoyl group (0.3
6), a methoxycarbonyl group (0.45), an ethoxycarbonyl group (0.45), and a phenoxycarbonyl (0.
44), a methanesulfonyloxy group (0.36), a pyrazolyl group (0.37), a dimethoxyphosphoryl group (0.
57). Among these substituents, those substituted with an alkyl group or an aryl group (for example, acetyl group, benzoyl group, methoxycarbonyl group, phenoxycarbonyl group, etc.) are further substituted with a substituent. For example, the following substituents fall into the category.

[0102]

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R ₁₁ represents a linear, branched or cyclic alkyl group; R ₁₂ represents a hydrogen atom, an aryl group or R ₁₁ ;
m represents an integer of 0 to 5, R ₁₃ is a nitro group, a cyano group,
Alkoxy group, aryloxy group, acyl group, acyloxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonyloxy group, halogen atom, aryl group , An alkylthio group, an arylthio group, an alkenyl group,
Represents a hydroxyl group or R _11, further alkyl groups represented by R ₁₁ may be substituted by substituents listed in R _13.

The general formulas (II), (IIa) to (IId), (II)
In a-1), (IIa-2) and (IId-1), the alkylene group having 1 to 4 carbon atoms in the main chain represented by Y and Y 'is specifically represented by the following general formula: Can be represented.

[0105]

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In the formula, R _{21 to} R ₂₈ represent a hydrogen atom or the aforementioned R
Represents the substituent described in ₁₃ , and n1, n2, and n3 represent 0 or 1. * Represents the side to be replaced with a nitrogen atom, and ** represents X
Or a side to be substituted with X '.

The alkylene group having 1 to 3 carbon atoms in the main chain represented by Y ₁ can be specifically represented by the following general formula.

[0108]

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In the formula, R _{21 to} R ₂₆ represent a hydrogen atom or the substituent described for R ₁₃ , and n1 and n2 represent 0 or 1. In addition, * represents the side substituted with a nitrogen atom, and ** represents the side substituted with X.

In the general formula (IId-2), the alkylene group having 1 to 3 carbon atoms in the main chain represented by Y ₂ includes Y ₂
Unlike that of ₁ , it can be represented by the following general formula (Y ₂ ).

[0111]

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In the formula, R ₂₁ ′ and R ₂₂ ′ represent a hydrogen atom or 1
Represents at least one of a hydrogen atom, at least one of R _{23 to} R ₂₆ represents a hydrogen atom or a substituent described above for R ₁₃ , n1 and n2 represent 0 or 1, and * represents nitrogen. The side substituted with an atom and ** represent the side substituted with X.

The biggest reason that the connecting group Y ₂ connecting the nitrogen atom to X of the compound represented by the general formula (IId-2) is different from Y ₁ is that the compound represented by the general formula (IId-2) Since both positions adjacent to the nitrogen atom are tertiary alkyl groups (that is, R _a ′, R _b ′, R _c ′ and R _d ′ in the general formula (IId-2) represent an alkyl group), The atom is less susceptible to a substitution reaction due to steric hindrance of the tertiary alkyl group, and therefore, when the substituents of R ₂₁ ′ and R ₂₂ ′ in the general formula (Y ₂ ) are sterically bulky, the reaction essentially proceeds. The synthesis yield is extremely low even if it does not proceed, or it is inconvenient in terms of production cost to use it as a photographic additive. Therefore, R ₂₁ ′ and R ₂₂ ′ in the general formula (Y ₂ ) represent a hydrogen atom or a primary alkyl group, and at least one of R ₂₁ ′ and R ₂₂ ′ represents a hydrogen atom. .

Accordingly, among the compounds represented by the general formula (IId), the linking group Y when R _c , R _d , _Re and R _f are simultaneously an alkyl group, and the compound represented by the general formula (IIa-1) Of the compounds represented by the following four substituents R _a , R _b , R _h , and R _g or R _c , R _d ,
R _e , R _f The linking group Y ₁ when the four types of substituents are simultaneously an alkyl group, and R _c , R _d , R _e , and R _{f of the} compound represented by the general formula (IId-1) simultaneously represent When the linking group Y ₁ is an alkyl group, the substituents R ₂₁ and R _{22 in the} general formula (Y) and the general formula (Y ₁ ) may be groups represented by R ₂₁ ′ and R ₂₂ ′, respectively. preferable. Further, among the compounds represented by the general formula (II),

[0115]

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In the case where both adjacent positions of the nitrogen atom represented by the formula are tertiary carbons, the general formulas (IIa), (IIb) and (IIc)
The same applies to the case where both adjacent positions of the ring nitrogen are tertiary carbons.

Formulas (II), (IIa) to (IId), (II)
a-1), (IIa-2), (IId-1), (IId-2)
At

[0118]

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The 5- to 7-membered nitrogen-containing heterocycle represented by [0119], in particular those having the following basic skeleton, the following heterocyclic rings may form a condensed ring, with R ₁₃ It may have the substituent described.

[0120]

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Formulas (I), (IIa) to (IId), and (II)
a-1), (IIa-2), (IId-1), (IId-2)
, R ₁ , R ₂ , R ₃ , R _{a to} R _j , R _a ′ to R _d ′,
The alkyl group represented by R _a ″ to R _d ″ may be linear, branched or cyclic, and may further have the substituent described for R ₁₃ .

The alkenyl group represented by R ₂ may be linear, branched or cyclic, and may further have the substituent described for R ₁₃ .

The aryl groups represented by R ₂ and R ₃ are basically a phenyl group, a 1-naphthyl group and a 2-naphthyl group, and may further have the substituent described for R ₁₃ .

Formulas (II), (IIa) to (IId), (II)
a-1), (IIa-2), (IId-1), (IId-2)
In among the electron-withdrawing substituents represented by X,

[0125]

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Formulas (I), (Ia) to (Id), (I
a-1), (Ia-2), (Id-1), (Id-2)
In the above, among the alkylene groups represented by Y, Y ₁ , and Y ₂ , n3 = 0 and n1, n2 in the general formula (Y) are preferable.
Is 0 or 1 (that is, represented by the general formula (Y ₁ )), and particularly preferred is n2 in the general formula (Y).
= N3 = 0 and n1 is 0 or 1, and most preferred are n1 = 1 and n2 = n3 = in the general formula (Y).
0.

Among the alkylene groups represented by formulas (Y), (Y ₁ ) and (Y ₂ ), the substituents represented by R _{21 to} R ₂₈ are a hydrogen atom or an alkyl group. It is more preferable that all are hydrogen atoms.

In the general formula (II),

[0129]

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The compound of the present invention is basically dissolved in a high boiling point organic solvent (HBS) and then dispersed in a binder such as gelatin for use. Therefore, the compound of the present invention is preferably water-insoluble, and preferably has high solubility in an organic solvent.

The basic amino group, which is an exclusion requirement described in the description of formula (II), has an electron-withdrawing group such as a carbonyl group, a sulfonyl group, a sulfinyl group, a phosphonyl group, or a cyano group. An amino group that does not exist specifically refers to an alkyl group, an alkenyl group, an aryl group, and an amino group substituted by a hydrogen atom, and examples thereof include the following substituents.

[0132]

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That is, for example, the following compounds are outside the scope of the present invention.

[0134]

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In the present invention, the water-insoluble compound is 25
It is a compound having a dissolvable amount of less than 0.1 g in 100 ml of pure water at 0 ° C., and it cannot be said unconditionally because the solubility in water is structurally changed by a skeleton or a substituent.
As a guide, those having a total carbon number of 14 or more are preferable, and those having 16 or more are more preferable.

The following are specific examples of the compound according to the present invention, but the present invention is not limited to these.

[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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When the compound of the formula (II) is added to the photosensitive layer, it may be added in an amount of 0.1 to 300 mol% based on the coupler.
Is preferably, more preferably 5 to 200 mol%,
When added to the non-photosensitive layer, 0.05 to all couplers
１００100 mol%.

The compound of the general formula (II) is preferably added to the photosensitive layer.

In the second aspect of the present invention, a non-photosensitive hydrophilic colloid layer is provided between the photosensitive layer closest to the support and the support. As the hydrophilic colloid, gelatin or a derivative thereof is preferable. The amount of the hydrophilic colloid applied is not limited, but is preferably 0.5 g / m ² or less, more preferably 0.2 to 0.01 g / m ² . It is preferable that the hydrophilic colloid layer contains a mercapto heterocyclic compound. Further, the hydrophilic colloid layer preferably contains a white pigment. When a white pigment is contained, it is more preferable to further contain a latex and / or a water-insoluble high-boiling organic solvent.

Next, the compound represented by the general formula (II) according to the third invention of the present invention:
The compound represented by I) will be described.

[0152]

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In the formula, each of R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ is
Hydrogen atom, halogen atom, alkyl group, alkenyl group,
Aryl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group , An alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group or an arylacyloxy group.

In the atoms or groups represented by R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ , examples of the halogen atom include fluorine, chlorine, bromine and the like, and examples of the alkyl group include
Methyl, ethyl, propyl, i-propyl, butyl, t
-Butyl, amyl, i-amyl, octyl, dodecyl,
Each group such as octadecyl, etc., is particularly preferable,
32 alkyl groups are preferred.

Examples of the alkenyl group include allyl, octenyl, oleyl and the like, and an alkenyl group having 2 to 32 carbon atoms is particularly preferable.

Examples of the aryl group include groups such as phenyl and naphthyl.

As the acyl group, acetyl, octanoyl, lauroyl and the like can be mentioned.

Examples of the cycloalkyl group include cyclohexyl, cyclopentyl and the like.

An alkoxy group is methoxy, ethoxy, dodecyloxy, etc .; an aryloxy group is phenoxy, an alkylthio group is methylthio, butylthio, dodecylthio, etc .; an arylthio group is phenylthio, an alkylacylamino group is acetylamino, arylacyl. Benzoylamino as an amino group, methylcarbamoyl as an alkylcarbamoyl group, phenylcarbamoyl as an arylcarbamoyl group, methylsulfonamide as an alkylsulfonamide group, phenylsulfonamide as an arylsulfonamide group, and phenylsulfonamide as an alkylsulfamoyl group. Methylsulfamoyl, phenylsulfamoyl as an arylsulfamoyl group, methylsulfonyl as an alkylsulfonyl group, Each group such as phenylsulfonyl as a reelsulfonyl group, methyloxycarbonyl as an alkyloxycarbonyl group, phenyloxycarbonyl as an aryloxycarbonyl group, acetyloxy as an alkylacyloxy group, and benzoyloxy as an arylacyloxy group is, respectively. No.

These groups include those having a substituent,
Examples of the substituent include an alkyl group, an aryl group, an aryloxy group, an alkylthio group, a cyano group, an acyloxy group,
Examples include an alkoxycarbonyl group, an acyl group, a sulfamoyl group, a hydroxyl group, a nitro group, an amino group, and a heterocyclic group.

In the compound represented by the general formula (III) used in the present invention, R ₃₁ and R ₃₃ are both branched alkyl groups having 4 or more carbon atoms, and preferably both R ₃₁ and R ₃₃ are each having 6 or more carbon atoms. And R ₃₂ and R ₃₄ are hydrogen atoms.

Specific examples of the compound represented by formula (III) are shown below, but it should not be construed that the invention is limited thereto.

[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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It is preferable that the compound of the general formula (III) is added in a very small amount. Specifically, it is preferably added at a ratio of 0.001 to 2 mol, and more preferably at a ratio of 0.002 to 0.1 mol, per 1 mol of the coupler.

Next, the oil pH according to the fourth invention of the present invention
A compound having a fluctuation value (ΔpH) of +0.11 or more will be described. The oil pH fluctuation value of the present invention represents a numerical value represented by the following formula.

Oil pH fluctuation value = ｛p at 25 ° C. of a 1 wt% solute ethanol / water = 8/2 (volume ratio) solution
H value｝-｛2 of ethanol / water = 8/2 (volume ratio) solution
The compound having a pH value at 5 ° C. ΔΔpH of +0.11 or more may be added to any layer, but is preferably added to the photosensitive layer. The amount of the compound to be added is preferably 1 to 100 mol%, more preferably 2 to 50 mol%, per 1 mol of the coupler.

Compounds having a ΔpH of +0.13 to +5.0 are more preferred.

Next, a compound having an oxidation potential of 0.95 V or more according to the fifth invention of the present invention will be described.

The compound is added to a non-photosensitive layer. Preferably, it is a non-photosensitive layer located between the photosensitive layer and another photosensitive layer. The addition amount of the compound is 30 to 300 mg / layer.
m ² is preferred, and more preferably 50 to 150 mg / m ^2.
It is.

The oxidation potential in the present invention is determined by a cyclic voltammetry method. That is, at 20 ° C. in acetonitrile, using a platinum as a working and control electrode, a saturated calomel electrode as a reference electrode, tetrabutylammonium perchlorate as a supporting electrolyte, and a cyclic voltagram at a sweep rate of 50 mV / sec. It can be determined by measuring.

Next, in the sixth invention of the present invention, at least one non-photosensitive layer contains a hydroquinone derivative, and the average molecular weight of all hydroquinone derivatives is 4%.
60 or more. Examples of the hydroquinone derivative include a compound represented by the general formula (III).

The average molecular weight of the hydroquinone derivative contained in at least one layer is preferably 470 or more, more preferably 490 or more. The number of types of hydroquinone derivatives contained in one layer is preferably four or more. The addition amount of all hydroquinone derivatives contained in one layer is preferably 30 to 300 mg / m ² per layer,
More preferably, it is 50 to 150 mg / m ² .

In the present invention, it is preferable to use two or more of the techniques described in claims 1 to 6 in combination.

The composition of the silver halide photographic emulsion according to the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide and the like. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. From the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable.

In order to obtain the above silver halide emulsion, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing silver bromide at a high concentration may be epitaxy-bonded to silver halide emulsion grains, may be a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. May simply have regions with different compositions. The composition may change continuously or may change discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion of the present invention, it is advantageous to contain heavy metal ions. Examples of heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; Group transition metals, and ions of lead, rhenium, molybdenum, tungsten, gallium, chromium, and the like. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to a silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex,
Examples of the ligand or ion include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion,
Chloride ions, bromide ions and the like are preferred.

In order to allow the silver halide emulsion to contain heavy metal ions, the heavy metal compound is added to the silver halide emulsion during the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, the heavy metal compound may be dissolved together with the halide salt and added continuously over the whole or a part of the grain forming step.

The amount of heavy metal ion added to the silver halide emulsion is from 1 × 10 ^-9 to 1 × 1 per mol of silver halide.
It is preferably from 0 to ² mol, and particularly preferably from 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737,
Octahedrons, tetradecahedrons, dodecahedrons, etc., by methods described in documents such as The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973). Can be produced and used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. The range is 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains is preferably a monodispersed silver halide grain having a coefficient of variation of 0.05 to 0.22, more preferably 0.05 to 0.15.
Particularly preferably, two or more monodispersed emulsions of 0.05 to 0.15 are added to the same layer. Where the coefficient of variation is
This is a coefficient indicating the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size referred to here is the diameter of spherical silver halide grains, or In the case of particles having a shape other than a cubic or a spherical shape, the diameter represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at a time, or may be grown after seed particles have been produced. The method for producing the seed particles and the method for growing the seed particles may be the same or different.

The form in which the soluble silver salt is reacted with the soluble halide may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but the method obtained by the simultaneous mixing method is preferable. . Further, as one form of the simultaneous mixing method, pA described in JP-A-54-48521 and the like are described.
g The controlled double jet method can also be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No. 92524, etc., a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt described in DE 2,921,164. And an apparatus for continuously adding an aqueous solution of a water-soluble halide while changing its concentration, Japanese Patent Publication No. 56-5017
No. 76, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, etc. can be used, but a sulfur sensitizer is preferable.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of the sulfur sensitizer to be added is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect, and the like.
10 ^{-10 to} 5 × 10 ^-5 mol, preferably 5 × 10 ^{-8 to} 3
A range of ^10-5 mol is desirable.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. Is preferably
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization of a silver halide emulsion includes:
A reduction sensitization method may be used.

The silver halide emulsion may contain a known antifoggant for the purpose of preventing fog generated during the preparation of the light-sensitive material, reducing performance fluctuation during storage, and preventing fog generated during development. Agents can be used. Preferred examples of the compound used for such purpose include a compound represented by the general formula [II] described in the lower column on page 7 of JP-A-2-14636, and more preferred specific compounds include II described on page 8 of the publication
a-1 to IIa-8, IIb-1 to IIb-7, 1
Compounds such as-(3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned.

These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, finishing the chemical sensitizing step, and preparing a coating solution. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ⁻² mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 ~ × 10 ^{- Two} moles are more preferred.
Further, when added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ⁻⁹ to 1 × 10 ⁻³ per m ^2.
Molar amounts are preferred.

As the light-sensitive material, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in JP-A-3770 are preferably used, and as the infrared absorbing dye, compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 are preferable. It is preferable because it has spectral characteristics, does not affect the photographic characteristics of the photographic emulsion, and does not stain due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of an unprocessed sample of the light-sensitive material is 0.7 to 3.0, and more preferably 0.8 to 3.0. More preferably, it is 3.0.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the whiteness can be improved. The compound preferably used is a compound represented by the general formula [I] described in JP-A-2-232652.
I].

When the light-sensitive material of the present invention is used as a color light-sensitive material, 400 to 900 nm
Has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the wavelength range of The silver halide emulsion contains one or more sensitizing dyes in combination.

As the spectral sensitizing dye used in the present invention, any of the known compounds can be used. Examples of the blue-sensitizing dye include BS-1 to BS-2 described in JP-A-3-251840, page 28. BS-8 can be preferably used alone or in combination. Green photosensitive sensitizing dyes include:
GS-1 to GS-5 described on page 28 of the publication are preferable,
Further, as the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye,
As the infrared-sensitive sensitizing dye, JP-A-4-285950
And the dyes IRS-1 to IRS-11 described on pages 6 to 8 are preferably used. These infrared, red, green, and blue light-sensitive sensitizing dyes include supersensitizers SS-1 to SS-9 and JP-A-5-6 described in JP-A-4-285950, pp. 8-9.
No. 6515, pages 15 to 17, compounds S-1 to S-
It is preferable to use 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or the like or water, or adding it as a solid dispersion. It may be added.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Although it is also possible to use, particularly typical couplers include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm,
Examples include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Preferable examples of the cyan coupler which can be preferably used include couplers represented by general formulas [CI] and [C-II] described in the lower left column of page 5 of JP-A-4-114154. As a specific compound, the publication 5
There can be mentioned those described as CC-1 to CC-9 in the lower right column of page 6 to the lower left column of page 6.

Examples of the magenta coupler that can be preferably used include couplers represented by general formulas [MI] and [M-II] described in the upper right column of page 4 of JP-A-4-114154. Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. Among the above magenta couplers, more preferred are those represented by the general formula [MI]
A coupler represented by the general formula [M-
The coupler of the formula (I) wherein R _M is a tertiary alkyl group is particularly preferred because of its excellent light resistance. M described in the upper column on page 5 of the publication
C-8 to MC-11 are preferable because they are excellent in reproduction of colors ranging from blue to purple and red, and are also excellent in detail description.

As the yellow coupler which can be preferably used, there can be mentioned a coupler represented by the general formula [YI] described in the upper right column of page 3 of JP-A-4-114154. YC on the lower left column of page 3
-1 to YC-9. Among them, a coupler of the formula [Y-I] in which R _Y1 is an alkoxy group or a coupler represented by the formula [I] described in JP-A-6-67388 is preferable because it can reproduce yellow having a preferable color tone. Of these, YC-8 and YC-9 and JP-A-6-673881 described in the upper left column of page 4 of JP-A-4-114154 are particularly preferred.
Compounds represented by Nos. (1) to (47) on pages 3 to 14 can be exemplified. The most preferred compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

When the oil-in-water type emulsification dispersion method is used to add the coupler or other organic compound used in the light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or more, if necessary. To dissolve in combination with a low boiling point and / or water-soluble organic solvent, and emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill,
A flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be included.

Examples of the high boiling point organic solvent which can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate and trioctyl phosphate. And the like are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination. .

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a preferred compound as a surfactant used for dispersing a photographic additive or adjusting the surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. Containing. Specifically, A-1 to A-1 described in JP-A-64-26854.
1 is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are
Usually, it is added to a coating solution containing a silver halide emulsion, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution to the coating are shorter, each being preferably within 10 hours. More preferably, within 3 hours and within 20 minutes.

Each of the above couplers is preferably used in combination with a discoloration inhibitor to prevent discoloration of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas [I] and [II] described in JP-A-2-66541, page 3, and phenols represented by general formula [IIIB] described in JP-A-3-174150. Amine compounds represented by the general formula [A] described in JP-A-64-90445;
General formulas (XII), (XIII) and (XI) described in No. 182741
V] and metal complexes represented by [XV] are particularly preferred for magenta dyes. Also, a compound represented by the general formula [I] described in JP-A-1-19649 and JP-A-5-1141.
The compound represented by the general formula [II] described in No. 7 is particularly preferable for yellow and cyan dyes.

Compounds such as compound d-11 described in the lower left column of page 9 of JP-A-4-114154 and compound A'-1 described in the upper left column of page 10 are used for shifting the absorption wavelength of the coloring dye. be able to. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to prevent fog or the like. Is preferably improved. As the compound for this, a hydroquinone derivative is preferred, and more preferably
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula [II] described in JP-A-4-133056, and the compounds II-1 to II-14 described on pages 13 to 14 of the same publication.
Compounds-1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog and improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula [III-] described in JP-A-1-250944.
3], a compound represented by the general formula [III] described in JP-A-64-66646, and a compound represented by JP-A-63-18
No. 7240, UV-1L to UV-27L;
Compounds represented by the general formula [I] described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder. If necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, A hydrophilic colloid such as a single or a synthetic hydrophilic polymer such as a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinylsulfone hardener, a chlorotriazine hardener or a carboxyl group-active hardener alone or in combination. JP-A-61-249054, 61-
It is preferable to use the compounds described in US Pat. Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15764 is incorporated in the colloid layer.
It is preferable to add a preservative and an antifungal agent as described in No. 6. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

As the support used for the light-sensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, and a white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferred.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as fine silica powder, synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, oxide Zinc, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by weight or more, and more preferably 15% by weight, in order to improve sharpness.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the variation coefficient described in the publication.

Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, more preferably 0.12 μm or less, since the effect of good gloss can be obtained.
Also, in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment, ultramarine blue, oil-soluble dyes, etc. It is preferable to add a small amount of a bluing agent or a reddish agent.

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, on the support surface, directly or undercoating (adhesion, antistatic property, dimensional stability on the support surface). , One or more undercoating layers for improving friction resistance, hardness, antihalation property, frictional properties and / or other properties).

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically formed on the photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. Printing may be performed by scanning while changing the light intensity.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display,
A light-sensitive material for color proof can be used. In particular, it is preferably applied to a photosensitive material having a reflective support.

[0233]

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 a 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 (Y-1), 6.68 g of color-forming reducing agent (CD-10), high boiling organic solvent (DBP)
To 3.33 g and 1.67 g of a high boiling point organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved. This solution was mixed with 220 ml of a 10% aqueous gelatin 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.

Each of the coating liquids for the second to seventh layers was 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.

(H-1), (H-2)
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 .

[0238]

[Table 1]

[0239]

[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 DPhP: 1,5-diphenyl-3-pyrazolidone HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di -Sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone

[0241]

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[0242]

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[0243]

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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) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added and 200 ml (Solution B) Silver nitrate 10 g Water was added and 200 ml (Solution C) Sodium chloride 102.7 g 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 carried out 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 subjected to chemical sensitization 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 monodispersed 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 subjected to chemical sensitization 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.

[0254]

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[0255]

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The sample thus prepared is designated as 101. Next, the same samples as the sample 101 were prepared except that the contents were changed to those described in Table 3 in the same manner as the sample 101.

Each of the samples thus obtained was subjected to blue light wedge exposure by a conventional method, and then subjected to the following processing. Each sample was similarly exposed after being stored at 50 ° C. and a relative humidity of 80% for 6 days.

Processing Steps Processing Temperature Time Color Development 40 ± 0.3 ° C. 30 seconds Bleaching and Fixing 40 ± 0.5 ° C. 45 seconds Rinse Room Temperature 60 Seconds Alkaline Processing Room Temperature 30 Seconds Drying 60-80 ° C. 30 Seconds The composition of each processing solution is shown below.

<Color developing solution> Water 600 ml Potassium phosphate 40 g Potassium chloride 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml Add water 1000 ml pH (at 25 ° C. aqueous potassium hydroxide solution) 12 <Bleaching and fixing Liquid> Water 600 ml Ammonium thiosulfate (700 g / liter) 93 ml Ammonium ferric ethylenediaminetetraacetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g pH (at 25 ° C. acetic acid and aqueous ammonia) 5.8 <Rinse liquid> Chlorination Sodium isocyanurate 0.02 g Deionized water (dielectric constant 5 μm / cm or less) 1000 ml pH 6.5 <Alkaline treatment liquid> Water 800 ml Potassium carbonate 30 g Water is added to 1000 ml pH (with 1N sulfuric acid or 1N potassium hydroxide) 10 This Each obtained in the yellow image of the sample, measuring the blue light reflection density of each step, the reflection density from 0.3 to 0.
The leg gradation (γ) of 8 was obtained (using the paper support used as a reference for the reflection density of 0). Photosensitive material, 50 ℃, 8
0% R. H. The magnitude Δγ of the difference in leg gradation between the sample before and after the storage was determined.

Δγ = | (γ of sample before storage over time) − (γ of sample after storage over time) | The results are shown in Table 3.

[0261]

[Table 3]

[0262]

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As is clear from Table 3, even when the color-forming reducing agent of the general formula (I) is incorporated in the light-sensitive material, the sample of the present invention shows a change in leg gradation due to simple and rapid processing during storage over time. Few. In addition, the sample of the present invention obtained an image with less fog than the comparative sample.

The samples 102, 104 to 106, 10
HCD-10 of the first, third and fifth layers 8 and 110
Each sample was prepared in the same manner as above except that was changed to HCD-1. Similarly, HCD-10 is replaced with HCD-30, 34,
Samples changed to 40, 49, 59 and 67 were also prepared.

When the same exposure and development processes were performed on each sample, the effects of the present invention were obtained.

Example 2 The blue-sensitive silver halide emulsion of the first layer of Sample 101 of Example 1 was 0.026 g / m ² (in terms of silver amount), and the green-sensitive silver halide emulsion of the third layer was 0%. .014g / m ^2, except that the red-sensitive silver halide emulsion of the fifth layer and 0.021 g / m ^2, was prepared by the same sample and the samples of example 1.

After exposing these samples in the same manner as in Example 1, the following processing was performed.

Processing Step Processing Temperature Time Current Image 40 ° C. 30 seconds Rinse Room Temperature 45 seconds Alkaline Processing Room Temperature 30 seconds <Developer> Water 600 ml Potassium phosphate 40 g Potassium chloride 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml 10 ml of hydrogen peroxide 1000 ml by adding water pH = 11.5 (adjusted with 25 ° C. aqueous solution of potassium hydroxide) <Rinse liquid> 0.02 g of chlorinated sodium isocyanurate Deionized water (dielectric constant 5 μS / cm or less) 1000 ml pH = 6.5 <Alkali-treated solution> 800 ml of water 30 g of potassium carbonate 1000 ml of water was added, and pH = 10 After the treatment, the image was evaluated in the same manner as in Example 1.

Also in this treatment, among the samples containing the compound of the general formula (I), the sample of the present invention could obtain a good color image with little change in the gradation of the legs during storage over time.

The effect of the present invention was also effective when the developing time was set to 14 seconds.

[0271]

According to the present invention, there is provided a silver halide photographic light-sensitive material which is capable of simple and rapid processing, and has little variation in leg gradation when the light-sensitive material is stored over time, and an image forming method using the light-sensitive material. Can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/407 G03C 7/407

Claims (8)

[Claims] 1. A silver halide photographic material having at least one photosensitive layer and at least one non-photosensitive layer on a support, wherein at least one layer contains a compound represented by the following general formula (I): And at least one layer represented by the following general formula (II)
A silver halide photographic material comprising a non-color-forming and water-insoluble compound represented by the formula: Formula (I) R ¹ -NHNH-LR ² [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). L
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 . [Formula 1] [Wherein, X represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.25 or more, Y represents an alkylene group having 1 to 4 carbon atoms in the main chain, and Z represents 5 to 5 together with the nitrogen atom. Represents a group of non-metallic atoms necessary for forming a 7-membered non-aromatic heterocyclic ring, and when a substitutable nitrogen atom is present in Z, the nitrogen atom is substituted by (-Y'-X ') And X '
Represents a group having the same meaning as X and Y 'has the same meaning as Y, and X and X' and Y and Y 'may be the same or different. However, There is no basic amino group other than the basic skeleton of the non-aromatic heterocyclic ring represented by the formula, and the total number of carbon atoms of the molecule is 14 or more. ] 2. A silver halide photographic material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, wherein at least one layer contains the compound represented by formula (I), A silver halide photographic material comprising a non-photosensitive hydrophilic colloid layer between the support and the photosensitive layer closest to the support. 3. A silver halide photographic material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, wherein at least one of the compound represented by formula (I) and A silver halide photographic material comprising a compound represented by the formula (III). Embedded image [Wherein, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each represent a hydrogen atom,
Halogen atom, alkyl group, alkenyl group, aryl group, cycloalkyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkylacylamino group, arylacylamino group, alkylcarbamoyl group, arylcarbamoyl group, Alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group,
Represents a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylacyloxy group or an arylacyloxy group. ] 4. A silver halide photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, each containing at least one compound represented by the formula (I), And a silver halide photographic light-sensitive material characterized in that at least one layer contains a compound having an oil pH fluctuation value (ΔpH) of +0.11 or more. 5. A silver halide photographic material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, wherein at least one layer contains the compound represented by formula (I), A silver halide photographic light-sensitive material characterized in that at least one non-light-sensitive layer contains a compound having an oxidation potential of 0.95 V or more. 6. A silver halide photographic material having at least one photosensitive layer and at least one non-photosensitive layer on a support, wherein at least one layer contains the compound represented by the formula (I), And a hydroquinone derivative contained in at least one non-photosensitive layer has an average molecular weight of 460 or more. 7. A silver halide photographic material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, wherein at least one layer contains the compound represented by the formula (I), And a silver halide photographic light-sensitive material characterized in that at least one coupler-containing layer contains the compound represented by formula (III) in an amount of 0.001 to 2 mol% based on the coupler. 8. An image forming method according to claim 1, wherein the color development time is 5 to 14 seconds in the processing of the silver halide photographic light-sensitive material.