JPH09152701A - Color developing agent, silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To attain satisfactory coloring at the time of development by using a specified color developing agent and to form an image having satisfactory coloring property and a fine hue even when a coupler whose position coupling with the oxidized body of the developing agent has been substd. is used. SOLUTION: This color developing agent is represented by the formula R<1> - NHNH-Z<1> (I), wherein Z<1> is acyl, carbamoyl, alkoxycarbonyl, aryloxycarbonyl or a group represented by formula II, R<1> is a 6-membered arom. hetero ring having >=3N atoms, the hammett's substituent constant σp of a substitutent on R<1> is 0-0.9, and in the case of two or more substituents, the sum is 0-1.8. In the formula II, X is -OR<5> or -NR<6> R<7> , each of R<4> , R<6> and R<7> is H, alkyl, etc., R<5> is alkyl, aryl, etc., and R<4> and R<5> , R<4> and R<6> or R<6> and R<7> may bond to each other to form a ring.

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 light-sensitive material using a novel color developing agent and a new image forming method, and in particular, a silver halide photographic light-sensitive material having good color forming property during development. Materials and imaging methods.

[0002]

2. Description of the Related Art In a color photographic light-sensitive material, after the material is exposed to light and color-developed, an oxidized color-developing agent reacts with a coupler to form an image. In this method, a color reproduction method based on a subtractive color method is used. To reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed.

In color development, an exposed color photographic light-sensitive material is dissolved in an alkaline aqueous solution (developing solution) in which a color developing agent is dissolved.
Achieved by immersion. However, there is a problem that a color developing agent made of an aqueous alkaline solution is unstable and easily deteriorates with time, and it is necessary to frequently replenish the developing solution in order to maintain stable developing performance. Further, the used developer containing the developing agent needs to be discarded, and in combination with the above-mentioned frequent replenishment, the processing of the used developer discharged in large quantities is a major problem. Thus, there is a strong demand for achieving low replenishment and low discharge of the developer.

As one of effective means for solving the problem of low replenishment and low discharge of a developing solution, there is a method of incorporating an aromatic primary amine developing agent or a precursor thereof into a hydrophilic colloid layer. Examples of suitable developing agents include, for example, U.S. Patent Nos. 803,783, 3,342,597, and 3,7.
19,492, 4,060,418, British Patent 1,069,061, West German Patent 1,159,758
No., JP-B-58-14,671 and No. 58-14,67
No. 2, JP-A-57-76,543 and JP-A-59-81,6
No. 43 and the like. However, color photographic light-sensitive materials containing these aromatic primary amine developing agents or their precursors have the disadvantage that sufficient color formation cannot be obtained during color development. Another effective means is a method of incorporating a sulfonylhydrazine type developing agent in a hydrophilic colloid. Examples of the developing agent which can be incorporated include, for example, US Pat. No. 4,481,268 and European Patent 5
45,491A1 and 565,165A1 and the like. However, even with the developing agents listed here, sufficient color development is not yet obtained during color development, and this sulfonylhydrazine type developing agent uses a coupler having a substituent at the coupling position with the oxidized main agent. When it did, there was a problem that it hardly developed color. As described above, the coupler having a substituent at the coupling position has advantages over the unsubstituted coupler in that the stain derived from the coupler can be reduced and the activity of the coupler can be easily adjusted. Therefore, there has been a strong demand for a developing agent which, even when incorporated, is capable of providing sufficient color development during development, and which is capable of providing an image with excellent color development even when a coupler having a substituted coupling position is used.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide a coupler in which a novel color developing agent is used, whereby sufficient color development is obtained at the time of development, and the coupling position with the oxidized main agent is substituted. It is an object of the present invention to provide a silver halide photographic light-sensitive material and an image forming method which can produce an image having a good hue even when used.

[0006]

The object of the present invention has been achieved by the following constitutions. (1) A color developing agent represented by the general formula (I). (2) The imagewise exposed silver halide photographic light-sensitive material is added in the presence of a color developing agent represented by the general formula (I) (for example, the main agent may be contained in the light-sensitive material or in the processing solution). It may be contained), and an image forming method characterized by developing. (3) A silver halide photographic light-sensitive material characterized by containing a compound represented by the following general formula (I) in at least one hydrophilic colloid layer provided on a support. It preferably contains a coupler. (4) An image forming method, wherein the photosensitive material of (1) is developed by heating at 50 to 200 ° C. (5) An image forming method, which comprises developing the photosensitive material according to (1) in a solution. (6) An image forming method, which comprises exposing a light-sensitive material to light and then treating it with a treatment liquid containing a color developing agent represented by formula (I). General formula (I) R ¹ -NHNH-Z ¹ (In the formula, Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a group represented by the general formula (II). R ¹ is 3 Represents a 6-membered aromatic heterocycle having the above nitrogen atom, and R ¹
The Hammett substituent constant σ p value of the above substituent is 0 or more and 0.9
It is below (when there are two, the sum is 0 or more and 1.8 or less).

[0007]

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(In the formula, X is a --OR ⁵ group or --NR ⁶
Represents an R ⁷ group. Here, R ⁴ , R ⁶ and R ⁷ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ⁵ represents an alkyl group, an aryl group or a heterocyclic group. R ⁴ and R ⁵ or R ⁶ , or R ⁶ and R ⁷ may be bonded to each other to form a ring. )

The color developing agent represented by the general formula (I) is preferably represented by the general formula (III).

[0010]

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(In the formula, R ¹ has the same meaning as in formula (I).
R ² and R ³ each represent a hydrogen atom or a substituent. The color developing agent represented by formula (III) is more preferably represented by formula (IV).

[0012]

[Chemical 6]

(In the formula, Q ¹ represents a group of nonmetallic atoms necessary for forming a 6-membered aromatic heterocycle having 3 or more nitrogen atoms together with C. R ² and R ³ are each represented by the general formula ( It has the same meaning as III).) The following are preferred embodiments. (1) A diffusion transfer type silver halide color photographic light-sensitive material comprising a color developing agent represented by the general formula (I). (2) An image forming method, which comprises thermally developing the photosensitive material according to (1) above. (3) When the photosensitive material according to the present invention is processed with a processing solution, the processing solution does not contain the color developing agent of the present invention.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention will be described below in detail. In formula (I), Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a group represented by formula (II). The acyl group is preferably an acyl group having 1 to 50 carbon atoms, more preferably 2 to 40 carbon atoms.
Specific examples include acetyl group, 2-methylpropanoyl group, cyclohexylcarbonyl group, n-octanoyl group, 2-hexyldecanoyl group, dodecanoyl group, chloroacetyl group, trifluoroacetyl group, benzoyl group, 4- Examples thereof include a dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, and a 3- (N-hydroxy-N-methylaminocarbonyl) propanoyl group. Z
^{When 1} is a carbamoyl group, general formula (III)
Will be described in detail.

The alkoxycarbonyl group and aryloxycarbonyl group are preferably an alkoxycarbonyl group having 2 to 50 carbon atoms and an aryloxycarbonyl group, more preferably 2 to 40 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group,
Isobutyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 4-octyloxyphenoxycarbonyl group, 2-hydroxymethylphenoxycarbonyl group, 2-dodecyloxyphenoxycarbonyl group and the like. Can be When Z ¹ is a group represented by the general formula (II), X represents a —OR ₅ group or a —NR ₆ R ₇ group. Here, R ⁴ , R ⁶ and R ⁷ are a hydrogen atom and an alkyl group (methyl, isopropyl,
Cyclohexyl, octyl, dodecyl, hexadecyl, etc.), aryl groups (phenyl, 1-naphthyl, 2-naphthyl, etc.), or heterocyclic groups (2-pyridyl, 3-
Pyrazolyl, 2-thiazolyl, 2-benzothiazolyl and the like). R ⁵ represents an alkyl group, an aryl group or a heterocyclic group, and specific examples thereof include R ⁴ , R ⁶ and R ^7.
Are the same as those mentioned in the explanation of. R ⁴ and R ⁵ or R ⁶ , or R ⁶ and R ⁷ may be bonded to each other to form a ring, and the ring formed is preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring. Is. R ⁴ ,
R ⁶ and R ⁷ are preferably a hydrogen atom, an alkyl group,
An aryl group, particularly preferably a hydrogen atom or an alkyl group. R ⁵ is preferably an alkyl group or an aryl group, and more preferably an alkyl group.
When R ⁴ , R ⁵ , R ⁶ , and R ⁷ represent an alkyl group, the number of carbon atoms is 1 or more and 40 or less, preferably 1 or more and 30 or less, and more preferably 1 or more and 20 or less. Also R
^{When 4} , R ⁵ , R ⁶ and R ⁷ represent an aryl group, the carbon number is 6 or more and 40 or less, preferably 6 or more and 30 or less, and more preferably 6 or more and 20 or less. Also R
^{When 4} , R ⁵ , R ⁶ , and R ⁷ represent a heterocyclic group, the number of carbon atoms is 1 or more and 30 or less, preferably 2 or more and 20 or less. Further, R ⁴ , R ⁵ , R ⁶ , and R ⁷ may each have a substituent, and examples of the substituent include those shown below as the substituents of X ¹ and X ² . In the general formula (I), R ¹ represents a 6-membered aromatic heterocycle having 3 or more nitrogen atoms (preferably 3 to 4 nitrogen atoms).
The aromatic hetero ring represented by R ¹ may have a substituent, and preferably 1 or 2. Preferably, R ¹ is represented by the following formula.

[0016]

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Here, Q ¹ represents, together with C, a group of non-metal atoms necessary for forming a 6-membered aromatic heterocycle having 3 or more nitrogen atoms. Further, the compound represented by the general formula (III) is preferably the following (D-1) to (D-9).
And more preferably (D-1),
(D-2), (D-4) and (D-5), particularly preferably (D-1) and (D-2).

[0018]

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In the formula, X ¹ and X ² represent a hydrogen atom or a substituent. Here, as an example of the substituent, a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example,
Trifluoromethyl, methyl, ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl,
Octyl, 2-ethylhexyl, dodecyl, etc.), linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms (eg, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), total carbon number 2 to 2 50 alkynyl groups (eg, ethynyl, 1-propynyl, etc.), having 6 to 6 carbon atoms
50 aryl groups (for example, phenyl, naphthyl, anthryl and the like), and an acyloxy group having 1 to 50 carbon atoms (for example,

Acetoxy, tetradecanoyloxy, benzoyloxy etc.), carbamoyloxy group having 1 to 50 carbon atoms (eg N, N-dimethylcarbamoyloxy etc.), carbonamido group having 1 to 50 carbon atoms (eg formamide) , N-methylacetamide, acetamide,
N-methylformamide, benzamide, etc.), having 1 carbon atom
To 50 sulfonamide groups (for example, methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.), 1 to 50 carbon atoms
Carbamoyl group (for example, N-methylcarbamoyl,
N, N-diethylcarbamoyl, N-mesylcarbamoyl, etc.), a sulfamoyl group having 0 to 50 carbon atoms (for example,
N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) sulfamoyl and the like), an alkoxy group having 1 to 50 carbon atoms (for example, retoxy, propoxy, isopropoxy, Octyloxy, t-octyloxy, dodecyloxy, 2-
(2,4-di-t-pentylphenoxy) ethoxy and the like), an aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4-methoxyphenoxy, naphthoxy and the like),
An aryloxycarbonyl group having 7 to 50 carbon atoms (for example, phenoxycarbonyl, naphthoxycarbonyl, etc.),

An alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), an N-acylsulfamoyl group having 1 to 50 carbon atoms (eg, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 50 carbon atoms (eg, ethoxycarbonylamino, etc.), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl , A hydroxy group, a sulfo group, a mercapto group, etc.), an alkylsulfinyl group having 1 to 50 carbon atoms (eg, methanesulfinyl, octanesulfinyl, etc.), an arylsulfinyl group having 6 to 50 carbon atoms (eg, benzenesulfinyl, 4-chlorophenyl) Sulfinyl, p-toluenesulfinyl, etc.), having 1 to 5 carbon atoms
An alkylthio group of 0 (eg,

Methylthio, octylthio, cyclohexylthio, etc.), arylthio groups having 6 to 50 carbon atoms (eg phenylthio, naphthylthio, etc.), 1 to 50 carbon atoms.
Ureido group (eg, 3-methylureido, 3,3-
Dimethylureide, 1,3-diphenylureide, etc.),
A heterocyclic group having 2 to 50 carbon atoms (as a hetero atom, for example, a 3- to 12-membered monocyclic or condensed ring containing at least one or more of nitrogen, oxygen and sulfur;
Furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,
2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl, trifluoroacetyl, etc.), carbon Sulfamoylamino groups of numbers 0 to 50 (e.g., N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), silyl groups of 3 to 50 carbon atoms (e.g., trimethylsilyl, dimethyl-t-butylsilyl, Triphenylsilyl and the like, and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like). The above substituents may further have a substituent,
Examples of the substituent include the substituents mentioned here. Further, X ¹ and X ² may combine with each other to form a condensed ring.

The carbon number of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 34 or less. Moreover, 1 or more is preferable. (D-1)
To (D-6), the sum of Hammett's substituent constant σ p values of X ¹ and X ² is 0 or more and 1.80 or less, preferably 0.1 or more and 1.60 or less, and more preferably 0.1. 1
It is 5 or more and 1.40 or less. Also, (D-7) to (D-
The Hammett substituent constant σ p value of X ¹ in 9) is 0 or more and 0.9 or less, preferably 0.05 or more and 0.8 or less, and more preferably 0.07 or more and 0.7 or less. If the σp value (sum) is smaller than these ranges, there is a problem such as insufficient color development. On the contrary, if it is large, the synthesis and availability of the compound itself becomes difficult and the stability of the compound decreases. It causes problems such as

Regarding the Hammett's substituent constants σ p and σ m, see, for example, Naoki Inamoto, “Hamet's Rule-Structure and Reactivity” (Maruzen), “New Experimental Chemistry Lecture 14, Synthesis and Reaction V of Organic Compounds” 2605. Page (edited by the Chemical Society of Japan, Maruzen), Tadao Nakaya, "Commentary on Theoretical Organic Chemistry", page 217 (Tokyo Kagaku Dojin), Chemical Review (Vol. 91), 165-195.
The book is described in detail in pages (1991).

R ² and R ³ in the general formula (III) represent a hydrogen atom or a substituent, and specific examples of the substituent include X ¹ and
It has the same meaning as described above for X ² , but preferably represents 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, or 1 to 1 carbon atoms. 50 substituted or unsubstituted heterocyclic groups, more preferably at least one of R ² and R ³ is a hydrogen atom.

When the main ingredient of the present invention is incorporated in a light-sensitive material, it is preferable that at least one of Z ¹ and R ^{1 to} R ⁷ has a ballast group. Further, when it is contained in the treatment liquid, it is preferable that at least one of Z ¹ and R ^{1 to} R ⁷ has a hydrophilic group.

Next, the novel color developing agents used in the present invention will be specifically shown, but the scope of the present invention is not limited to these specific examples.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The color developing agents of this invention can be synthesized by a variety of methods, such as US Pat. No. 4,481,
No. 268 and Japanese Patent Application Nos. 7-49287 and 7-55204
Issue A. R. Edited by Katritzky “Comprehensive Heteroc
yclic Chemistry ", Volume 3 (Pergamon Press, 19
1984) etc. can be referred to. Typical synthetic examples of the compounds used in the present invention are shown below. (Synthesis Example 1) Synthesis of Exemplified Compound D-1

[0035]

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1a (0.1 mol) and tetramethylguanidine (0.2 mol) were mixed in acetonitrile, 1b (0.1 mol) was added thereto, and the mixture was reacted at room temperature for 2 hours.
Water was added thereto and extracted twice with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated to obtain 1c in 91% yield. Then 1c (0.09 mol) 16
N, N-dimethylacetamide was added to the crystals produced by heating at 0 ° C. for 2 hours, the mixture was stirred at room temperature for 1 hour, water was added, and the crystals were collected by filtration to give 1d of crude crystals in a yield of 70%. Obtained. 1d (0.06 mol) was reacted with phosphorus oxychloride (0.18 mol) in acetonitrile (120 ml) under reflux for 3 hours, cooled to room temperature and poured into ice water. The precipitated crystals were collected by filtration and washed with water, whereby 1e could be obtained in a yield of 90%.

A mixture of 1e (0.05 mol) and tetrahydrofuran (100 ml) was added to hydrazine hydrate (0.2
(5 mol) was added and the mixture was reacted at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. Water was added thereto, and the precipitated crystals were collected by filtration to obtain 1f of crude crystals (0.025 mol, a value converted as a pure product). Then, a solution of tetrahydrofuran (200 ml) for 1 h (0.0122 mol) was ice-cooled, and
g (0.0367 mol) and triethylamine (0.07
34 mol) was added and reacted for 2 hours. Crude crystals of 1f (0.025 mol) were added thereto and reacted at room temperature for 3 hours. Thereafter, water and ethyl acetate were added to the reaction solution to remove the aqueous layer, and the organic layer was washed with 1N hydrochloric acid. When the residue obtained by drying and concentrating the organic layer with magnesium sulfate was analyzed with a mass spectrometer, it was confirmed that Exemplified Compound D-1 was produced.

Synthesis Example 2 Synthesis of Exemplified Compound D-4

[0039]

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4b (0.2 mol) and 4a (0.2 mol)
Was mixed in ethanol (200 ml), a 28% methanol solution of sodium methoxide (equivalent to 0.04 mol of sodium methoxide) was added thereto, and the mixture was refluxed for 9 hours. After the solvent was distilled off under reduced pressure, water was added. The precipitated crystals were collected by filtration to give 4c (0.14 mol). 4c
(0.045 mol) was reacted with phosphorus oxychloride (0.135 mol) in acetonitrile (100 ml) under reflux for 4 hours, cooled to room temperature and poured into ice water. The precipitated crystals are collected by filtration,
By washing with water, 4d (0.04 mol) was obtained. This was prepared in the same manner as in Synthesis Example 1 with hydrazine monohydrate, 4f,
Exemplified Compound D-4 could be obtained by reacting with 4 g.

The color developing agent of the present invention is used together with a compound (coupler) which forms a dye by an oxidative coupling reaction. This coupler may be a coupler whose coupling position with the oxidized form of the main agent is unsubstituted or substituted, but in the present invention, a substituted coupler is preferred. Specific examples of couplers include Theory of Photographic Process (4th Ed., Edited by TH James, Macmillan, 1977), pages 291 to 334, and 3.
54-361, JP-A-58-12353, 58-
No. 149046, No. 58-149047, No. 59-1
Nos. 1114, 59-124399, 59-174
No. 835, No. 59-231539, No. 59-2315
No. 40, No. 60-2951, No. 60-14242,
No. 60-23474, No. 60-66249 and the like.

Examples of couplers preferably used in the present invention are listed below. The couplers preferably used in the present invention include compounds having the structures represented by the following general formulas (1) to (12). These are compounds generally referred to as active methylene, pyrazolone, pyrazoloazole, phenol, naphthol, and pyrrolotriazole, respectively, and are compounds known in the art.

[0043]

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[0044]

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[0045]

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The general formulas (1) to (4) represent couplers called active methylene couplers, in which R ¹⁴ represents an acyl group which may have a substituent, a cyano group, a nitro group, an aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group. In the general formulas (1) to (3), R ¹⁵ is an alkyl group, an aryl group or a heterocyclic residue which may have a substituent. In the general formula (4), R ¹⁶ is an aryl group which may have a substituent or a heterocyclic residue. R ¹⁴ ,
Examples of the substituent which R ¹⁵ and R ¹⁶ may have include the aforementioned X ¹
The above-mentioned examples can be given as examples of ~ X ⁵ .

In the general formulas (1) to (4), Y is a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of a developing agent. Examples of Y are heterocyclic groups (saturated or unsaturated 5- to 7-membered monocyclic or condensed rings containing at least one of nitrogen, oxygen, sulfur and the like as a hetero atom, and examples thereof include succinimide and malein. Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole,
Benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-
2-one, oxazolin-2-one, thiazoline-2-
ON, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6 -Dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6
-Pyridazone, 2-pyrazone, 2-amino-1,3,4
-Thiazolidine, 2-imino-1,3,4-thiazolidine-4-one and the like), a halogen atom (for example, a chlorine atom,
A bromine atom, an aryloxy group (e.g., phenoxy, 1-naphthoxy, etc.), a heterocyclic oxy group (e.g.,
Pyridyloxy, pyrazolyloxy etc.), acyloxy group (eg acetoxy, benzoyloxy etc.), alkoxy group (eg methoxy, dodecyloxy etc.), carbamoyloxy group (eg N, N-diethylcarbamoyloxy, morpholinocarbonyloxy etc.) , An aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), an alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), an arylthio group (eg, phenylthio, naphthylthio, etc.), a heterocyclic thio group (eg, Tetrazolylthio, 1,3,4-thiadiazolylthio, 1,
3,4-oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy group (eg, methanesulfonyloxy etc.), arylsulfonyloxy group (eg, benzenesulfonyl) Oxy, toluenesulfonyloxy etc.), carbonamide group (eg acetamide, trifluoroacetamide etc.), sulfonamide group (eg methanesulfonamide, benzenesulfonamide etc.), alkylsulfonyl group (eg methanesulfonyl etc.), Arylsulfonyl group (eg, benzenesulfonyl etc.), alkylsulfinyl group (eg, methanesulfinyl etc.), arylsulfinyl group (eg, benzenesulfinyl etc.), arylazo group (eg. If, phenylazo, naphthylazo etc.), carbamoylamino group (e.g., N- methylcarbamoyl amino, etc.) and the like.

Y may be substituted with a substituent,
Examples of the substituent for substituting Y include those described for X ^{1 to} X ⁵ . Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group.

In the general formulas (1) to (4), R ¹⁴ and R
¹⁵ , R ¹⁴ and R ¹⁶ may combine with each other to form a ring.
Formula (5) represents a coupler called a 5-pyrazolone-based coupler, wherein R ¹⁷ is an alkyl group, an aryl group,
Represents an acyl group or a carbamoyl group. R ¹⁸ represents a phenyl group or a phenyl group substituted with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups.

Among the 5-pyrazolone type couplers represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group, and R is
A phenyl group in which ¹⁸ is substituted with one or more halogen atoms is preferred. To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-
Methoxyphenyl group, 2-chloro-5-tetradecanamidophenyl group, 2-chloro-5- (3-octadecenyl-1-succinimido) phenyl group, 2-chloro-5
An aryl group such as -octadecylsulfonamidophenyl group or 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group or an acetyl group, 2- (2,4-di- t-pentylphenoxy) butanoyl group, benzoyl group, 3-
(2,4-di-t-amylphenoxyacetamido) benzoyl group and like acyl groups, which may further have a substituent, which may be a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is an organic substituent or a halogen atom to be linked. Y has the same meaning as described above. R ¹⁸ is a 2,4,6-trichlorophenyl group,
A substituted phenyl group such as a 2,5-dichlorophenyl group and a 2-chlorophenyl group is preferred.

The general formula (6) represents a coupler called a pyrazoloazole coupler, and in the formula, R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Among the pyrazoloazole couplers represented by the general formula (6), imidazo [1,2-
b] pyrazoles, pyrazolo [1,5-b] -1,2,4-triazoles described in U.S. Pat. No. 4,500,654, and pyrazolo [5 described in U.S. Pat. No. 3,725,067. , 1-c] -1,2,4-triazoles are preferred. For details of the substituent of the azole ring represented by substituents R ¹⁹ and Q ³ , see, for example, US Pat. No. 4,540,
No. 654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-65
No. 245, a pyrazoloazole coupler in which a branched alkyl group is directly bonded to the 2-, 3- or 6-position of a pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
09457 or 63-307453, pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position, and Japanese Patent Application No. 1-22.
No. 279 is a pyrazolotriazole coupler having a carbonamide group in the molecule. Y has the same meaning as described above.

Formulas (7) and (8) are couplers referred to as phenol couplers and naphthol couplers, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent. In formulas (7) and (8), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2 and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. As the substituents of R ^{21 to} R ^23, the above X ¹ to
Those mentioned as examples of X ⁵ may be mentioned. Y has the same meaning as described above.

Preferred examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396;
Nos. 4,334,011, 4,327,173
No. 3,329,729, West German Patent Publication No.
2,5-diacylaminophenol-based compounds described in US Pat. No. 4,696,956, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427. Examples thereof include 2-phenylureido-5-acylaminophenol-based compounds described in No. 767 and the like. Y is the same as that described above.

Preferred examples of the naphthol coupler represented by the general formula (8) include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
No. 200, etc., and 2-carbamoyl-1-naphthols described in US Pat. No. 4,690,889 and the like.
-Carbamoyl-5-amido-1-naphthol type and the like. Y is the same as that described above.

The general formulas (9) to (12) are couplers called pyrrolotriazole, and R ³² , R ³³ and R ³⁴ represent a hydrogen atom or a substituent. Y is as described above. ^Examples of the substituent of R ³² , R ³³ and R ³⁴ include the aforementioned X
Include those mentioned above as examples of the ¹ to X ^5. Preferred examples of the pyrrolotriazole-based couplers represented by the general formulas (9) to (12) include European Patent 488,248.
A1, No. 491,197 A1, No. 545,30
A coupler in which at least one of R ³² and R ³³ described in No. 0 is an electron-withdrawing group can be mentioned. Y is the same as that described above.

In addition, couplers having a structure such as condensed ring phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-condensed heterocycle, and 5,6-condensed heterocycle can be used. As a condensed ring phenol type coupler, U.S. Pat. No. 4,327,173
No. 4,564,586 and 4,904,57
The couplers described in No. 5, etc. can be used. U.S. Pat. No. 4,818,672, as imidazole couplers,
The couplers described in JP-A-5,051,347 and the like can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used. Active methylene and active methine couplers are described in US Pat. Nos. 5,104,783 and 5,162,196.
The couplers described in (1) and (2) can be used. 5,5-Fused heterocyclic couplers include US Pat. No. 5,164,289.
Pyrropyrazole-based couplers described in
Pyrroloimidazole couplers described in No. 74429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, and EP 556.
The couplers described in No. 700 can be used.

In the present invention, in addition to the above-mentioned coupler, West German Patent Nos. 3,819,051A and 3,823,049 are also included.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
No. 4-179949, No. 4-182645, No. 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
The couplers described in JP-A No. 4-204731, JP-A No. 4-204732, and the like can also be used.

Specific examples of the coupler that can be used in the present invention are shown below, but the present invention is not limited thereto.

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The addition amount of the coupler used in the present invention depends on its molar absorption coefficient (ε). When the coupler is about 5,000 to 500,000, the coating amount is 0.001 to 100 mmol /
m ² , preferably about 0.01 to 10 mmol / m ² , more preferably about 0.05 to 5 mmol / m ² .
When the color developing agent of the present invention is contained in a light-sensitive material, any layer (eg, emulsion layer, intermediate layer, etc.) may be used.
Preferably, it is contained in the emulsion layer. When there are a plurality of emulsion layers, it is preferable to include them in all the layers. The addition amount of the color developing agent of the present invention is 0.01 to 100 times, preferably 0.1 to 10 times the amount of the coupler.
Times, more preferably 0.2 to 5 times. Further, instead of being contained in the light-sensitive material, it may be contained in the processing solution for use. In this case, preferably 0.
1 g to 100 g, and more preferably 1 g to 20 g.

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 from the color developing agent to the silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably a compound of the general formula The compound is an electron-emitting compound represented by (B-1) or the general formula (B-2), which conforms to the Kendall-Peltz rule. Among them, those represented by (B-1) are particularly preferred.

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In the general formulas (B-1) and (B-2),
R ^{51 to} R ⁵⁴ 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 represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group,
Heterocyclic group, alkoxy group, cycloalkyloxy group,
Aryloxy group, heterocyclic oxy 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 A cycloalkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a sulfamoyloxy group, an alkanesulfonyloxy group, an arenesulfonyloxy group,
Acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, sulfamoylamino Group, alkylsulfinyl group, arenesulfinyl group, alkanesulfonyl group, arenesulfonyl group, sulfamoyl group, sulfo group, phosphinoyl group,
Represents a phosphinoylamino group. q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different. R ⁶⁰ represents an alkyl group or an aryl group.

The compounds represented by formula (B-1) or (B-2) are specifically shown, but the auxiliary developing agent used in the present invention is not limited to these examples.

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In the present invention, a blocked photographic reagent which releases a photographically useful group upon processing as represented by the general formula (A) can be used. General formula (A) A- (L) n-PUG A represents a block group in which the bond with (L) n-PUG is cleaved during development, and L is the bond on the left side of L in the general formula (A). After that, the right side of L represents a linking group which is cleaved, n represents an integer of 0 to 3, and PUG represents a photographically useful group.

The group represented by formula (A) will be described below. As the blocking group represented by A, the following known ones can be applied. That is, JP-B-48-9968, JP-A-52-8828, and 57-88.
No. 82834, U.S. Pat. No. 3,311,476, and Japanese Patent Publication No. 47-44805 (U.S. Pat.
No. 617) and the like, and a blocking group such as an acyl group or a sulfonyl group, and JP-B-55-17369 (U.S. Pat. No. 3,888,677), and JP-B-55-9696 (U.S. Pat. No. 830), No. 55-34927 (U.S. Pat. No. 4,009,029), and JP-A-56-7.
No. 7842 (U.S. Pat. No. 4,307,175) and No. 5
No. 9-105640, JP-A-59-105641, and JP-A-59-105542, and a blocking group utilizing a reverse Michael reaction.
Nos. 3,674,478 and 3,932.
480, 3,993,661, JP-A-57-13
Nos. 5944, 57-135,945 (U.S. Pat. No. 4,420,554), 57-136640, 61-196239, and 61-196240 (U.S. Pat. No. 4,702,999). 61-185743
No. 61-124941 (U.S. Pat. No. 4,639,
No. 408) and JP-A-2-280140, and the like, a blocking group utilizing the formation of a quinone methide or a compound similar to the quinone methide by intramolecular electron transfer, U.S. Pat. Nos. 4,358,525 and 4,330, 617
JP-A-55-53330 (U.S. Pat. No. 4,31,31)
0,612), No. 59-121328, No. 59-2
No. 18439 and 63-318555 (European Patent Publication No. 0295729) and the like, a blocking group utilizing an intramolecular nucleophilic substitution reaction, JP-A-57-76.
Nos. 541 (U.S. Pat. Nos. 4,335,200) and 57
No. 135949 (U.S. Pat. No. 4,350,752)
No.), No. 57-179842, No. 59-137945
Nos., 59-140445 and 59-219741
No. 59-202459, No. 60-41034 (US Pat. No. 4,618,563), No. 62-599.
No. 45 (U.S. Pat. No. 4,888,268);
No. 65039 (US Pat. Nos. 4,772,537), 62-80647, and JP-A-3-236047 and 3-238445.
Block group utilizing ring cleavage of member ring, JP-A-59-20
1057 (U.S. Pat. No. 4,518,685), 6
1-95346 (U.S. Pat. No. 4,690,885)
No. 61-95347 (U.S. Pat. No. 4,892,892).
811), JP-A-64-7035, and JP-A-64-4.
2650 (U.S. Pat. No. 5,066,573), JP-A-1-245255, 2-207249, 2-.
235055 (US Pat. Nos. 5,118,596) and 4-186344, and the like, a blocking group utilizing the addition reaction of a nucleophile to a conjugated unsaturated bond,

JP-A-59-93442 and 61-32.
Nos. 839 and 62-163051 and 5-3
No. 7299 and the like, a blocking group utilizing a β-elimination reaction, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes described in JP-A-61-188540, No. 187850, a block group utilizing the Rossen rearrangement reaction.
Nos. 80646, 62-144163 and 62-
No. 147457, a block group utilizing the reaction of an N-acyl compound of thiazolidine-2-thione with an amine, JP-A-2-296240 (U.S. Pat.
No. 19,492), No. 4-177243, No. 4-17
No. 7244, No. 4-177245, No. 4-177724
No. 6, 4-177247, 4-177248,
4-177249, 4-179948, 4-
184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419 and JP-A-5-4581.
JP-A-3-236047 and JP-A-3-238445, a blocking group having two electrophilic groups and reacting with a dinucleophile described in JP-A No. 6-360.

In the compound represented by the general formula (A), L
The group represented by may be any linking group capable of cleaving (L) n-1-PUG after being released from the group represented by A during the development processing. For example, a group utilizing cleavage of a hemiacetyl tar ring described in U.S. Pat. Nos. 4,146,396, 4,652,516 or 4,698,297;
8,962, 4,847,185 or 4,857,440, a timing group for causing an intramolecular nucleophilic substitution reaction, US Pat. No. 4,409,3.
No. 23 or 4,421,845, a timing group for causing a cleavage reaction utilizing an electron transfer reaction, and the hydrolysis reaction of an imino ketal described in US Pat. No. 4,546,073. To cause a cleavage reaction, a group to cause a cleavage reaction by utilizing a hydrolysis reaction of an ester described in West German Published Patent No. 2,626,317, or a sulfite ion described in European Patent No. 0572084. A group that causes a cleavage reaction by utilizing the reaction with

Next, PUG in the general formula (A) will be described. PUG in the general formula (A) represents a photographically useful group such as an antifoggant and a photographic dye, but in the present invention, auxiliary development represented by the general formulas (B-1) and (B-2). The main drug is particularly preferably used for PUG. When the auxiliary developing agent represented by the general formulas (B-1) and (B-2) corresponds to the PUG of the general formula (A), the bonding position is the oxygen atom or nitrogen atom of the auxiliary developing agent. . 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, and forming a photosensitive silver halide or dye-forming layer on any of the photographic constituent layers. And a color-forming coupler. The main agent that directly reacts with the silver salt is called a color developing agent, and the main agent that indirectly reacts with the silver salt via a mediator such as an auxiliary developing agent is called a color-forming reducing agent, and the compound of the present invention is used for any of them. be able to. Although both terms are used herein, they are not strictly distinct and, in many cases, can be considered synonymous. The dye-forming coupler and the color-forming reducing agent used in the present invention are most commonly added to the same layer, but if they are in a reactive state, they can be divided and added to different layers. 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.

The color-forming reducing agent and coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods such as the method described in US Pat. The oil-in-water dispersion method is preferred, in which an organic solvent is used in combination), and the mixture is emulsified and dispersed in a gelatin aqueous solution and added to a silver halide emulsion. If necessary, boiling point 50
It can be used in combination with a low boiling point organic solvent of up to 160 ° C. These dye-donating compounds, a nondiffusible reducing agent,
Two or more high boiling point organic solvents can be used in combination.
The high boiling point organic solvent that can be used in the present invention has a melting point of 10
It is preferably a compound which is not miscible with water and has a boiling point of 140 ° C. or higher and a temperature of 0 ° C. or lower, and is a good solvent for the color-forming reducing agent and coupler. The melting point of the high boiling point organic solvent is more preferably 8
0 ° C. or less. However, in the case of a heat-developable photosensitive material, the melting point of the high-boiling organic solvent may exceed 100 ° C. The boiling point of the high boiling point organic solvent is more preferably 160 ° C. or higher, and further preferably 170 ° C. or higher. For details of these high boiling point organic solvents, see JP-A-62-21527.
No. 2 published specification, page 137, lower right column to page 144, upper right column. In the present invention, the amount of the high-boiling organic solvent used may be any amount. 0.02 to 5 are more preferable, and 0.2 to 4 are particularly preferable. In the present invention, a known polymer dispersion method may be used. The steps, effects, and specific examples of the latex for impregnation as a latex dispersion method as one of the polymer dispersion methods are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. No. 2,541,230, Japanese Examined Patent Publication No. 53-41091, European Patent Publication No. 029104, etc., and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723. ing.

The average particle size of the lipophilic fine particles containing the reducing agent for color development of the present invention may be any particle size. It is preferable to set the thickness to 0.05 to 0.3 µ from the viewpoint of color development. Further, 0.05 μ to 0.2 μ is more preferable.

Generally, in order to reduce the average particle size of the lipophilic fine particles, the kind of the surfactant is selected, the amount of the surfactant used is increased, the viscosity of the hydrophilic colloid solution is increased, and the lipophilicity is increased. This can be achieved by reducing the viscosity of the organic layer by using a low-boiling point organic solvent in combination, increasing the shearing force such as increasing the rotation of the stirring blade of the emulsifying device, or increasing the emulsification time. The particle size of the lipophilic fine particles can be measured, for example, by a device such as Nanosizer manufactured by Coulter Co. of England.

In the present invention, when the dye produced from the color-forming reducing agent and the dye-forming coupler is a diffusible dye, a dye fixing element is used together with the light-sensitive material. The dye fixing element may be applied separately on a support different from the light-sensitive material, or may be applied on the same support as the light-sensitive material. The relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer are described in US Pat.
0,626 and the like. The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. When the present invention is applied to such a form, it is not necessary to immerse in an alkali to form a color, and therefore, the image stability after the processing is remarkably improved.
The mordant of the present invention may be used in any layer, but when added to a layer containing the reducing agent for color formation of the present invention, the stability of the reducing agent for color formation deteriorates, and It is preferably used for a layer containing no reducing agent. Furthermore, the dye formed from the color-forming reducing agent and the coupler diffuses through the swollen gelatin film during the treatment and dyes the mordant. Therefore, it is preferable that the diffusion distance is short in order to obtain good sharpness. Therefore, the layer to which the mordant is added is preferably added to the layer adjacent to the layer containing the color-forming reducing agent. Further, since the dye formed from the color-forming reducing agent of the present invention and the coupler of the present invention is a water-soluble dye, it may flow out into the processing solution. Therefore, the layer to which the mordant is added to prevent this is preferably on the side opposite to the support with respect to the layer containing the color-forming reducing agent. However, when the barrier layer as described in JP-A-7-168335 is provided on the side opposite to the support with respect to the layer to which the mordant is added, the layer to which the mordant is added contains a color-forming reducing agent. It is also preferred that it is on the same side of the support as the layer.

The mordant of the present invention may be added to a plurality of layers. Particularly, when there are a plurality of layers containing a color-forming reducing agent, the mordant should be added to each adjacent layer. Is also preferable.

The coupler forming the diffusible dye may be any coupler as long as the diffusible dye formed by coupling with the color-forming reducing agent of the present invention reaches the mordant. The dye preferably has at least one dissociating group having a pKa (acid dissociation constant) of 12 or less, more preferably has at least one dissociating group having a pKa of 8 or less, and particularly preferably has at least one dissociating group having a pKa of 6 or less. It is a thing. The molecular weight of the formed diffusible dye is preferably 200 or more and 2000 or less. Further, (the molecular weight of the formed dye / the number of dissociating groups having a pKa of 12 or less) is 10
It is preferably from 0 to 2,000, more preferably from 100 to 1,000. Here, as the value of pKa, a value measured using dimethylformamide: water = 1: 1 as a solvent is used.

The coupler forming the diffusible dye is 1 × 10 ^{-6 in} an alkaline solution having a solubility of 25 ° C. and a pH of 11 at the diffusible dye formed by coupling with the reducing agent for color formation of the present invention.
It is preferable to dissolve at least mol / l and 1 × 10 ⁻⁵
It is more preferable that the amount is 1 mol / liter or more.
It is particularly preferable to dissolve ^0-4 mol / l or more. The coupler forming the diffusible dye is dissolved in an alkaline solution having a diffusion constant of 25 ° C. and a pH of 11 at a concentration of 10 ⁻⁴ mol / liter in an alkaline solution having a diffusible dye formed by coupling with the color-forming reducing agent of the present invention. In this case, it is preferably 1 × 10 ⁻⁸ m ² / s ⁻¹ or more, more preferably 1 × 10 ⁻⁷ m ² / s ⁻¹ or more, and 1 × 10 ⁻⁶ m ² / s ^−. It is particularly preferred that it is ¹ or more.

The mordant which can be used in the present invention can be arbitrarily selected from the commonly used mordants.
Among them, a polymer mordant is particularly preferable. Here, the polymer mordant is a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic portion, a polymer having a quaternary cation group thereof, or the like.

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group include US Pat. Nos. 4,282,305 and 4,11.
No. 5,124, No. 3,148,061, JP-A-60
No. 118834, No. 60-122941, No. 62-
No. 244043, No. 62-244036 and the like.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, and 1,594. , 961, U.S. Pat. Nos. 4,124,386, 4,115,12.
4, No. 4,450,224, JP-A-48-283.
No. 25, etc.

Other preferable specific examples of homopolymers and copolymers having a vinyl monomer unit having a quaternary ammonium salt include US Pat. No. 3,709,690.
No. 3,898,088, No. 3,958,99
No. 5, JP-A-60-57836 and JP-A-60-60643.
No. 60-122940, No. 60-122942
And No. 60-235134.

Others, US Pat. No. 2,548,564
No. 2,484,430 and 3,148,16
No. 3,756,814 and the like, vinylpyridine polymer and vinylpyridinium cationic polymer; US Pat. No. 3,625,694
No. 3,859,096, No. 4,128,53
8, polymer mordants crosslinkable with gelatin and the like disclosed in GB 1,277,453 and the like; US Pat. Nos. 3,958,995 and 2,721,852
No. 2,798,063, JP-A-54-1152
No. 28, No. 54-145529, No. 54-26027
Aqueous sol-type mordant disclosed in US Pat. No. 3,898,088; water-insoluble mordant disclosed in US Pat. No. 3,898,088; US Pat. No. 4,168,976 (Japanese Patent Laid-Open No. 54-137333) No. 3,709,690, 3,788,855, and 3,642,482; reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification. No. 3,488,706,
No. 3,557,066, No. 3,271,147
No., JP-A-50-71332 and JP-A-53-30328.
Nos. 52-155528, 53-125, 5
Examples include mordants disclosed in the specification of JP-A-3-1024. Other US Pat. No. 2,675,316
And the mordants described in JP-A-2,882,156.

The molecular weight of the polymer mordant of the present invention is 1,0.
100 to 1,000,000 is suitable, and especially 10,000
00 to 200,000 is preferred. The above-mentioned polymer mordant is usually used by being mixed with a hydrophilic colloid. As the hydrophilic colloid, a hydrophilic colloid, a highly hygroscopic polymer or both of them can be used, and gelatin is most typical. The mixing ratio between the polymer mordant and the hydrophilic colloid, and the amount of the polymer mordant applied, are easily determined by those skilled in the art according to the amount of the dye to be morded, the type and composition of the polymer mordant, and the image forming process used. But the mordant / hydrophilic colloid ratio is 20/80
~ 80/20 (weight ratio), mordant applied amount is 0.2 ~ 15
g / m ² is suitable, preferably for use in the 0.5 to 8 g / m ^2.

The support used in the present invention includes glass,
Any support such as paper and plastic film which can be coated with a photographic emulsion layer can be used as long as it is a transmission or reflection support. As the plastic film used in the present invention, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film, a polystyrene film and the like can be used. The "reflective support" that can be used in the present invention refers to a support that enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer. A substrate coated with a hydrophobic resin containing a light-reflective substance such as titanium oxide, zinc oxide, calcium oxide, or calcium sulfate, or a hydrophobic resin itself containing a light-reflective substance dispersed therein was used as a support. Things included. For example, polyethylene-coated paper, polyester-coated paper, polypropylene-based synthetic paper, supports provided with a reflective layer or combined with a reflective substance, for example, glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide films , Polycarbonate film, polystyrene film, and vinyl chloride resin. As the polyethylene-coated paper, polyester-coated paper containing polyethylene terephthalate as a main component described in European Patent EP 0,507,489 is preferably used.

The reflective support used in the present invention is preferably a paper support whose both surfaces are coated with a water-resistant resin layer, in which at least one of the water-resistant resins contains white pigment fine particles. The white pigment particles are preferably contained at a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflective white pigment, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable that the surface of the pigment particles is treated with a divalent to tetravalent alcohol. In the present invention, a support having a surface of diffuse reflection of the second kind can be preferably used. What is the second type diffuse reflectance?
Diffusive reflectivity obtained by imparting irregularities to a surface having a mirror surface and dividing the surface into minute mirror surfaces facing different directions to disperse the divided minute surface (mirror surface) directions. The unevenness of the surface of the second kind diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1
Is about 1.2 μm. Details of such a support are described in JP-A-2-239244.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. To be For example, three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and three layers of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer are coated on the support in combination. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary. In the photosensitive material, the photosensitive layer and the protective layer, an undercoat layer, an intermediate layer,
A photographic constituent layer comprising various protective layers such as an antihalation layer and a back layer can be provided. Further, various filter dyes can be added to the photographic component layer in order to improve color separation. Specifically, the layer structure as described in the above patent, the undercoat layer as described in US Pat. No. 5,051,335, JP-A-1-167,838, and JP-A-61
No. 20,943, an intermediate layer having a solid pigment, JP-A-1-120,553, and JP-A-5-34,884.
And DIR as described in No. 2-64,634
Intermediate layer with compound, US Pat. No. 5,017,454
No. 5,139,919 and JP-A-2-23504.
4, an intermediate layer having an electron transfer agent as described in
It is possible to provide a protective layer having a reducing agent as described in JP-A-249,245 or a layer in which these are combined.

As the dye that can be used in the yellow filter layer and the antihalation layer, those dyes that are decolored or dissolved during development and do not contribute to the density after processing are preferable. The fact that the dye in the yellow filter layer and the antihalation layer is erased or removed at the time of development means that the amount of the dye remaining after the processing is 1/3 or less, preferably 1 /
The dye component may be 10 or less, and the components of the dye may be eluted from the light-sensitive material or transferred into the processing material at the time of development, or may be changed to a colorless compound by reacting at the time of development.

As the dye that can be used in the light-sensitive material of the present invention, known dyes can be used. For example, a dye that dissolves in the alkali of the developing solution, or a type of dye that decolorizes by reacting with components in the developing solution, sulfite ions, the base agent, and the alkali can be used. Specifically, dyes described in European Patent Application EP 549,489A and JP-A-7-15
No. 2129, ExF2-6 dyes. Dyes dispersed in a solid as described in Japanese Patent Application No. 6-259805 can also be used. This dye can be used when the photosensitive material is developed with a processing solution, but is particularly preferable when the photosensitive material is thermally developed using a processing sheet described later. In addition, a mordant and a binder can be dyed with a dye. In this case, as the mordant and the dye, those known in the photographic field can be used.
No. 58-59, No. 500,626, and JP-A-61-88.
256, page 32 to 41, JP-A-62-244043,
Examples include mordants described in JP-A-62-244036. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the mobile dye can be released with an alkali at the time of development and eluted in a processing solution or transferred and removed to a processing sheet. Specifically, U.S. Pat. Nos. 4,559,290 and 4,783,396, European Patent 220,746A2, and JP-A-87-611.
No. 9 and paragraphs 0080 to 0081 of Japanese Patent Application No. 6-259805.

It is also possible to use a leuco dye capable of decoloring, and specifically, a silver halide containing a leuco dye previously developed with a developer of an organic acid metal salt in JP-A-1-150,132. A light sensitive material is disclosed. Since the leuco dye and the developer complex react with heat or an alkaline agent to erase the color, a combination of the leuco dye and the developer is preferred when the light-sensitive material of the present invention undergoes thermal development. Known leuco dyes can be used, and Moriga,
Yoshida, "Dyes and Chemicals", 9, 84 pages (Chemical Products Association),
"New Edition Dye Handbook" 242 (Maruzen, 1970), R. Ga
rner "Reports on the Progress of Appl. Chem" 5
6, p. 199 (1971), "Dyes and chemicals" 19, 23
Page 0 (Chemical Products Association, 1974), “Coloring Materials” 62, 2
88 (1989), "Dyeing Industry" 32, 208, etc. As the developer, a metal salt of an organic acid is preferably used in addition to the acid clay-based developer and phenol formaldehyde resin. As metal salts of organic acids, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodan salts, metal salts of xanthogenates, and the like are useful, and zinc is particularly preferable as the metal.
Among the above-mentioned color developing agents, oil-soluble zinc salicylate is disclosed in U.S. Pat.
Nos. 6,941, and Japanese Patent Publication No. 52-1327 can be used.

The light-sensitive material of the present invention is preferably hardened with a hardener. U.S. Pat.
678,739, column 41, 4,791,042,
JP-A-59-116,655 and 62-245,26.
No. 1, No. 61-18,942, JP-A-4-218,0
No. 44 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-methylol-based hardeners (such as dimethylol urea), boric acid, metaboric acid and polymer hardeners (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the hydrophilic binder.

Various antifoggants or photographic stabilizers and their precursors can be used in the light-sensitive material. Specific examples thereof include the above-mentioned Research Disclosure, U.S. Pat. (9) page, (57) ~
(71) and (81)-(97), U.S. Pat.
No. 5,610, No. 4,626,500, No. 4,98
3,494, JP-A-62-174,747, 62.
-239,148, JP-A-1-150,135, 2-110,557, 2-178,650, RD
No. 17,643 (1978), pages (24) to (25), and the like. The amount of these compounds is preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver, and further 1
^X10-5 to ^1x10-2 mol is preferably used.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. The calcium content of gelatin is preferably 800 ppm or less, more preferably 200 ppm or less, and the iron content of gelatin is preferably 5 ppm or less, more preferably 3 ppm or less. Further, in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, Japanese Patent Application Laid-Open No.
It is preferable to add an antifungal agent as described in Japanese Patent No. 1247.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. Further, using the light-sensitive material of the present invention as a photographic light-sensitive material, development is carried out by a heat development method having a development temperature of 60 ° C. or higher and 150 ° C. or lower, and the obtained color negative image information is converted into a digital signal, and the above-mentioned thermal development is carried out. When printing with a light-sensitive material, you can perform everything from shooting to printing without using the processing liquid used in conventional color photography. Also,
Even if you use PICTROSTAT 330 from Fuji Photo Film Co., Ltd., and optically read image information with the NSE unit and output it, you can perform everything from shooting to printing without using any processing liquid.

The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as rodin silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are desired, silver halide grains having a high silver chloride content are desirable. Further, in the case of suppressing development appropriately, it is preferable to contain silver iodide.
The preferred silver iodide content depends on the intended light-sensitive material.

The silver halide emulsion of the present invention preferably has a distribution or structure in terms of halogen composition in its grains. A typical example is JP-B-43-131.
No. 62, JP-A-61-215540 and JP-A-60-2
No. 22845, JP-A-60-143331, JP-A-6-143331
No. 1-75337 and JP-A-60-222844.

In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be prepared. Examples of these are JP-A-59
-133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.

In the case of a joint structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodan or silver carbonate may be combined with silver halide to form a joint structure.

In the case of grains such as silver iodobromide having these structures, it is a preferred embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred.
Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable.

It is important to control the halogen composition near the surface of the grain. Increase the silver iodide content near the surface,
Alternatively, increasing the silver chloride content can be selected according to the purpose because the adsorption property of the dye and the developing speed are changed.

The silver halide grains used in the present invention, even if they are normal crystals not containing twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photographs (Corona Publishing Co.), P.P. 163, a parallel multiple twin crystal containing two or more parallel twin planes, a non-parallel multiple twin crystal containing two or more non-parallel twin planes, and the like are used according to the purpose. be able to. An example of mixing particles having different shapes is US Pat. No. 4,865,
No. 964. In the case of normal crystals (10
A cube consisting of a 0) plane, an octahedron consisting of a (111) plane,
JP-B-55-42737, JP-A-60-222842
No. 12, dodecahedral particles having a (110) plane can be used. In addition, Journalof Imaging S
Cience Vol. 30, p. 247 Particles having a (hlm) plane as reported in 1986 can be selected and used according to the purpose. A tetrahedral particle in which (100) plane and (111) plane coexist in one particle, a particle in which (100) plane and (110) plane coexist, or a particle in which (111) plane and (110) plane coexist, Particles in which two faces or many faces coexist can be selected and used according to the purpose.

The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Practice.
(1930)), 131; Gatov, Photographic Science and Engineering (Gutoff, Ph
otographic Science and Engineering), Volume 14, 2
48-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,43
It can be prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, and the like. U.S. Pat.
No. 6 describes this in detail. 80 of the total projected area of the grain
It is desirable that the average aspect ratio of 1% or more is 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. The shape of the tabular grains can be selected from triangles, hexagons, and circles. A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,797,354, is a preferred form.

The equivalent circle diameter of the projected area is often used as the grain size of tabular grains.
No. 8,106 has an average diameter of 0.6.
Submicron particles are preferred for high image quality. Also preferred are emulsions having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable.

Particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations are preferably selected according to the purpose. It is also possible to select a dislocation or a dislocation that is introduced linearly with respect to a specific direction of the crystal orientation of the grain, or to introduce the entire grain, or to introduce only a specific portion of the grain, for example. The dislocation can be introduced only in the fringe portion of the particle. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of normal grains or irregular grains typified by potato grains.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1, or West German Patent No. 2,306,447C2. , JP Sho 60
The surface may be modified as disclosed in JP-A-221320.

A structure in which the particle surface is flat is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532, JP-A-60-22132
0 or U.S. Pat. No. 4,643,966.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and grain thickness, or the sphere equivalent diameter of the volume determined by the Coulter counter method. Can be evaluated. It can be selected from ultrafine particles having a sphere-equivalent diameter of 0.01 micron or less, and coarse particles having a diameter of more than 10 microns. Preferably, grains having a size of 0.1 to 3 microns are used as photosensitive silver halide grains.

The emulsion used in the present invention may be a so-called polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. As a scale representing the size distribution, a variation coefficient of a circle equivalent diameter of a projected area of a particle or a sphere equivalent diameter of a volume may be used. When a monodispersed emulsion is used, the coefficient of variation is 25% or less,
It is more preferable to use an emulsion having a size distribution of 20% or less, more preferably 15% or less.

In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed in the same layer in the emulsion layers having substantially the same color sensitivity. Alternatively, it can be applied in multiple layers as separate layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphkid, published by Paul Montell (P. G.
lafkides, Chimie et Physique Photographique Paul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emuls
ion Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VL Zelikman et al, Making and Coating Photogra
Phic Emulsion, Focal Press, 1964) and the like. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is more preferable. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. It is also effective in some cases to add fine particles having various halogen compositions to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by the halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,14.
2,900, EP 273,429, EP 273,
No. 430, West German Published Patent No. 3,819,241, and the like. A solution of a soluble halogen or silver halide grains can be added to convert the silver salt into a sparingly soluble silver salt.

In addition to the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480; U.S. Pat. No. 3,650,757;
The particle formation method of changing the concentration or changing the flow rate as described in JP-A-4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide to be supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time.

A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is described in US Pat. No. 2,996,287.
Nos. 3,342,605 and 3,415,650
No. 3,785,777, West German published patent 2,55
6,885 and 2,555,364.

A silver halide solvent is useful for the purpose of promoting ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in the dispersion medium in the reactor before adding the silver and halide salts,
A halide salt, silver salt or deflocculant can be added and introduced into the reactor.

Examples of these include ammonia, thiocyanates (such as rhodan potassium and rhodan ammonium) and organic thioether compounds (for example, US Pat. No. 3,574,743).
No. 628, No. 3,021,215, No. 3,057,7
No. 24, No. 3,038,805, No. 4,276,37
4, No. 4,297,439, No. 3,704,130
No. 4,782,013, JP-A-57-10492.
Compounds described in No. 6 and the like. ), A thione compound (for example, tetrasubstituted thiourea described in JP-A-53-82408, 55-77737, U.S. Pat. No. 4,221,863, etc., and JP-A-53-144319). Compound), a mercapto compound capable of promoting the growth of silver halide grains described in JP-A-57-202531, and an amine compound (for example, JP-A-54-10).
No. 0717 etc.) and the like.

As the protective colloid used in the preparation of the emulsion of the present invention and as the binder of the other hydrophilic colloid layers, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. A variety of synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers; Can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan.
The enzyme-treated gelatin as described in No. 16, P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. JP-A-1-1-1
It is preferable to use the low molecular weight gelatin described in No. 58426 for preparing tabular grains.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain and a method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example, CdB
r ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ ,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (N
H _{4) 4} [Fe (CN) _{6], K 3 IrCl 6, (NH} 4) 3
RhCl ₆ , K ₄ Ru (CN) _{6 and the} like can be mentioned. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains of the present invention have at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three types are collectively called chalcogen sensitization), noble metal sensitization, or reduction sensitization. It can be applied at any step of the process for producing a silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. The chemical sensitization that can be preferably carried out in the present invention is a chalcogen sensitization and a noble metal sensitization alone or in combination thereof, and is written by James (TH James), The Photographic Process, 4th Edition, published by Macmillan Inc.,
1977, (TH James, The Theory of the Photog
raphic Process, 4th ed, Macmillan, 1977) 67-
It can be done using activated gelatin as described on page 76, and can also be done by Research Disclosure Ite.
m 12008 (April 1974); same item 13452
(June 1975); Item 307105 (1989)
Nov.), U.S. Pat. Nos. 2,642,361 and 3,
297,446, 3,772,031, 3,8
57,711, 3,901,714, 4,26
6,018, and 3,904,415, and British Patent 1,315,755.
It can be carried out with Ag of 5 to 10, pH of 5 to 8 and a temperature of 30 to 80 ° C. with sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers.

In sulfur sensitization, an unstable sulfur compound is used, and specifically, a thiosulfate (eg, hypo),
Thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanins, mercaptos, thioamides, thiohydantoins, 4-oxo-oxazolidine-2-thiones, di- or polysulfides, polythionic acid Salt and elemental sulfur, and U.S. Pat. Nos. 3,857,711, 4,266.
Known sulfur-containing compounds described in No. 018 and No. 4,054,457 can be used. Sulfur sensitization is often used in combination with noble metal sensitization.

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mol of silver halide.
10 ^-7 to 1 × 10 ^-3 mol, more preferably 5
X 10 ^-7 to 1 X 10 ^-4 mol.

In the selenium sensitization, known unstable selenium compounds are used, for example, US Pat. No. 3,297,44.
No. 6,297,447 and the like, and specific examples thereof include colloidal metal selenium and selenoureas (eg, N, N-dimethylselenourea, tetramethylselenourea). Etc.), seleno ketones (eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg, diethyl selenide, triphenylphosphine selenide), Selenium compounds such as selenophosphates (for example, tri-p-tolyl selenophosphate) can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

[0144] The amount of the selenium sensitizer, the selenium compound used, the silver halide grains will vary by the chemical ripening condition and the like, generally per mol of silver halide 10 ^-8 to 10 ^-4 mol, preferably 10 ^{- About 7} to 10 ^-5 mol is used.

The tellurium sensitizers used in the present invention include Canadian Patent No. 800,958 and British Patent Nos. 1,2.
Nos. 95,462 and 1,396,696, Japanese Patent Application No. 2-
Compounds described in, for example, 333819 and 3-131598 can be used.

In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
Known compounds such as gold selenide can be used.
The palladium compound means a divalent palladium salt or a tetravalent salt. A preferred palladium compound is R ₂ PdX ₆
Alternatively, it is represented by R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group.
X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂
PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate.

The emulsion of the present invention is preferably combined with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-7 to 1 × 10 ^-3 mol, and more preferably 5 × 10 ^{-7 to} 5 × 10 ^-4 mol, per mol of silver halide. The preferred range of the palladium compound is 5 × 10 ^-7 to 1 × 10 ^-3 mol. The preferred range of the thiocyan compound or selenocyan compound is 1 × 10 ^{−6 to} 5 × 10 ⁻² mol.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
7, a method of growing or aging in a low pAg atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11, which is called high pH aging, can be selected. Also, two or more methods can be used in combination.

As the reduction sensitizer, known reduction sensitizers such as stannous salt, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidinesulfinic acid, silane compounds and borane compounds are selected. And two or more compounds can be used in combination. Stannous chloride as reduction sensitizer,
Aminoiminomethanesulfinic acid (common name: thiourea dioxide), dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds.

The chemical sensitization can be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. Nos. 2,131,038 and 3,4.
11,914, 3,554,757, JP-A-58.
No. 126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pages 138-143.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2Na
_{CO 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2
Na ₂ SO ₄ .H ₂ O ₂ .2H ₂ O), peroxy acid salts (for example, K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ),
Peroxy complex compound (for example, K ₂ [Ti (O ₂ ) C ₂
O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti (O ₂ ) OH ・ S
_{O 4 · 2H 2 O, Na} 3 _{[VO (O 2) (C 2} H 4) 2 · 6
H ₂ O), permanganate (eg KMnO ₄ ), chromate (eg K ₂ Cr ₂ O ₇ ) and other oxyacid salts,
There are halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), salts of high-valent metal (eg potassium hexacyanoferrate) and thiosulfonates.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and chloramine T). , Chloramine B).

It is a preferred embodiment that the reduction sensitization and the oxidizing agent for silver are used in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole)
Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene), many compounds known as antifoggants or stabilizers such as pentaazaindenes and the like can be added.
For example, US Pat. Nos. 3,954,474 and 3,98
Nos. 2,947 and 52-28660 can be used. One of the preferred compounds is the compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,52
No. 2,052, No. 3,527,641, No. 3,61
7,293, 3,628,964, 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377 and 3,76
9,301, 3,814,609, 3,83
Nos. 7,862, 4,026,707, British Patent Nos. 1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12,375, JP-A-52 Nos. -110,618 and 52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
As described in JP-A Nos. 8,969 and 4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or can be added before the completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978).
Month), the same Item 18716 (November 1979) and the same Item 307105 (November 1989), and the relevant parts are summarized below.

Additive type RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 996 page 2 Sensitivity enhancer same as above 3 Spectral sensitizer, page 23 to page 648 right column to 996 right to 998 right strong color Sensitizer page 649 right column 4 whitening agent page 24 998 right 5 antifoggant page 24 to 25 page 649 right column 998 right to 1000 right and stabilizer 6 light absorber, page 25 to 26 page 649 right column ~ 1003 Left to 1003 Right Filter, page 650 Left column UV absorber 7 Anti-stain agent Page 25 Right column 650 Left to right column 8 Dye image stabilizer page 25 9 Hardener 26 pages 651 page Left column 1004 Right to 1005 Left 10 Binder page 26 Same as above 1003 Right to 1004 right 11 Plasticizer, lubricant 27 page 650 Right column 1006 Left to 1006 right 12 Coating aid, surface 26 to 27 Same as above 1005 Left to 1006 left Activator 13 Static prevention Page 27 Same as above 1006 Right to 1007 Left agent In the present invention, an organic metal salt is used as an oxidizing agent together with the photosensitive silver halide. It is also possible to. Among such organic metal salts, organic silver salts are particularly preferably used. Examples of the organic compound that can be used to form the above organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52 to 53. U.S. Pat. No. 4,775,6
Acetylene silver described in No. 13 is also useful. The organic silver salt is
Two or more kinds may be used in combination. These organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of the photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is 0.0 in terms of silver.
5 to 10 g / m ² , preferably 0.1 to 4 g / m ² is suitable.

The method of developing the light-sensitive material of the present invention after exposure is, for example, heat development, an activator method in which a developing agent is incorporated in the light-sensitive material and developed with an alkali processing solution, and a processing solution containing a developing agent / base. There is a method of developing with.

The heat treatment of a light-sensitive material is known in the art, and the heat-developable light-sensitive material and its process are
For example, the basics of photographic engineering (Published by Corona Publishing Company in 1979)
Pages 553-555, published April 1978, video information 4
Page 0, Nebletts Handbook of Photography and Reprogra
phy 7th Ed. (Van Nostrand and Reinhold Company) 3
Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075, British Patent 1,131,10
No. 8, No. 1,167,777 and Research Disclosure June 1978, pp. 9-15 (RD-
17029).

The activator processing means a processing method in which a color developing agent is incorporated in a light-sensitive material and development processing is carried out with a processing solution containing no color developing agent. The processing solution in this case is characterized in that it does not contain a color developing agent contained in a normal developing solution component, and may contain other components (for example, an alkali, an auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,
It is illustrated in known documents such as 491A1 and 565,165A1.

The method of developing with a processing solution containing a developing agent / base is described in RD. No. 17643, pp. 28-29, No. 1
No. 30710, left column to right column, and No. 30710
5, pp. 880-881. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and representative examples and preferred examples thereof are EP 556700A, pp. 28, 43-52.
The compounds mentioned in the row are mentioned. These compounds can be used in combination of two or more depending on the purpose. The color developing solution includes a pH buffering agent such as an alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. In addition, if necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, trimethanolamine and catecholsulfonic acids,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-
Auxiliary developing agents such as 3-pyrazolidone, viscosity-imparting agents,
Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylimino Diacetate, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Add ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. P of color developer
H is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area with the air in the processing tank. The processing effect of the contact between the photographic processing liquid and air in the processing tank is the aperture ratio (= [contact area between processing liquid and air cm
² ] ÷ [volume of processing solution cm ³ ]). This aperture ratio is preferably 0.1 or less,
More preferably, it is 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method of providing a movable lid described in JP-A-1-82032 and JP-A-63-216
The slit developing method described in No. 050 can be mentioned. The aperture ratio is not limited to both the color development step and the black and white development step, and the subsequent steps such as bleaching, bleach-fixing,
It is preferable to reduce the amount in all steps such as fixing, washing with water and stabilizing. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for the color developing process is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, a high pH and using a high concentration of the color developing agent.

Next, the processing material and processing method used in the case of the activator processing in the present invention will be described in detail.

The processing material and processing method used in the present invention will be described in detail. In the present invention, the photosensitive material is subjected to development (silver development / cross-oxidation of a built-in reducing agent), desilvering, and washing or stabilization. After the washing or stabilizing treatment, a treatment for enhancing color development such as alkali addition may be performed.

In the development processing of the light-sensitive material of the present invention, the developer functions as a developing agent of silver halide, and /
Alternatively, a compound having a function of cross-oxidizing a color-forming reducing agent contained in a light-sensitive material by an oxidized product of a developing agent generated in silver development is used. Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones.

Pyrazolidones include 1-phenyl-3
-Pyrazolidones are preferred, and 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4 , 4-Dihydroxymethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p
-Chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl -2-hydroxymethyl-5-phenyl-3-pyrazolidone and the like.

Examples of dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone,
And potassium hydroquinone monosulfonate.

As the reductones, ascorbic acid or a derivative thereof is preferable, and the compounds described on pages 3 to 10 of JP-A-6-148822 are used. Particularly, sodium L-ascorbate and sodium erythorbate are preferred.

As p-aminophenols, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p- Aminophenol, etc.

These compounds are usually used alone, but it is also preferable to use two or more kinds in combination in order to enhance the developing and cross-oxidizing activities. The amount of these compounds used in the developer is 2.5 × 10 ⁻⁴ mol / liter to 0.2 mol / l.
Liter, preferably 0.0025 mol / liter or more
It is 0.1 mol / l, more preferably 0.001 mol / l to 0.05 mol / l.

Examples of the preservatives used in the developing solution of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde bisulfite and hydroxyamine sulfate. The amount used is 0.1 mol / liter or less, preferably 0.001 to
It may be used in the range of 0.02 mol / liter. When a high silver chloride emulsion is used in the light-sensitive material, the above compound may be contained in an amount of 0.001 mol / liter or less, and preferably not contained at all. In the present invention, it is preferable to contain diethylhydroxylamine, sialylhydroxylamines described in JP-A-4-97355, and an organic preservative in place of the hydroxyamine and sulfite ion.

In the present invention, the developing solution contains halogen ions such as chlorine ion, bromine ion and iodine ion. Here, the halide may be directly added to the developing solution, or may be eluted from the light-sensitive material to the developing solution during the development processing.

The pH of the developer used in the present invention is preferably 8 to 13, more preferably 9 to 12. The above p
In order to retain H, it is preferable to use various buffers. Preference is given to using carbonates, phosphates, tetraborates and hydroxybenzoates.

The amount of the buffer added to the developing solution was 0.05.
Mol / liter or more, preferably 0.1 mol / liter or more.
It is particularly preferred that the molar ratio is from mol to 0.4 mol / liter.

In addition, various chelating agents can be used as a precipitation inhibitor of calcium or magnesium in the developing solution or for improving the stability of the developing solution. The amount of these chelating agents added may be an amount sufficient to mask the metal ions in the developing solution, and is, for example, about 0.1 g to 10 g per liter.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds are used. The addition amount of the nitrogen-containing heterocyclic compound is 1 × 10 ⁻⁵
~ 1 x 10 ^-2 mol / l, preferably 2.5 x 1
It is 0 ⁻⁵ to 1 × 10 ⁻³ mol / liter.

Any development accelerator can be added to the developing solution if necessary.

The developer preferably contains a fluorescent whitening agent. In particular, it is preferable to use a 4,4'-diamino-2,2'-disulfostilbene compound.

The processing temperature of the developing solution applied to the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. It is preferable that the replenishing amount is small, but 15 to ⁶ per 1 m ^{2 of} light-sensitive material
00 ml, preferably 25 to 200 ml, more preferably 3
5 to 100 ml.

After the development, desilvering processing is performed. The desilvering process includes a fixing process and a bleaching and fixing process. When the bleaching and fixing treatments are carried out, the bleaching treatment and the fixing treatment may be carried out individually or simultaneously (bleach-fixing treatment). Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Also, without desilvering after development,
It is also preferable in some cases to perform the stabilizing treatment to stabilize the silver salt or the color image.

After development, West German Patent (OLS) 1,
813,920, 2,044,993, 2,7
35,262, JP-A-48-9728, and 49-8
No. 4240, No. 49-102314, No. 51-538
No. 26, No. 52-13336, No. 52-73731, etc. can be subjected to an image reinforcing treatment (intensification) using a peroxide, a halogenous acid, an iodoso compound and a cobalt (III) complex compound. . In order to further enhance the image reinforcement, an oxidizing agent for reinforcing the image may be added to the developer, and the development and the image intensification may be simultaneously performed in one bath.
In particular, hydrogen peroxide is preferable because of its high amplification factor. These image intensification methods can significantly reduce the amount of silver in the photosensitive material, so that bleaching is not required and it is not necessary to discharge silver (or silver salt) for stabilization, etc. This is a preferable treatment method.

Examples of the bleaching agent used in the bleaching solution and the bleach-fixing solution include iron (III), cobalt (III) and chromium (I
V), compounds of polyvalent metals such as copper (II), peracids, quinones and nitro compounds. Among these, ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts of aminopolycarboxylic acid iron (II
I), hydrogen peroxide, persulfate and the like are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. PH of bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts
Is used in 3 to 8, preferably 5 to 7. The pH of the bleaching solution using persulfate or hydrogen peroxide is used at 4 to 11, preferably 5 to 10.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.

For the bleaching solution, the bleach-fixing solution and the fixing solution, conventionally known additives such as a rehalogenating agent, a pH buffering agent and a metal corrosion inhibitor can be used. Especially, in order to prevent bleach stain, the acid dissociation constant (pka) is 2 to 7
It is preferable that the organic acid is contained.

The fixing agents used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioureas, a large amount of iodide salts and JP-A-4-365037, pp. 11-2.
Examples thereof include a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound described on page 1 and 5-66540, pages 1088 to 1092. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like.

The processing temperature of the desilvering step is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. The replenishment amount is preferably smaller, but is preferably 15 to 600 ml, preferably 25 to 200 ml, more preferably 35 to 100 ml per m ^{2 of} the light-sensitive material. It is also preferable to perform the treatment without replenishment, to the extent that the evaporation amount is supplemented with water.

The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process, JP-A-57-8543 and JP-A-58-1483 are used.
Nos. 4 and 60-220345, and JP-A-5-220345.
8-127926, 58-13837, 58
All known methods described in JP-A-140741 can be used. Further, a washing step and a stabilizing step in which a stabilizing bath containing a dye stabilizing agent and a surfactant represented by processing of a color light-sensitive material for photographing is used as a final bath may be performed. Sulfite salts; hard water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid, organic aminophosphonic acid; metal salts such as Mg salt, Al salt, Bi salt; surfactants; hardeners A film agent; a pH buffering agent; an optical brightening agent; a silver salt forming agent such as a nitrogen-containing heterocyclic compound can be used. Examples of the dye stabilizer of the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.

The pH of the washing or stabilizing solution is 4-9, preferably 5-8. The treatment temperature is 15 to 45 ° C, preferably 25 ° C to 40 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 40 seconds. The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step.

The amount of washing water and / or the stabilizing solution can be set in a wide range depending on various conditions, but the replenishing amount is preferably 15 to 360 ml per 1 m ² of the light-sensitive material, and 25 to 120 ml.
Is more preferred. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks and carry out the method in a multistage countercurrent system.

In the present invention, water obtained by treating the overflow liquid or the liquid in the tank with a reverse osmosis membrane can be used for saving water. For example, the treatment by reverse osmosis is preferably performed on the water in the second tank and subsequent tanks for multistage countercurrent washing and / or stabilization.

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods of strengthening the stirring are described in JP-A-62-183460 and JP-A-62-1834.
No. 61, a method of impinging a jet jet of a processing liquid on an emulsion surface of a light-sensitive material, a method of increasing a stirring effect by using a rotating means of JP-A-62-183461, and a wiper blade provided in a liquid A method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such stirring improving means include a developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution, a stabilizing solution,
It is useful in any washing. These methods are effective in that the supply of the effective component in the liquid into the photosensitive material and the diffusion of the unnecessary component in the photosensitive material are promoted.

In the present invention, the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] of any bath shows excellent performance, but from the viewpoint of stability of liquid components. The liquid opening ratio is preferably ⁰ to 0.1 cm ^-1 . In continuous treatment, the range of 0.001 cm ^{-1 to} 0.05 cm ^-1 is preferable in practical use, and more preferably 0.002 to 0.03 cm.
It is ^-1 .

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
No. 8, No. 60-191259. Such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for shortening the processing time of each step and reducing the replenishing amount of the processing solution. In order to shorten the processing time, it is preferable to shorten the crossover time (air time).
For example, Japanese Patent Application Laid-Open No. 4-86659, FIG.
Also, a method in which each process described in FIG. 4 or FIG. 5 of JP-A-5-66540 is conveyed via a blade having a shielding effect is preferred. In the case where each processing solution is concentrated by evaporation in the continuous processing, it is preferable to add water to correct the concentration.

The processing time of the step in the present invention means the time required from the start of the processing of the photosensitive material in one step to the start of the processing in the next step. The actual processing time in an automatic developing machine is usually determined by the linear velocity and the capacity of the processing bath.
000 mm / min. In particular, in the case of a small developing machine, the speed is preferably 500 to 2500 mm / min. The total processing step, that is, the processing time from the developing step to the drying step is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from the immersion of the photosensitive material in the developing solution to the exit from the drying section of the processor.

Various additives are used in the treatment agent according to the present technology, and more specifically, Research Disclosure
It is described in Item 36544 (September 1994), and the relevant parts are summarized below.

Processing Agent Type Page Developer 536 Preservative for developer 537 Left column Antifoggant 537 Chelating agent 537 Right column Buffer 537 Right column Surfactant 538 Left column and 539 Left column Bleach 538 Bleach accelerator 538 right column to 539 left column bleaching chelating agent 539 left column rehalogenating agent 539 left column fixing agent 539 right column fixing agent preservative 539 right column fixing chelating agent 540 left column stabilizing surfactant 540 Left side Stabilization scum agent 540 Right side Stabilizing chelating agent 540 Right side Antibacterial and antifungal agent 540 Right side Color image stabilizer 540 Right side

For details of the water saving technology of this technology, see Research Disclosure Item 36544 (199).
(September 4, 2004) 540, right column to 541, left column.

Next, the processing materials and processing methods used in the case of the heat development processing in the present invention will be described in detail.

In the light-sensitive material of the present invention, it is preferable to use a base or a base precursor for the purpose of accelerating silver development and dye forming reaction. As base precursors, salts of organic acids and bases that decarboxylate by heat, intramolecular nucleophilic substitution,
There are compounds that release amines by Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat. Nos. 4,514,493 and 4,657,848 and Known Technology No. 5 (March 22, 1991, Aztec Co., Ltd.), pp. 55-86. Have been.
Further, as described in European Patent Publication No. 210,660 and U.S. Pat. No. 4,740,445, which will be described later, a basic metal compound which is poorly soluble in water and a metal ion which constitutes the basic metal compound, A method in which a base is generated by a combination of compounds capable of a complex formation reaction (referred to as a complex formation compound) using water as a medium may be used. The amount of the base or base precursor used is 0.1 to 20 g / m ² , preferably 1 to 10 g / m ² .

A heat solvent may be added to the light-sensitive material of the present invention for the purpose of promoting heat development. Examples include U.S. Pat. Nos. 3,347,675 and 3,667,9.
Organic compounds having a polarity as described in JP-A No. 59-59 are exemplified. Specifically, amide derivatives (benzamide etc.), urea derivatives (methyl urea, ethylene urea etc.), sulfonamide derivatives (compounds described in JP-B-1-40974 and JP-B-4-13701, etc.), polyol compounds Sorbitols), and polyethylene glycols. When the thermal solvent is insoluble in water, it is preferably used as a solid dispersion. The layer to be added may be either a photosensitive layer or a non-photosensitive layer depending on the purpose. The amount of the hot solvent added is 10% of the binder of the layer to be added.
Wt% to 500 wt%, preferably 20 wt% to 300
% By weight.

The heating temperature in the heat development step is about 50 ° C. to 2 ° C.
Although it is 00 ° C, 60 ° C to 150 ° C is particularly useful.

In the heat development step, air is blocked during heat development, vaporization of material from the light-sensitive material is prevented, material for processing is supplied to the light-sensitive material, In order to remove the material (YF dye, AH dye, etc.) or unnecessary components generated during development, a material different from the photosensitive material may be superposed on the photosensitive material surface and heated. As the support and binder of the processing sheet used in this case, the same materials as those for the light-sensitive material can be used. A mordant may be added to the treatment sheet for the purpose of removing the above-mentioned dye and other purposes. As the mordant, those known in the photographic field can be used, and US Pat. No. 4,50,626, columns 58 to 59 and JP-A No. 61-88256, 32-41.
Page, JP-A-62-244043, JP-A-62-244
The mordants described in No. 036 and the like can be mentioned. Further, a dye-receptive polymer compound described in US Pat. No. 4,463,079 may be used.

When a processing sheet is used, it is preferable that the base or the base precursor is contained in a separate sheet in order to improve the raw storability of the photographic material. The hot solvent may be put in either the light-sensitive material or the processed sheet, or both, depending on the purpose.

In the case of heat development using a treatment sheet,
A solvent may be used for the purpose of accelerating development, accelerating transfer of the processing material, and accelerating diffusion of unnecessary substances. Specifically, U.S. Pat. Nos. 4,704,245 and 4,470,445.
And JP-A-61-238056.
In this method, the heating temperature is preferably equal to or lower than the boiling point of the solvent used. For example, when the solvent is water, 50 ° C. to 10
0 ° C. is preferred. Examples of the solvent used for accelerating the development and / or for diffusion transfer of the processing material include water, a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include an image forming accelerator). The solvent described in the above section is used), or a low boiling point solvent or a mixed solution of a low boiling point solvent and water or the basic aqueous solution.
Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent.
Water is preferably used as the solvent used in these heat development steps, but any commonly used water may be used. Specifically, distilled water, tap water,
Well water, mineral water, etc. can be used.
Further, in the thermal developing apparatus using the photosensitive material and the image receiving element of the present invention, water may be used up or may be used repeatedly. In the latter case, water containing components eluted from the material will be used. In addition, JP-A-63-
144,354, 63-144,355, 62
-38,460, JP-A-3-210,555 and the like or water may be used. These solvents can be applied to the photosensitive material, the processing sheet, or both. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method for applying this water, for example, JP-A-62-253,159 (5)
Page, the method described in JP-A-63-85,544 and the like are preferably used. Further, the solvent may be enclosed in microcapsules, or may be incorporated in advance in the form of a hydrate in the light-sensitive material or the processed sheet or both. The temperature of the water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85,544.

When heat development is carried out in the presence of a small amount of water or a solvent, as described in European Patent Publication 210,660 and US Pat. No. 4,740,445, a basic substance which is poorly soluble in water is used. It is effective to employ a method in which a base is generated by a combination of a metal compound and a metal ion constituting the basic metal compound and a compound capable of complexing reaction with water as a medium (referred to as a complex forming compound). In this case, it is desirable from the viewpoint of raw storability that the basic metal compound which is hardly soluble in water is added to the light-sensitive material and the complex-forming compound is added to the processing sheet.

The heating method in the developing step is as follows: contact with a heated block or plate, contact with a heat plate, hot presser, heat roller, heat drum, halogen lamp heater, infrared or far infrared lamp heater, etc. Alternatively, there is a method of passing through a high temperature atmosphere.
A method for superposing a light-sensitive material and a processing sheet is disclosed in JP-A-62-62.
No. 253,159 and JP-A No. 61-147,244, page (27) can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, Japanese Patent Application Nos. 4-277,517 and 4
-243,072, 4,244,693, 6-
Devices described in JP-A-164,421 and JP-A-6-164,422 are preferably used. As a commercially available device, there can be used Pictrostat 100, Pictrostat 200, Pictrostat 300, Pictrostat 330, Pictrostat 50, Pictrograph 3000, Pictograph 2000, etc., manufactured by Fuji Photo Film Co., Ltd. .

The light-sensitive material and / or the processing sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development. As the heat generating element of the present invention, those described in JP-A-61-145544 can be used.

Various surfactants can be used in the light-sensitive material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, JP-A-62-17.
3,463 and 62-183,457. The photosensitive material may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, improving peelability, and the like. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57
No. 9053, columns 8 to 17, JP-A-61-20944
No. 62-135826 and hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin. Can be

The light-sensitive material preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane. And polymethylphenylsiloxane. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
O ₂ , TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO,
A crystal having a particle size of 0.001 to 1.0 μm in which at least one selected from MoO ₃ and V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Metal oxides or their composite oxides (Sb, P, B, In,
Fine particles of S, Si, C, etc., and also fine particles of sol-like metal oxides or composite oxides thereof. Preferably 5 to 500 mg / m ² as the content of the sensitive material, particularly preferably from 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is 1/30.
0-100 / 1 is preferable, and 1/100 is more preferable.
１００100/5.

The composition of the light-sensitive material or the processing sheet (including the back layer) includes dimensional stabilization, curl prevention, adhesion prevention,
Various polymer latexes can be contained for the purpose of improving film physical properties such as prevention of cracking of the film and prevention of pressure increase / decrease sensation. Specifically, JP-A Nos. 62-245258 and 62
Any of the polymer latexes described in JP-B-136648 and JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

When a matting agent is used in the light-sensitive material of the present invention, the matting agent may be either the emulsion side or the back side.
It is particularly preferred to add it to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid =
9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and the average particle size of 0.
It is preferable that 90% or more of the total number of particles be contained within the range of 9 to 1.1 times. Also, 0.8μ to improve matte
It is also preferable to simultaneously add fine particles of m or less, such as polymethylmethacrylate (0.2 μm), poly (methylmethacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), polystyrene particles (0.25 μm).
m) and colloidal silica (0.03 μm). Specifically, it is described in JP-A-61-88256, page (29). In addition, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, and the like are disclosed in JP-A-63-274944 and JP-A-63-274954.
There is a compound described in No. In addition, the compounds described in the above Research Disclosure can be used.

As the support of the light-sensitive material and the processing sheet when used in the heat development system, those capable of withstanding the processing temperature are used. In general, papers and synthetic polymers (films) described in the Photographic Society of Japan, "Basics of photographic engineering-silver halide photography-", pages 223 to 240, published by Corona Co., Ltd. (1979). And photographic supports.
Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride,
Examples include polystyrene, polypropylene, polyimide, and celluloses (for example, triacetyl cellulose). These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, JP-A-62-253159, pages (29) to (31), JP-A-1-161,236 pages (14) to (17), and JP-A-62-153.
Supports described in JP-A-3-316,848, JP-A-2-22,651, JP-A-3-56,955, and US Pat. No. 5,001,033 can be used.

Particularly when heat resistance and curl characteristics are severely demanded, it can be used as a support for a light-sensitive material.
No. 6-43581, No. 6-51426, No. 6-
No. 51437, No. 6-51442, Japanese Patent Application No. 4-251
No. 845, No. 4-231825, No. 4-253545
Nos. 4-258828, 4-240122, 4-221538, 5-21625, 5-15
No. 926, 4-331919, 5-199704
And the support described in JP-A-6-13455 and JP-A-6-14666 can be preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

Further, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. In the undercoat layer, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates,
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), epichlorohydrin resin,
Examples thereof include active vinyl sulfone compounds.
SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Further, as the support, for example, Japanese Patent Application Laid-Open No. 4-1 is used.
24645, 5-40321, 6-35092
It is also possible to use a support having a magnetic recording layer described in Japanese Patent Application No. 5-58221 and Japanese Patent Application No. 5-106979 so that photographic information and the like can be recorded.

The magnetic recording layer is formed by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder. Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co-coated magnetite,
Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co
Co-coated ferromagnetic iron oxide, such as γ-Fe ₂ O _3, is preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0.
× 10 ⁵ A / m, particularly preferably 4.0 × 10 ⁴ to
2.5 × 100 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in JP-A-6-1610.
As described in No. 32, the surface thereof may be treated with a silane coupling agent or a titanium coupling agent. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer described in JP-A-4-219569, a natural product. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, reaction products of these isocyanates with polyalcohols (for example, reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and condensation products of these isocyanates. Examples of the polyisocyanate include, for example, JP-A-6-5935.
No. 7.

As a method for dispersing the above-mentioned magnetic material in the above-mentioned binder, a kneader, a pin-type mill, an annular-type mill or the like is preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 0.01.
~ ² g / m ² , more preferably 0.02-0.5 g / m ²
It is. The transmission yellow density of the magnetic recording layer is 0.01 to
0.50 is preferable, 0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, improvement of lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. Photosensitive materials having a magnetic recording layer are described in US Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874 and EP466,130. .

The polyester support preferably used in the above-mentioned photosensitive material having the magnetic recording layer will be further described. For details, including the photosensitive material, processing, cartridge and examples, refer to JP-A-Technical Publication No. 94-6023. (Invention Society; 1994. 3.15). Polyester is formed by using diol and aromatic dicarboxylic acid as essential components, and the aromatic dicarboxylic acid is 2,6-, 1,5.
-, 1,4-, and 2,7-naphthalenedicarboxylic acid,
Terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is 2,6-naphthalenedicarboxylic acid in an amount of 50 mol% to 10 mol%.
It is a polyester containing 0 mol%. Among them, polyethylene 2,6-naphthalate is particularly preferable. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester is 50 ° C. or higher, and 9
0 ° C. or higher is preferred.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. The surface is provided with irregularities (for example,
Conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ) may be applied) to improve the surface condition. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light piping, the purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, a film cartridge which can be loaded with a light-sensitive material when used as a photographic light-sensitive material will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A Nos. 1-312537 and 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the cartridge may be the same as the current 135 size, and it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to miniaturize the camera. The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of plastic used for the patrone and patrone case is 5 to 15g.
Is preferred.

Further, a patrone that rotates the spool to feed the film may be used. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are U
S4, 834, 306 and 5, 226, 613.

As a method for producing a print on a color paper or a photothermographic material using this color photographic material,
JP-A-5-241251, JP-A-5-19364, and JP-A-5-19364
-19363 can be used.

[0235]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate. A photographic printing paper (100) having a three-layer structure shown in 1 was produced. The coating solution was prepared as follows. Second layer coating liquid coupler (ExY) 17 g, color-forming reducing agent (R-1) 20 g, solvent (Solv-1) 80 g
Was dissolved in ethyl acetate, and this solution was emulsified and dispersed in 400 g of a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion A. On the other hand, a silver chlorobromide emulsion A (a cubic, a 3: 7 mixture of a large size emulsion A having an average grain size of 0.10 μm and a small size emulsion A having an average grain size of 0.08 μm (silver molar ratio). The variation coefficient of the grain size distribution is 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide in each size emulsion were locally contained in a part of the surface of the grain based on silver chloride). In this emulsion, blue-sensitive sensitizing dyes A, B and C shown below were added to the large-sized emulsion A per mol of silver in an amount of 7.1 × 1 each.
0 ^-4 mol, and to the small size emulsion A, 8.5 x 10 ^-4 mol each were added. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the second layer so as to have the following composition. The emulsion coating amount is the silver equivalent coating amount.

The coating solutions for the first layer and the third layer were prepared in the same manner as the coating solution for the second layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 62.0mg / m} 2, 50.0mg / m 2 and 10.
0 mg / m ² was added. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of the second layer.

[0238]

Embedded image

1- (5-methylureidophenyl)
^-3 -Mercaptotetrazole was added in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. (Layer constitution) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver. The fine solid dispersion of 1,5-diphenyl-3-pyrazolidone added to the first layer is disclosed in JP-A-2-23504.
It was prepared by the method described on page 20 of No. 4.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First layer gelatin 1.10 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state)

Second layer Silver chlorobromide emulsion A 0.01 Gelatin 1.54 Yellow coupler (ExY) 0.17 Coloring reducing agent (R-1) 0.20 Solvent (Solv-1) 0.82

Third Layer (Protective Layer) Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

Except for replacing the yellow coupler and the color-forming reducing agent in the coating solution for the second layer with the yellow coupler and the color-forming reducing agent shown in Table a in equimolar amounts, the same procedure as in the preparation of Sample (100) was conducted. To prepare samples (101) to (106).

Further, the silver chlorobromide emulsion A in the coating solution for the second layer was replaced with the silver chlorobromide emulsion B shown below with an equal silver amount, and the coupler and the color-forming reducing agent were changed to the magenta coupler shown in Table b. Samples (200) to (209) were produced in exactly the same manner as the sample (100) except that the reducing agent was replaced with equimolar amount.

Silver chlorobromide emulsion B: Cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.10 μm and small size emulsion B of 0.08 μm (Ag molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was contained in a part of the grain surface based on silver chloride in each size emulsion.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion B, respectively.

[0248]

Embedded image

(Sensitizing dye D per mol of silver halide is 1.5 × 10 ⁻³ mol for large size emulsion, 1.8 × 10 ⁻³ mol for small size emulsion, and Sensitizing dye E per mol of silver halide is 2.0 × 10 ⁻⁴ mol for large size emulsion and 3.6 for small size emulsion.
× 10 ^-4 mol of sensitizing dye F per mol of silver halide, 1.0 × 10 ^-3 mol for large-size emulsion, and 1.4 × 10 ^-3 mol for small-size emulsion. Added)

Further, the silver chlorobromide emulsion A in the coating solution for the second layer was replaced with the silver chlorobromide emulsion C shown below with an equal silver amount, and the coupler and the color-forming reducing agent were replaced by the cyan couplers and color-forming agents shown in Table c. Samples (300) to (305) were prepared in exactly the same manner as the sample (100) except that the reducing agent was replaced with equimolar amount. Silver chlorobromide emulsion C: cubic, average grain size 0.10 μm
1: 4 mixture (Ag molar ratio) of the large size emulsion C of the formula (1) and the small size emulsion of 0.08 μm. The coefficient of variation of the grain size distribution was 0.09 and 0.11, and AgBr was used for each size emulsion.
0.8 mol% was locally contained in a part of the surface of the grain based on silver chloride. The following spectral sensitizing dyes were used for silver chlorobromide emulsion C, respectively.

[0251]

Embedded image

(2.5 × 10 ⁻⁴ mol was added to the large-sized emulsion and 3.9 × 10 ⁻⁴ mol was added to the small-sized emulsion, per mol of silver halide)

[0253]

Embedded image

[0254]

Embedded image

[0255]

Embedded image

A blue filter for sensitometry was used for samples (100) to (106) prepared as described above using an FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200 ° K). , Samples (200) to (2
09) was subjected to gradation exposure with a green filter for sensitometry, and samples (300) to (305) were subjected to gradation exposure with a red filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Treatment process 1 Treatment process Temperature Time Image 40 ℃ 40 seconds Rinse room temperature 45 seconds

Developer (hydrogen peroxide-containing alkali activating solution) Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml H ₂ O ₂ 10 ml Water was added. 1000 ml pH (at 25 ℃ / potassium hydroxide) 11.5

As the rinse liquid, deionized water (conductivity: 5
μS / cm or less) to which sodium chlorinated isocyanurate (0.02 g / liter) was added (pH 6.
5) was used.

For the samples (100) to (106), the maximum color density portion of the processed sample was measured using blue light and sample (2).
00) to (209), green light, sample (300)
(305) was measured with red light. The results are shown in Table 1, Table 2 and Table 3, respectively.

[0261]

[Table 1]

[0262]

[Table 2]

[0263]

[Table 3]

As is clear from Tables 1, 2, and 3, by using the color-forming reducing agent of the present invention, a high color development is obtained even when the auxiliary developing agent is incorporated in the light-sensitive material and intensified with hydrogen peroxide. It can be seen that the concentration is obtained.

Example 2 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and various photographic constituent layers were further coated thereon. A multilayer color photographic paper (400) having the layer structure shown was produced. The coating solution was prepared as follows.

First layer coating liquid: 17 g of coupler (ExY), reducing agent for color formation (R-1) 2
0 g and a solvent (Solv-2) 80 g were dissolved in ethyl acetate, and this solution was dissolved in 400 g of a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid.
To prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion D (cubic, a large emulsion D having an average grain size of 0.88 μm and a small emulsion D having an average grain size of 0.70 μm:
7 mixtures (silver molar ratio). The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively. For each size emulsion, 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride). did. In this emulsion, the blue-sensitive sensitizing dyes A, B, and C used in Example 1 were added to the large-sized emulsion D per mol of silver in an amount of 1.4 × 10 ⁻⁴ mol, respectively.
For the small-sized emulsion D, 1.7 × 10
^-4 mol is added. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion D were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount is the silver equivalent coating amount.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Cpd-2, Cpd-
3, the total amount of each of Cpd-4 and Cpd-5 was 15.0.
^{mg / m 2, 58.0mg / m} 2, 50.0mg / m 2 and 11.
0 mg / m ² was added. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

Blue Sensitive Emulsion Layer The blue sensitizing dyes A, B and C used in Example 1 were used in the following amounts. (Per mol of silver halide, 1.4 × 10 ^-4 mol was added to the large-size emulsion and 1.7 × 10 ^-4 mol was added to the small-size emulsion, respectively.)

Green Sensitive Emulsion Layer The green sensitizing dyes D, E and F used in Example 1 were used in the following amounts. (The amount of sensitizing dye D per mol of silver halide is 3.0 × 10 ^-4 mol for large-size emulsion, 3.6 × 10 ^-4 mol for small-size emulsion, and sensitizing dye E Per mole of silver halide, 4.0 for large emulsions.
× 10 ^-5 mol, 7.0 × 10 ^-5 for small size emulsions
The sensitizing dye F was added to the silver halide emulsion in an amount of 2.0 × 10 ⁻⁴ mol for the large size emulsion and 2.8 × 10 ⁻⁴ mol for the small size emulsion per mol of silver halide. Sensitive Emulsion Layer The red sensitizing dyes G and H used in Example 1 were used in the following amounts. Fifth layer (red) (5.0 × 10 ⁻⁵ mol for large-size emulsion and 8.0 × 10 ⁻⁵ mol for small-size emulsion per mol of silver halide) Further, 2.6 × 10 ^-2 mol of the following compound per mol of silver halide was added to the ^light- sensitive layer).

[0270]

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For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
3.6 × 10 ⁻⁴ moles, 3.0 × 10 ⁻³ moles per mole,
2.5 × 10 ^-4 mol was added. In addition, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0272]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion D 0.20 Gelatin 1.48 Yellow Coupler (ExY) 0.17 Coloring reducing agent (R-1) 0.20 Solvent (Solv-1) 0.79

Second Layer (Color Mixing Prevention Layer) Gelatin 1.10 Color mixing inhibitor (Cpd-6) 0.11 Solvent (Solv-2) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09 1,5-Diphenyl-3-pyrazolidone 0.03 (fine particle solid dispersion state)

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion E (cubic, 1: 3 mixture of large size emulsion E having an average grain size of 0.55 μm and small size emulsion E having a grain size of 0.39 μm (Ag (Mole ratio). Coefficients of variation of grain size distribution are 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was contained in a part of grain surface based on silver chloride for each size emulsion.) 0.20 Gelatin 1.52 Magenta coupler (ExM) 0.24 Coloring reducing agent (R-1) 0.20 Solvent (Solv-1) 0.80

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.76 Color mixing inhibitor (Cpd-6) 0.08 Solvent (Solv-2) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 1,5-diphenyl-3-pyrazolidone 0.02 (fine particle solid dispersion state)

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion F (cubic, 1: 4 mixture of large size emulsion F having an average grain size of 0.5 μm and small size emulsion F of 0.41 μm (Ag (Mole ratio). The variation coefficient of the grain size distribution was 0.09 and 0.11, and AgBr 0.8 mol% was locally contained in a part of the grain surface based on silver chloride in each size emulsion.) 0.20 Gelatin 1.50 Cyan coupler (ExC) 0.21 Coloring reducing agent (R-1) 0.20 Solvent (Solv-1) 0.81

Sixth Layer (UV Absorbing Layer) Gelatin 0.62 UV Absorbing Agent (UV-1) 0.39 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-6) 0.05

Seventh layer (protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

[0280]

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[0281]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Samples (401) to ((100)) were prepared in the same manner as in the preparation of sample (400) except that the coupler and the color-forming reducing agent were replaced with equimolar amounts of the coupler and the color-forming reducing agent shown in Table d. 407) was prepared.

[0283]

[Table 4]

For all the samples prepared as described above, FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source 3
(200 ° K.) to give a gradation exposure of a three-color separation filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing process Temperature Time Image 40 ℃ 30 seconds Bleaching and fixing 40 ℃ 45 seconds Rinse room temperature 90 seconds

Developer (alkali activation solution) Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml Water was added to 1000 ml pH (25 ° C / hydroxylation). (In potassium) 12

Bleach-fixing solution Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water is added to 1000 ml pH (25 ° C./acetic acid and aqueous ammonia) 5.8 The rinse liquid used in Example 1 was used as the rinse liquid. The maximum color density portion of the processed sample was measured with red light, green light, and blue light. Table 5 shows the results.

[0288]

[Table 5]

As is clear from Table d, a high color density can be obtained even in the case of a multi-layered light-sensitive material in which an auxiliary developing agent is incorporated in the light-sensitive material. It was also found that the image obtained from the light-sensitive material of the present invention is excellent in hue and stability.

Example 3 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate. A photographic printing paper (500) having a three-layer structure shown in 1 was produced. The coating solution was prepared as follows. First layer coating liquid: coupler (Y-1) 17 g, color-forming reducing agent (R-1) 2
0 g and 80 g of the solvent (Solv-2) were dissolved in ethyl acetate, and this solution was emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion D. The emulsified dispersion A and the silver chlorobromide emulsion D used in Example 2 were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coating amount is the silver equivalent coating amount. The coating solutions for the second and third layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-
Triazine sodium salt was used. In addition, Cpd-
2, Cpd-3, Cpd- 4 and Cpd-5 to 15.0 mg / m ² is the total amount, ^{respectively, 60.0mg / m 2, 50.0mg /} m 2
And 10.0 mg / m ² were added. The blue sensitizing dye A used in Example 2 was used for the first layer of silver chlorobromide emulsion,
B and C were used in the same amounts as used in Example 2. Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added in an amount of 3.0 × 10 3 per mol of silver halide.
^-3 mol was added. (Layer constitution) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and bluish dye (ultramarine)]

First layer Silver chlorobromide emulsion D 0.20 Gelatin 1.54 Yellow coupler (Y-1) 0.17 Coloring reducing agent (R-1) 0.20 Solvent (Solv-2) 0.84

Second layer Gelatin 3.25 Mordant (Cpd-8) 3.30 Third layer (protective layer) Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

[0293]

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Sample (501) was prepared in exactly the same manner as sample (500), except that the color-forming reducing agent in the coating liquid for the first layer was replaced with the color-forming reducing agent shown in Table 6 in an equimolar amount. did.

Further, the silver chlorobromide emulsion D in the coating solution for the first layer was replaced with the silver chlorobromide emulsion E used in Example 2 in the same silver amount,
Samples (5) except that the coupler and the color-forming reducing agent were replaced with the magenta coupler and the color-forming reducing agent shown in Table 6 in equimolar amounts.
00), samples (600) to (601)
Was prepared. Green sensitizing dyes D, E, and F used in Example 2 were used in silver chlorobromide emulsion E in the same amounts as those used in Example 2.

The silver chlorobromide emulsion D in the coating solution for the first layer was replaced with the silver chlorobromide emulsion F used in Example 2 in the same silver amount, and the coupler and the color-forming reducing agent were the cyan couplers shown in Table 6. Samples (700) to (701) were prepared in exactly the same manner as the sample (500) except that the reducing agent for color formation was replaced with an equimolar amount. Red sensitizing dyes G and H used in Example 2 were used in silver chlorobromide emulsion F in the same amounts as those used in Example 2.

A blue filter for sensitometry was used for samples (500) to (501) produced as described above using an FWH type sensitometer manufactured by Fuji Film Co., Ltd. (color temperature of light source: 3200 ° K). , Samples (600) to (6
01) was subjected to gradation exposure with a green filter for sensitometry, and samples (700) to (701) were subjected to gradation exposure with a red filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing process Temperature Time Image 40 ℃ 20 seconds Bleaching and fixing 40 ℃ 45 seconds Rinse room temperature 45 seconds

Developer water 600 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml 1- Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1 g Water was added to 1000 ml pH (25 ° C./potassium hydroxide) 12

As the bleach-fixing solution and the rinsing solution, the developing solution, the bleach-fixing solution and the rinsing solution used in Example 2 were used. Samples (500) to (50) represent the maximum color density portion of the processed sample.
For 1), blue light, samples (600) to (601)
Was measured with green light, and samples (700) to (701) were measured with red light. Table 6 shows the results.

[0301]

[Table 6]

As is clear from Table 6, by using the color-forming reducing agent of the present invention, a high color-forming density can be obtained even when a mordant is contained in the light-sensitive material.

Example 4 <Preparation Method of Photosensitive Silver Halide Emulsion> Well-stirred aqueous gelatin solution (inactive gelatin 3 in 1000 ml of water).
0 g, potassium bromide 2 g) and ammonia
Add ammonium nitrate as a solvent and keep the temperature at 75 ° C.
To this, 1,000 ml of an aqueous solution containing 1 mol of silver nitrate and 1000 ml of an aqueous solution containing 1 mol of potassium bromide and 0.03 mol of potassium iodide were simultaneously added over 78 minutes. After washing with water and desalting, the mixture was redispersed by adding inert gelatin to obtain a sphere equivalent diameter of 0.1.
A silver iodobromide emulsion having an iodine content of 3 .mu.% Of 76 .mu.m was prepared. Equivalent sphere diameter is model TA of Coulter Counter
Measured at -II. Potassium thiocyanate, chloroauric acid and sodium thiosulfate were added to the above emulsion at 56 ° C. for optimum chemical sensitization. Sensitizing dyes corresponding to the respective spectral sensitivities were added to the emulsion at the time of preparing the coating solution to give color sensitivity.

<Preparation Method of Zinc Hydroxide Dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained.

<Preparation Method of Emulsified Dispersion of Coupler> Table 7
The oil phase component and the water phase component having the compositions shown in
Make a uniform solution at 0 ° C. The oil phase component and the aqueous phase component were combined, and in a stainless steel container of 11, with a dissolver equipped with a disperser having a diameter of 5 cm, 2 at 10,000 rpm.
Dispersed for 0 minutes. To this, warm water in the amount shown in Table 7 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0306]

[Table 7]

[0307]

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[0308]

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Using the materials thus obtained, a heat-developable color photosensitive material 801 having a multilayer structure shown in Table 8 was produced.

[0310]

[Table 8]

[0311]

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[0312]

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[0313]

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Further, a processing material R-1 having the contents shown in Tables 9 and 10 was prepared.

[0315]

[Table 9]

[0316]

[Table 10]

[0317]

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[0318]

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Next, as shown in Table 11, a light-sensitive material 802 having exactly the same composition as 801 except that the developing agent was changed.
˜807 were produced respectively. In the light-sensitive materials 801 to 807 thus produced, the density B continuously changed,
It was exposed for 0.01 seconds at 2500 lux through G and R filters. 15 ml of warm water at 40 ℃ is applied to the exposed surface
/ M ^{2 was applied,} and the treated sheet and the respective film surfaces were superposed on each other, and then heat-developed for 30 seconds at 83 ° C. using a heat drum. When the image receiving material was peeled off after the processing, clear color images of cyan, magenta and yellow were obtained corresponding to the filters exposed on the light-sensitive material side. Immediately after the treatment, the maximum density portion (Dmax) and the minimum density portion (Dmin) of this sample were subjected to X-ri.
Table 12 shows the results of measurement with a te densitometer.

[0320]

[Table 11]

[0321]

[Table 12]

[0322]

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[0323]

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To summarize the results in Table 12, first, for the samples (801 to 804) using the developing agent of the comparative example,
Almost no dye image is obtained. On the other hand, in the samples (805 to 807) using the developing agent of the present invention, it is understood that an image excellent in discrimination is obtained. From the above, the effect of the present invention is clear. Further, according to the light-sensitive material of the present invention, the hue and stability of the formed dye can be greatly improved.

[0325]

When the developing agent of the present invention is used, the color developability is remarkably improved and the hue is greatly improved. Here, a significant improvement in hue means that the absorption of the formed dye becomes remarkably sharp. Further, since the produced dye is very stable as a dissociator, a stable image can be obtained.

Front page continuation (72) Inventor Toshiki Taguchi, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (8)

[Claims] 1. A color developing agent represented by the general formula (I). General formula (I) in R ¹ -NHNH-Z ¹ (wherein, Z ¹ represents an acyl group, a carbamoyl group, .R ¹ to an alkoxycarbonyl group, a group represented by an aryloxycarbonyl group or the general formula (II) is 3 Represents a 6-membered aromatic heterocycle having at least one nitrogen atom, and R
The Hammett's substituent constant σ p value of the substituents on 1 is 0 or more and 0.9 or less (when there are two, the sum thereof is 0 or more and 1.8 or less). Embedded image (Wherein X represents a ⁵ group or -NR ⁶ R ⁷ group -OR. Wherein R ^4, R ^6, R ⁷ each represent a hydrogen atom, an alkyl group, .R ⁵ representing an aryl group or a heterocyclic group
Represents an alkyl group, an aryl group or a heterocyclic group. R ⁴ and R ⁵ or R ⁶ , or R ⁶ and R ⁷ may be bonded to each other to form a ring. ) 2. A color developing agent represented by the general formula (III). Embedded image (.R ² wherein R ¹ has the same meaning as R ¹ in formula (I),
Each R ³ represents a hydrogen atom or a substituent. ) 3. An image forming method, which comprises developing an image-exposed silver halide photographic light-sensitive material in the presence of a color developing agent represented by formula (I). 4. A color developing agent represented by the general formula (IV). Embedded image (In the formula, Q ¹ has 3 or more nitrogen atoms together with C 6
Represents a non-metal atomic group necessary for forming a membered aromatic heterocycle. R ^2, R ³ have the same meanings as R ^2, R ³ in the general formula (III). ) 5. A silver halide photographic light-sensitive material characterized by containing a compound represented by the general formula (I) in at least one hydrophilic colloid layer provided on a support. 6. An image forming method, which comprises developing the silver halide photographic light-sensitive material according to claim 5 by heat treatment at 50 ° C. or higher and 200 ° C. or lower. 7. An image forming method, which comprises developing the silver halide photographic light-sensitive material according to claim 5 in a solution. 8. An image forming method comprising developing a silver halide photosensitive material with a processing solution containing a color developing agent represented by the general formula (I).