JPH1184603A - Silver halide color photographic sensitive material and image forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stabilize image hues and to improve storage stability for a long period by using a nondiffusive quaternary ammonium salt in the presence of a dye-forming coupler and a specified reducing agent for color development. SOLUTION: The photographic constituent layers including at least one photosensitive silver halide emulsion layer are laminated on a support and one of these constituent layers contains the coemulsion comprising at least one kind of dye-forming coupler and the reducing agent for color development represented by formula and, as a counter ion, the nondiffusive quaternary ammonium salt. In the formula, R<11> is an aryl or heterocyclic group; R<12> is an alkyl, alkenyl, alkynyl, aryl, or heterocyclic group; X is a -SO2 -, -CO-, -COCO-, -CO-O-, -CO-N(R<13> )-, or -SO2 -N(R<13> )- group; and R<13> is an H atom or R<12> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material containing a color-forming reducing agent (developer) and an image forming method using the same.

[0002]

2. Description of the Related Art In general, a silver halide color photographic material is formed into an image through a color developing step and a silver removing step.
In the color development step, the exposed silver halide grains are developed (reduced) by an aromatic primary amine developing agent, and a color reaction image is obtained by the subsequent reaction of the oxidized product with the coupler. For example, in color paper processing, 4-amino-N-ethyl-N- (β
-Methanesulfonamidoethyl) -aniline sulfate.

[0003] When the above-mentioned color developing agent or the like is converted to an alkaline solution, it is oxidized in the air and significantly deteriorated. Therefore, a large amount of preservative and a large amount of replenisher are used, and the liquid composition and photographic performance are maintained. In recent years, in this industry, it has been desired to reduce the environmental load and the amount of waste and reuse the same, and the reduction in the processing chemicals of the color developing solution and the drastic replenishment thereof have been actively promoted. However, in order to maintain both photographic performance in continuous processing and light processing, and to reduce the amount of replenishment, it is necessary to further concentrate the processing chemicals in the replenisher, and the processing chemicals have not yet been reduced. It is the current situation. Further, when the replenishment is reduced, there arises a problem that the fluctuation of the stain and the photographic performance due to the accumulated component is remarkably increased.

As an effective solution for reducing the amount of processing chemicals and reducing replenishment, it is conceivable to incorporate a color developing agent or a precursor thereof into a light-sensitive material and process with an alkaline solution containing no developing agent. 4,060,4
No. 18, etc. However, these aromatic primary amine developing agents and their precursors are unstable, and have a drawback that stain occurs during long-term storage or color development of unprocessed photosensitive materials. Other than the color development method described so far, for example, European Patent No. 054
There is known a method in which a sulfonylhydrazine type compound and a coupler described in JP-A Nos. 5491A1 and 0565165A1 are incorporated in a photosensitive layer to form a coupling image during development. This sulfonylhydrazine-type compound had a disadvantage that almost no color was formed when a 2-equivalent coupler was used. For example, a 2-equivalent coupler has advantages over a 4-equivalent coupler in that the stain during storage of the coupler itself can be reduced and various functions can be imparted to the leaving group. For example, carbamoylhydrazine is a hydrazine compound which exhibits sufficient color development even when a 2-equivalent coupler is used, as disclosed in JP-A-8-234388 and JP-A-8-234388.
-320542. JP-A-8-297354 describes that a simple and rapid processing system can be obtained by subjecting a low silver content photosensitive material containing carbamoylhydrazine to hydrogen peroxide amplification.

On the other hand, the dye obtained from the hydrazine compound and the coupler for forming a dye is a dissociative dye, and dissociates into anions to exhibit color. Therefore, in order to sufficiently develop color, it is necessary to immerse in an alkali bath after image formation. However, when the dye is dissociated under such conditions, the remaining hydrazine compound and the dye-forming coupler itself are partially dissociated, resulting in a problem that a high stain is generated in the long-term storage of the processed image. The use of an electron-donating oil as a solvent in order to promote the dissociation and sufficient color development even after the treatment (after washing with water) is disclosed in JP-A-8-320542.
No. However, even in this case, when an acidic solution such as a carbonated beverage or vinegar is dripped on an image, a problem arises in that the portion becomes non-dissociated and discolors (hue change). To solve the above problems, there has been a demand for the development of a technology for stabilizing the hue of an image and improving long-term storability.

[0006]

In a method for obtaining a color image by using a color-forming reducing agent such as sulfonylhydrazine or carbamoylhydrazine in a light-sensitive material according to the present invention,
The hue stability and storage stability of the color image after processing were poor, and the generation of stain was large. That is, an object of the present invention is to provide a silver halide color photographic light-sensitive material suitable for greatly reducing the amount of replenishment and processing chemicals, and to provide a silver halide color photographic light-sensitive material capable of a simple and rapid processing system. It is. Also, the hue of the processed image is stabilized,
It is also an object of the present invention to provide a silver halide color photographic light-sensitive material in which color image fastness due to long-term storage is improved and generation of stain is suppressed.

[0007]

In view of such a problem,
As a result of intensive studies, the present inventors have found that the above object can be achieved by the following means.

(1) In a silver halide light-sensitive material having a photographic component layer including at least one photosensitive silver halide emulsion layer on a support, at least one type of coupler for forming a dye may be added to any of the photographic component layers. And a co-emulsion with at least one color-forming reducing agent represented by the following general formula (I) and a nondiffusible quaternary ammonium salt having an anionic organic compound as a counter ion. Silver halide color photographic light-sensitive material. General formula (I)

[0009]

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In the general formula (I), R ¹¹ is an aryl group or a heterocyclic group, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X is _{-SO 2 -, - CO -,} - COCO-, -C
O-O -, - CO- N (R 13) -, - COCO-O-,
-COCO-N (R ¹³⁾ - or -SO ₂ -N (R ¹³⁾
-. Here, R ¹³ is a hydrogen atom or a group described for R ¹² .

(2) The silver halide color photographic light-sensitive material as described in (1), wherein the compound represented by formula (I) is represented by formula (II) or (III). General formula (II), General formula (III)

[0012]

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Wherein Z ¹ is an acyl group, a carbamoyl group,
X represents an alkoxycarbonyl group or an aryloxycarbonyl group; Z ² represents a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group;
¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm value of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ³ represents a heterocyclic group.

(3) The silver halide according to item (2), wherein the compound represented by formula (II) or (III) is represented by formula (IV) or (V), respectively. Color photographic light-sensitive material. General formula (IV), General formula (V)

[0015]

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In the formula, R ¹ and R ² represent a hydrogen atom or a substituent, and X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. Here, the Hammett substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett substituent constant σm of X ² and X ⁴
Is 0.80 or more and 3.80 or less. R ³ represents a heterocyclic group.

(4) The silver halide according to item (3), wherein the compound represented by formula (IV) or (V) is represented by formula (VI) or (VII), respectively. Color photographic light-sensitive material. General formula (VI), (VII)

[0018]

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In the formula, R ⁴ and R ⁵ represent a hydrogen atom or a substituent, and X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, Represents a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group or a heterocyclic group. However, the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less. Q ¹ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5- to 8-membered heterocyclic ring together with C.

(5) Fourth having anionic organic compound
The silver halide color photographic material as described in the above item (1), (2), (3) or (4), wherein the quaternary ammonium salt is represented by a salt represented by the following general formula (Q). General formula (Q)

[0021]

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In the formula, n is 1 or 2. When n = 2, A is alkylene, arylene, alkenylene, -O
_{-, - SO 2 -, -} SO -, - C (= O) -, - N (-
R ₁₅ )-[R ₁₅ represents a hydrogen atom, an alkyl group or an aryl group] alone or in combination, and represents a divalent organic group. When n = 1, A is the same as R ₁₁ , R ₁₂ and R ₁₃ , and each represents a substituted or unsubstituted alkyl group;
Represents an aryl group or a polymer chain. R ₁₁ , R ₁₂ , R ₁₃
May be linked to form a ring structure. R ₁₄ represents a substituted or unsubstituted alkyl group, aryl group, alkoxy group, aryloxy group or heterocyclic group. X ^- is SO ₃ ^-
And / or COO ⁻ .

(6) The dye-forming coupler, the color-forming reducing agent and the quaternary ammonium salt are dissolved in the same high-boiling solvent and dispersed in the photographic constituent layer as a coemulsion. The silver halide color photographic light-sensitive material according to the above (1), (2), (3), (4) or (5).

(7) The total amount of silver in all coating layers contains 0.003 to 0.3 g / m ² of silver halide in terms of silver. 2),
(3) The silver halide color photographic light-sensitive material according to the above (4), (5) or (6). (8) (1), (2), (3), (4), (5),
An image forming method, wherein the silver halide color photographic light-sensitive material according to the above item (6) or (7) is exposed by scanning exposure with an exposure time per pixel of 10 ^-8 to 10 ^-4 seconds.

The image obtained by using the color-forming reducing agent and the coupler of the present invention exhibits a high color-forming density and a low minimum density, and is excellent in long-term storage stability of the photographic material. On the other hand, the hue of the obtained image is unstable and has a low pH of 6 or less.
When immersed in a solution, the color changes and the image density also decreases. Further, the color image fastness is also deteriorated. By using the non-diffusible quaternary ammonium salt of the present invention, the hue is stabilized and the color image fastness is further improved. When an inorganic anion such as chloride ion is used as a quaternary ammonium counterion, the sensitivity is lowered or the minimum density is increased during storage of the photosensitive material. And had excellent storage stability. Further, when the color-forming reducing agents represented by the general formulas (II) and (III) are used, the effect of improving the fastness of a color image to light by the non-diffusible quaternary ammonium salt of the present invention is particularly large. Further, the color-forming reducing agents of the general formulas (II) and (III) give high quality images in combination with a 2-equivalent coupler and have less stain.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific configuration of the present invention will be described in detail. The non-diffusible quaternary ammonium salt of the present invention will be described in more detail. "Non-diffusive" above
This means that it does not substantially dissolve in water, a developing solution, an alkali activator (described later), or the like, and does not diffuse or elute from the photosensitive material during processing. The “substantially insoluble amount” means that the amount dissolved in water or 100 cc of a 0.01N alkaline solution is 0.1 g or less, preferably 0.01 g or less,
More preferably, the amount is 0.005 g or less. In the present invention, the compound represented by the general formula (Q) is preferable, and will be described in detail below.

In the general formula (Q), n is 1 or 2. For n = 2, A is an alkylene, arylene, alkenylene (each preferably having a carbon number of 20 or less, more preferably 8 or less), - O -, - SO 2 -, - SO-,
-C (= O) -, - N (-R 15) - [R 15 is a hydrogen atom,
Represents an alkyl group or an aryl group] alone or in combination. In addition, the number of carbon atoms in the divalent organic group is preferably 20 or less, the S-linkage is preferably 8 or less, and the O-linkage is preferably 3 or less. When n = 1, A is the same as R ₁₁ , R ₁₂ , and R ₁₃ and represents a substituted or unsubstituted alkyl group, aryl group or polymer chain having 30 or less carbon atoms. As the substituent, an aryl group, an aralkyl group, an alkenyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxy group, an aryloxy group, an amide group, a sulfamoyl group, a carbamoyl group,
It represents a ureido group, an amino group, a cyano group, a sulfonyl group, a mercapto group, an alkylthio group, or an aralkylthio group.
A plurality of substituents may be present. R ₁₁ , R ₁₂ and R ₁₃ may be linked to form a ring structure. For example, R ₁₁ and R ₁₃ are linked to represent a morpholino group, a piperidyl group, or a pyrrolidinyl group.

R ₁₄ is a substituted or unsubstituted alkyl group (eg, dodecyl group, cetyl group, hexadecyl group, octadecyl group, etc.), an aryl group (eg, butylphenyl group, octylphenyl group, dodecylphenyl group, naphthyl group) ), An alkoxy group (eg, dodecyloxy group, cetyloxy group, hexadecyloxy group, polyoxyethylene alcohol ether group, etc.), an aryloxy group (eg, butylphenoxy group, dodecylphenoxy group, naphthoxy group, etc.) or heterocyclic ring Group (for example,
Octylpyridyl group, dodecylfuryl group, etc.).
The carbon number of R ₁₄ can be selected in a wide range, but is preferably 8 or more, particularly preferably 10 or more and 40 or less. X ⁻ represents SO ₃ ⁻ and / or COO ⁻ . The counter anion of the cation preferably has at least 70 mol% of the anion. It is particularly preferred that the content be 90 mol% or more.

Preferred cation parts and anion parts of the compound represented by formula (Q) are listed below, but the invention is not limited by these.

[0030]

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[0031]

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[0032]

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[0033]

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As specific examples, T-2, T-3, T-
9, T-12 or T-13 and W-3, W-9, W-1
Compounds in each case with 0 or W-13 are preferably used, but this does not limit the invention. The compound used in the present invention can be obtained by ion exchange of a quaternary salt compound having an inorganic anion as a counter ion known in the art or the like with the compound having an anion moiety in the present invention. The preparation example is shown below.

[Preparation method] 7.8 g of tetraoctyl ammonium bromide (salt of T-2 and bromine ion) and W-
8.7 g of sodium salt of 3 was added to 100 cc of a mixture of ethyl acetate and distilled water at a volume ratio of 1: 1 and shaken.
After standing, the aqueous phase was removed and the ethyl acetate phase was separated.
This step was repeated three times. After confirming the absence of bromine ions in the ethyl acetate phase by ion chromatography, the ethyl acetate was distilled off under reduced pressure to obtain the non-diffusible quaternary ammonium salt (T-2 · W-3) of the present invention. . When preparing an emulsion, it is preferable to use an ethyl acetate solution which has not been removed by distillation and also serve as an auxiliary solvent.

The non-diffusible quaternary ammonium salt of the present invention is used in the presence of a coupler for forming a dye and a reducing agent for forming a color, and is particularly soluble in a high-boiling organic solvent (oil) and contains a hydrophilic colloid such as gelatin. It is preferable to use it dispersed within. The amount used is 0.1 to 10 times, preferably 0.5 to 5 times, more preferably 1 to 3 times the molar amount of the reducing agent for coloring used in the coloring layer.

Hereinafter, the color-forming reducing agent used in the present invention will be described in detail. The color-forming reducing agent represented by the general formula (I) used in the present invention reacts directly with the exposed silver halide in an alkaline solution and is oxidized, or is oxidized by the exposed silver halide. A compound characterized by being oxidized by a redox reaction with a developing agent, the oxidized product reacting with a dye-forming coupler,
It is a compound characterized by forming a dye. Hereinafter, the structure of the color-forming reducing agent represented by the general formula (I) will be described in detail.

In the general formula (I), R ¹¹ represents an aryl group or a heterocyclic group which may have a substituent. The aryl group of R ^11, preferably that of 6 to 14 carbon atoms include, for example, phenyl or naphthyl. R ¹¹
As the heterocyclic group, preferably, nitrogen, oxygen, sulfur,
It is a saturated or unsaturated 5-, 6- or 7-membered ring containing at least one of selenium. These may be condensed with a benzene ring or a hetero ring. R
Examples of ¹¹ heterocycles are furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl,
Pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, purinyl,
Pteridinyl, azepinyl, benzoxepinyl and the like.

Examples of the substituent for R ¹¹ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group and a heterocyclic thio group. , Acyloxy group, acylthio group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group, arylamino group, amide group, alkoxycarbonylamino group An aryloxycarbonylamino group, a ureido group, a sulfonamide group, a sulfamoylamino group,
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylcarbamoyl group,
Carbamoylcarbamoyl group, sulfonylcarbamoyl group, sulfamoylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfamoyl group,
Examples include acylsulfamoyl, carbamoylsulfamoyl, halogen, nitro, cyano, carboxyl, sulfo, phosphono, hydroxyl, mercapto, imide, and azo groups. R ¹² represents an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group.

The alkyl group represented by R ¹² is preferably a linear, branched or cyclic C 1-16 alkyl group such as methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl, cyclopentyl, cyclooctyl. And the like. The alkenyl group for R ¹² is preferably a chain or cyclic group having 2 to 16 carbon atoms, and includes, for example, vinyl, 1-octenyl and cyclohexenyl. The alkynyl group for R ¹² preferably has 2 to 16 carbon atoms, such as 1-butynyl and phenylethynyl. As the aryl group and heterocyclic group for R ¹² , those described for R ¹¹ can be mentioned. R ¹²
Examples of the substituent of R ¹¹ include those described for the substituent of R ¹¹ . X represents -SO _2- , -CO-, -COC
O -, - CO-O - , - CON (R 13) -, - COCO
-O -, - COCO-N ( R 13) - or -SO ₂ -N
(R ¹³⁾ - and the like. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . Among these groups, -CO-,-
CON (R ¹³ ) — and —CO—O— are preferable, and —CON (R ¹³ ) — is particularly preferable in that color developing properties are particularly excellent. Among the compounds represented by the general formula (I), the compounds represented by the general formulas (II) and (III) are preferable,
The compounds represented by the general formulas (IV) and (V) are more preferable, and the compounds represented by the general formulas (VI) and (VII) are more preferable. Hereinafter, the compounds represented by formulas (II) to (VII) will be described in detail.

The general formula (II) and Z ¹ in the general formula (III) represents an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group,, Z ²
Represents a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. The acyl group is preferably an acyl group having 1 to 50 carbon atoms, and more preferably 2 to 40 carbon atoms. Specific examples include acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, n-octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, Dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group, 3
-(N-hydroxy-N-methylaminocarbonyl) propanoyl group. The case where Z ¹ and Z ² are carbamoyl groups will be described in detail in general formulas (VI) to (VII). As the alkoxycarbonyl group and the aryloxycarbonyl group, an alkoxycarbonyl group and an aryloxycarbonyl group having 2 to 50 carbon atoms are preferable, and more preferably 2 to 40 carbon atoms. As a specific example,
Methoxycarbonyl group, ethoxycarbonyl group, isobutyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 4-octyloxyphenoxycarbonyl group, 2-hydroxymethylphenoxycarbonyl group, 2- And a dodecyloxyphenoxycarbonyl group.

X ¹ , X ² , X ³ , X ⁴ and X ⁵ each represent a hydrogen atom or a substituent. Here, examples of the substituent include 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.), having 2 to 50 carbon atoms in total.
(E.g., ethynyl, 1-propynyl, etc.), an aryl group having 6 to 50 carbon atoms (e.g., phenyl, naphthyl, anthryl, etc.), and an acyloxy group having 1 to 50 carbon atoms (e.g., acetoxy, tetradecanoyloxy) , Benzoyloxy, etc.), a carbamoyloxy group having 1 to 50 carbon atoms (eg, N, N-dimethylcarbamoyloxy), a carbonamide group having 1 to 50 carbon atoms (eg, formamide, N-methylacetamide, acetamide, N -Methylformamide, benzamide, etc.),
C1-C50 sulfonamide groups (e.g., methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.) and C1-C50 carbamoyl groups (e.g., N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl and the like, a sulfamoyl group having 0 to 50 carbon atoms (for example, N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) ) Sulfamoyl, etc.), C1-C50 alkoxy groups (for example, methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, dodecyloxy, 2- (2,4-di-t-pentylphenoxy) ethoxy, etc. ), An aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4 Methoxyphenoxy, naphthoxy, etc.), an aryloxycarbonyl group of 7 to 50 carbon atoms (e.g., 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
0 alkylthio groups (eg, methylthio, octylthio, cyclohexylthio, etc.), arylthio groups having 6 to 50 carbon atoms (eg, phenylthio, naphthylthio, etc.),
A ureido group having 1 to 50 carbon atoms (for example, 3-methylureide, 3,3-dimethylureide, 1,3-diphenylureide and the like), a heterocyclic group having 2 to 50 carbon atoms (for example, nitrogen, A 3- to 12-membered monocyclic or condensed ring containing at least one or more oxygen and sulfur atoms, for example, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino,
-Quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), having 1 to 50 carbon atoms
(E.g., acetyl, benzoyl, trifluoroacetyl, etc.) and a sulfamoylamino group having 0 to 50 carbon atoms (e.g., N-butylsulfamoylamino, N
-Phenylsulfamoylamino, etc.), having 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, and examples of the substituent include the substituents mentioned here. X ¹ , X ² , X ³ , X ⁴ and X ⁵ may be bonded to each other to form a condensed ring. 5 to 5
A 7-membered ring is preferred, and a 5- to 6-membered ring is more preferred.

The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 34 or less. Also, one or more is preferable. X ¹ , X ² , X ³ , X ⁴ , X in the general formulas (II) and (III)
Regarding ⁵ , the sum of the Hammett's substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm value of X ² and X ⁴ is 0.80 or more and 3.80 or less. X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ in the general formula (VI) represent a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Represents an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group or a heterocyclic group, which may further have a substituent and may be bonded to each other to form a condensed ring. X ¹ , X ² , X ³ ,
It is the same as that described for X ⁴ and X ⁵ . However, the general formula (V
In I), the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less; It is preferably from 1.50 to 3.80, and more preferably 1.70.
Above is 3.80 or less. Here, if the sum of the σp value and the σm value is less than 0.80, there is a problem that the coloring property is not sufficient, and if it exceeds 3.80, it becomes difficult to synthesize and obtain the compound itself. .

The Hammett's substituent constants σp and σm are described, for example, by Naoki Inamoto, “Hammet Rule—Structure and Reactivity—” (Maruzen), “New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds V” 2605. (Chemical Society of Japan, Maruzen), Tadao Nakaya, "Explanation of Theoretical Organic Chemistry", 217 pages (Tokyo Kagaku Dojin), Chemical Review (91), 165-195
The book is described in detail in pages (1991). R ¹ , R ² , (VI) and (VI) in the general formulas (IV) and (V)
R ⁴ and R ⁵ in I) represent a hydrogen atom or a substituent, and specific examples of the substituent include X ¹ , X ² , X ³ , X ⁴ ,
Represent the same meanings as those described for X ^5, preferably a substituted or unsubstituted alkyl group having a hydrogen atom or 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, 1 to carbon atoms 50 substituted or unsubstituted heterocyclic groups, more preferably at least one of R ¹ and R ² and at least one of R ⁴ and R ⁵ are hydrogen atoms.

In the general formulas (III) and (V), R ¹ represents a heterocyclic group. Here, a preferred heterocyclic group has 1 carbon atom.
-50 heterocyclic groups, wherein the heteroatoms include, for example, at least one nitrogen, oxygen and sulfur atom, and are a saturated or unsaturated 3- to 12-membered (preferably 3- to 8-membered) monocyclic ring. Or a condensed ring, and specific examples of the hetero ring include furan, pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, Thiazole, quinazoline, isothiazole,
Pyridazine, indole, pyrazole, triazole,
Quinoxaline and the like. These heterocyclic groups may have a substituent, and preferably have at least one electron-withdrawing group. Here, the electron-withdrawing group means a group having a positive Hammett σp value. When the color-forming reducing agent of the present invention is incorporated in a light-sensitive material, at least one of Z ¹ , Z ² , R ^{1 to} R ⁵ , and X ^{1 to} X ¹⁰ has a ballast group (a color-forming reducing agent represented by ( 5 carbon atoms for easy solubilization and immobilization in high boiling organic solvents
To 50, preferably 8 to 40 groups). Next, the novel color-forming reducing agent used in the present invention will be specifically described, but the scope of the present invention is not limited to these specific examples.

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As couplers preferably used in the present invention, there are compounds having 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.

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Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl group, cyano group, nitro group, 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 or a heterocyclic residue which may have a substituent. R ¹⁴ ,
Examples of the substituent which R ¹⁵ and R ¹⁶ may have include the aforementioned X ¹
Those mentioned above as examples for to X ⁵ may be mentioned.

In the general formulas (1) to (4), Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized form of a color-forming reducing agent. Examples of Y include a heterocyclic group (a heterocyclic atom is a saturated or unsaturated monocyclic or condensed 5- to 7-membered ring containing at least one nitrogen, oxygen, sulfur or the like, and examples thereof include succinimide and maleic Imide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidin-2,4-dione , Thiazolidine-2,4-dione, imidazolidine-2-one, oxazolin-2-one, thiazoline-2
-One, 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, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), aryloxy group (eg, phenoxy, 1-naphthoxy, etc.), hetero A ring oxy group (eg, pyridyloxy, pyrazolyloxy, etc.), an acyloxy group (eg, acetoxy, benzoyloxy, etc.),
Alkoxy group (eg, methoxy, dodecyloxy, etc.), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.), alkoxycarbonyloxy group (Eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio groups (eg, phenylthio, naphthylthio, etc.), heterocyclic thio groups (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 Si group (eg, benzenesulfonyloxy, toluenesulfonyloxy, etc.), carbonamide group (eg, acetamide, trifluoroacetamide, etc.), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl group ( For example, methanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl), alkylsulfinyl group (eg, methanesulfinyl), arylsulfinyl group (eg, benzenesulfinyl), arylazo group (eg, phenylazo, naphthylazo) Carbamoylamino group (for example, N-methylcarbamoylamino 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. General formula (1)
In (4), R ¹⁴ and R ¹⁵ , and R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring. Formula (5) represents a coupler called a 5-pyrazolone-based coupler, wherein R ¹⁷ represents an alkyl group, an aryl group, 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.

In the 5-pyrazolone coupler represented by the general formula (5), R ¹⁷ is an aryl group or an acyl group,
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) is an acyl group such as a benzoyl group, and these groups may further have a substituent, and these groups may be a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a connecting organic substituent or a halogen atom. Y has the same meaning as described above.

R ¹⁸ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group. The general formula (6) represents a coupler called a pyrazoloazole coupler, wherein 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 described in U.S. Pat. U.S. Patent No. 4,
No. 500,654, pyrazolo [1,5-b]-
1,2,4-triazoles, U.S. Pat.
No. 067, pyrazolo [5,1-c] -1,2,4
-Triazoles are preferred.

For details of the substituents on the azole ring represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the 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;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 201443 is a pyrazolotriazole coupler having a carboxamide 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 the general formulas (7) and (8), R ²¹ represents a substituent, r represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When r and m are 2 or more, R ²¹ may be different from each other. Examples of the substituent of R ^{21 to} R ²³ include those described as examples of X ^{1 to} X ^{5 in} the general formulas (II) and (IV). Y has the same meaning as described above.
Preferred examples of the phenolic coupler represented by the general formula (7) include U.S. Pat. Nos. 2,369,929, 2,801,171, 2,772,162 and 2, 2-acylamino-5-alkylphenols described in 895,826 and 3,772,002, etc .; U.S. Pat. Nos. 2,772,162 and 3,75
No. 8,308, No. 4,126,396, No. 4,3
34,011, 4,327,173, West German Patent Publication 3,329,729, JP-A-59-16695.
No. 6, etc. 2,5-diacylaminophenol-based,
U.S. Pat. Nos. 3,446,622 and 4,333,9
No. 99, No. 4,451,559, No. 4,427,
No. 767, etc., and 2-phenylureido-5-acylaminophenols. Y is the same as described above.

A naphthol coupler represented by the general formula (8)
Preferable examples of US Pat. No. 2,474,29
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
2-carbamoyl-1-naphthol described in No. 200, etc.
And 2 described in U.S. Pat. No. 4,690,889.
-Carbamoyl-5-amido-1-naphthols and the like.
I can do it. Y is the same as above
is there. General formulas (9) to (12) represent pyrrolotriazole
Is a coupler called R ³², R³³, R³⁴Is a hydrogen atom
Or a substituent. Y is as described above.
You. R³², R³³, R³⁴Is a substituent of the aforementioned X¹~ X
^FiveAre mentioned as examples. General formula (9)
Preferred are pyrrolotriazole couplers represented by (12).
A good example is EP 488,248 A1,
No. 491,197A1 and No. 545,300
R³², R³³At least one is an electron-withdrawing group
Couplers. Same as above for Y
The same. In addition, fused phenol, imidazole,
Roll, 3-hydroxypyridine, other active methyl
Ren, active methine, 5,5-fused heterocycle, 5,6-fused ring
A coupler having a structure such as a heterocyclic ring can be used.

Examples of fused phenol couplers include US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used. As the imidazole coupler, couplers described in U.S. Pat. Nos. 4,818,672 and 5,051,347 can be used. As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 and the like can be used.

As active methylene and active methine couplers, US Pat. Nos. 5,104,783 and 5,16
The couplers described in 2,196 and the like can be used. 5,5
-As a fused heterocyclic coupler, US Pat.
Pyrrolopyrazole couplers described in JP-A-4,289, and pyrroleimidazole couplers described in JP-A-4-174429 can be used. Examples of 5,6-fused heterocyclic couplers include pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585 and JP-A-4-20473.
No. 0, pyrrolotriazine couplers described in EP-A-556700, and the like can be used.

In the present invention, in addition to the above-mentioned couplers, West German Patent Nos. 3,819,051A and 3,823,049.
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,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 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 of course not limited thereto.

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The color-forming reducing agent of the present invention is used in an amount of 0.01 to 10 mmol per color-forming layer in order to obtain a sufficient color-forming density.
/ M ² . A more preferred amount is 0.05 to 5 mmol / m ² , and a particularly preferred amount is 0.1 to 1 mmol / m ² . The amount of the coupler in the color-forming layer in which the color-forming reducing agent of the present invention is used is preferably 0.05 to 20 times, more preferably 0.1 to 10 times, particularly preferably 0.1 to 10 times the molar amount of the color-forming reducing agent. Is 0.2 to 5 times.

The color-forming reducing agent, quaternary ammonium salt and coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, and are dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination). An oil-in-water dispersion method in which the emulsion is dispersed in an aqueous gelatin solution and added to the silver halide emulsion is preferred. The high boiling organic solvent that can be used in the present invention has a melting point of 100
It is a compound which is immiscible with water having a boiling point of 140 ° C. or lower and a boiling point of 140 ° C. or higher and can be used as long as it is a good solvent for the color-forming reducing agent and the coupler. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. For details of these high-boiling organic solvents, see JP-A-62-21.
No. 5,272, published from the lower right column on page 137 to the upper right column on page 144. In the present invention, when using a high-boiling organic solvent, the amount of the high-boiling organic solvent used may be any amount, but preferably with respect to the color-forming reducing agent,
The ratio by weight of the high-boiling organic solvent / color-forming reducing agent is preferably 20 or less, more preferably 0.02 to 5, and particularly preferably 0.2 to 4. In the present invention, a known polymer dispersion method may be used. The steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) 2,541,274, and US Pat. 2,541,2
No. 30, JP-B-53-41091 and European Patent Publication No. 029104. As a more preferable method, a dispersion method using a water-insoluble and organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00.
723.

The average particle size of the lipophilic fine particles containing the color-forming reducing agent of the present invention is not particularly limited, but is preferably from 0.05 to 0.3 μm from the viewpoint of color-forming properties. Further, the thickness is more preferably 0.05 to 0.2 μm. Generally, in order to reduce the average particle size of the lipophilic fine particles, to select the type of surfactant, increase the amount of surfactant used,
Increasing the viscosity of the hydrophilic colloid solution, decreasing the viscosity of the lipophilic organic layer by using a low-boiling organic solvent, etc.,
Alternatively, it can be achieved by increasing the shearing force such as increasing the rotation of the stirring blade of the emulsifying device, or by lengthening the emulsifying time. The particle size of the lipophilic fine particles can be measured by, for example, a device such as Nanosizer manufactured by Coulter, UK.

In the present invention, it is preferable to use an auxiliary developing agent and its precursor in the light-sensitive material, and these compounds will be described below. The auxiliary developing agent used in the present invention is a compound having an action of promoting electron transfer from a color-forming reducing agent to silver halide in the course of developing silver halide grains, and preferably, an exposed silver halide. A compound capable of developing particles and oxidizing the particles to oxidize a color-forming reducing agent (hereinafter referred to as cross-oxidation). As the auxiliary developing agent used in the present invention, pyrazolidones, dihydroxybenzenes, reductones or aminophenols are preferably used, and pyrazolidones are particularly preferably used. The diffusivity of these compounds in the hydrophilic colloid layer is preferably low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0% or less. .01%
It is as follows. The precursor of the auxiliary developing agent used in the present invention is a compound which is stably present in the light-sensitive material, but which releases the above-mentioned auxiliary developing agent quickly once it is processed with a processing solution. In this case, it is preferable that the diffusivity in the hydrophilic colloid layer is low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less. The solubility of the auxiliary developing agent released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility. The auxiliary developing agent precursor of the present invention is preferably represented by the general formula (A).

Formula (A) A- (L) n-PUG A represents a block group in which the bond to (L) n-PUG is cleaved during development processing, and L represents L and A in formula (A). Represents a linking group in which the bond between L and PUG is cleaved after the bond is cleaved, n represents an integer of 0 to 3, and PUG represents an auxiliary developing agent. As the auxiliary developing agent, an electron-emitting compound according to the Kender Rupertz rule other than the p-phenylenediamine compounds is used, and the above-mentioned pyrazolidones are preferably used. As the blocking group represented by A, the following known ones can be applied. That is, a blocking group such as an acyl group or a sulfonyl group described in U.S. Pat. No. 3,311,476, a blocking group utilizing a reverse Michael reaction described in JP-A-59-105542 or the like;
No. 280140, a blocking group utilizing quinone methide or a compound similar to quinone methide by intramolecular electron transfer, JP-A-63-318555 (European Patent Publication 0)
No. 295729), a blocking group utilizing an intramolecular nucleophilic substitution reaction, a blocking group utilizing an addition reaction of a nucleophile to a conjugated unsaturated bond described in JP-A-4-186344, and the like. 62-163051, a blocking group utilizing a β-elimination reaction, JP-A-61-188540, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes, and JP-A-62-187850. Group utilizing the Rossen rearrangement reaction of
No. 7457, a blocking group utilizing the reaction of an N-acyl compound of thiazolidine-2-thione with an amine, and a blocking group having two electrophilic groups described in WO 93/03419. Blocking groups that react with a nucleating agent can be exemplified. The group represented by L is a linking group capable of cleaving (L) n-1-PUG after leaving from the group represented by A during development processing. Absent. Specific examples of the auxiliary developing agent or its precursor are shown below, but the compounds used in the present invention are not limited to these specific examples.

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These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer and the protective layer. When the compound contains an auxiliary developing agent, it is preferably used by adding it to a non-photosensitive layer. As a method of incorporating these compounds into the photosensitive material, a method of dissolving in a water-miscible organic solvent such as methanol and directly adding the compound to the hydrophilic colloid layer, and coexisting with a surfactant to form an aqueous solution or a colloidal dispersion. The method of addition, after dissolving in a solvent or oil that is substantially immiscible with water,
A method of adding a substance dispersed in water or a hydrophilic colloid, a method of adding a dispersion in the form of a solid fine particle dispersion, and the like can be used, and a conventionally known method can be applied alone or in combination. The method for preparing the solid fine particle dispersion is described in detail in page 20 of JP-A-2-23544. The amount added to the light-sensitive material is 1 mole based on the color-forming reducing agent.
% To 200 mole%, preferably 5 mole% to 10
0 mole%, more preferably 10 mole% to 50 m
ole%.

In the silver halide photographic light-sensitive material of the present invention,
In addition, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the permeable support include permeable films such as cellulose triacetate film and polyethylene terephthalate, and 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (E).
G) with polyester or NDCA, terephthalic acid and EG
A material in which an information recording layer such as a magnetic layer is provided on polyester or the like is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio in the case of mixing with the water-resistant resin is preferably 0.0005 to 3% by weight with respect to the resin, and more preferably 0.1 to 3% by weight.
001 to 0.5% by weight. As a reflective support,
On a transmissive support, or a reflective support as described above,
It may be provided with a hydrophilic colloid layer containing a white pigment. In addition, the reflection-type support is a mirror-reflective or
It may be a support having a seed diffuse reflective metal surface.

The silver halide emulsion used in the present invention has a silver chloride content of 95 mol% from the viewpoint of rapid processing.
The silver chloride or silver chlorobromide emulsion described above is preferred, and a silver halide emulsion having a silver chloride content of 98 mol% or more is more preferred. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable since high sensitivity can be obtained and photographic performance can be stabilized.

The above-mentioned reflection type support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Emulsifying and dispersing methods for cyan, magenta, yellow couplers, etc., color image preservability improvers (stain inhibitors and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive materials, pH of photosensitive material coatings, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

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The total coated silver amount of the light-sensitive material of the present invention is preferably 0.003 to 12 g per m ^{2 in} terms of silver. In the case of a transmission material such as a color negative film, the weight is preferably 1 to 12 g, more preferably 3 to 10 g.
0.003 to 1 g for reflective materials such as color paper
Is preferred in terms of rapid processing and low replenishment. In this case, the amount of each layer added is preferably 0.001 to 0.4 g per photosensitive layer. In particular, when the light-sensitive material of the present invention is subjected to intensification processing (processing of enhancing color development of a light-sensitive material having a low silver content with hydrogen peroxide or the like to obtain a sufficient color density), the amount is preferably 0.003 g to 0.3 g. It is preferably 0.01 to 0.1 g, particularly preferably 0.015 to 0.05 g. In this case, the amount is preferably 0.001 to 0.1 g, more preferably 0.003 g to 0.03 g, for one photosensitive layer. In the present invention, 1 m ² per 0.00 silver coverage of the light-sensitive layer
If the amount is less than 1 g, the dissolution of the silver salt proceeds, and a sufficient color density cannot be obtained.
An increase in min and air bubbles are generated, and it becomes difficult to endure appreciation.

The total amount of gelatin in the light-sensitive material of the present invention is 1 m ²
1.0 to 30 g, preferably 2.0 to 20 g
g. In the swelling of the present photosensitive material using an alkaline solution having a pH of 12, the saturated swelling film thickness (90% of the maximum swelling film thickness) is obtained.
%) Is preferably 15 seconds or less, more preferably 10 seconds or less. The swelling ratio [(maximum swollen film thickness−film thickness) / film thickness × 100] is 50 to
300% is preferable, and especially 100-200% is preferable.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a light emitter that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a luminous body which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signals of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color to sequentially emit light of each color, and exposing through a filter for cutting a color other than that color (plane sequential exposure) may be adopted. However, since a high-resolution cathode ray tube can be used, it is preferable for high image quality.

The photosensitive material of the present invention is a second harmonic generation light source (SHG) in which a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source is combined with a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red.

The exposure time in such scanning exposure is as follows:
If the pixel size when the pixel density is 400 dpi is defined as the exposure time, the preferable exposure time is 1
It is ^0-4 seconds or less, more preferably ^10-6 seconds or less. In particular, it is preferable that the exposure time per pixel is 10 ^-8 to 10 ^-4 seconds and the reciprocity law failure is improved by performing the exposure using the scanning exposure in which the adjacent rasters overlap.
Regarding the preferred scanning exposure method applicable to the present invention,
The details are described in the patents listed in the above table.

The method of developing the light-sensitive material incorporating the color-forming reducing agent of the present invention after exposure is as follows: an activator processing method of developing with an alkaline processing solution not containing a color developing agent; an auxiliary developing agent / base , A method in which the alkaline processing solution is spread on a photosensitive material by a diffusion transfer method, and a method in which thermal processing is performed.

Activator processing refers to a processing method in which a color-forming reducing agent is incorporated in a light-sensitive material and is developed with a processing solution containing no color-developing agent. In the present invention, the "activator liquid" is characterized in that it does not substantially contain a p-phenylenediamine-based color developing agent as conventionally used, and other components (eg, alkali, halogen, chelating agent, etc.) ) May be included. In some cases, it is preferable that a reducing agent is not contained in order to maintain processing stability. In this case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites, and the like are not substantially contained. Here, "substantially not contained" means preferably 0.5 mmol / liter or less, more preferably 0.1 mmol / liter or less. In particular, it is preferable not to contain at all. The pH of the alkaline processing solution is
It is preferably 9 to 14, particularly preferably 10 to 13.
It is. Regarding the light-sensitive material for activator processing and its processing, see, for example, JP-A-8-234388, and Japanese Patent Application No. 7-33.
Nos. 4190, 7-334192, 7-334419
No. 7 and No. 7-344396.

The process of developing an alkaline processing solution by the diffusion transfer method is known in the art as an instant processing system, and includes at least one photosensitive layer / dye-forming layer (the photosensitive layer and the dye-forming layer are composed of the same layer). The photosensitive material having a mordant layer for capturing and mordanting the diffusible dye formed from the photosensitive layer / dye-forming layer on the same support or on a separate support is subjected to alkaline treatment. This means that the liquid is developed at a thickness of 500 μm or less, preferably 50 to 200 μm.

When an auxiliary developing agent is incorporated, it is preferable that the alkaline processing solution for producing or storing the processing solution does not contain the auxiliary developing agent. In the case of the diffusion transfer method, the pH of the alkaline treatment liquid is preferably 10 to 14
And particularly preferably 12 to 14. See The Theory of Photog for the process of instant materials.
The fourth edition of the raphic Process (1977, Macmillan) and the specific composition of film units are described in
No. 3-226649. Examples of the materials included in the film unit and various layers including the same are described below.

The dye receiving layer and the mordant contained therein are described in JP-A-61-252551, US Pat. Nos. 2,548,564, 3,756,814 and 4,124,386. No. 3,625,694. The neutralizing layer for lowering the pH of the photosensitive material after developing the alkaline processing solution is described in
-122753, U.S. Pat. No. 4,139,383,
RD-No. 16102, the timing layer used in combination with this neutralizing layer is disclosed in
136328, U.S. Pat. No. 4,267,262,
Nos. 4,009,030 and 4,268,604. As the emulsion, any emulsion can be used. Preferred autopositive emulsions for photographic light-sensitive materials are described in JP-A-7-333770 and JP-A-7-33377.
No. 1 and the like.

In addition, if necessary, a light-shielding layer, a reflective layer, an intermediate layer, an isolation layer, an ultraviolet absorbing layer, a filter layer, an overcoat layer, an adhesion improving layer, and the like can be provided. The processing solution for processing the above-mentioned light-sensitive material contains processing components necessary for development, and usually contains a thickening agent and spreads uniformly on the light-sensitive material. Thickening agents such as carboxymethylcellulose and hydroxyethylcellulose are preferable as the thickener. Details of the photosensitive layer and the processing solution are described in JP-A-7-337377.

The heat treatment in the heat development of the light-sensitive material is known in the art and can be applied to the light-sensitive material of the present invention. For the photothermographic material and its process, see, for example, 553-
555 pages, published in April 1978, 40 pages of video information, Nobletts Handb
ook of Photography and Reprography 7th Ed. (Van Nos
trand and Reinhold Company), pages 32 to 33, U.S. Pat. Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075;
British Patent Nos. 1,131,108 and 1,167,7
Issue 77 and Research Disclosure, June 1978
It is described in the month issue, pages 9 to 15 (RD-17029).

The light-sensitive material of the present invention is prepared in accordance with US Pat. No. 4,514,49 for the purpose of accelerating silver development and a dye-forming reaction.
Nos. 3, 657, 848 and No. 5 (March 22, 1991, issued by Aztec Co., Ltd.)
It is preferable to apply a base precursor described on page, etc., or a base generation method described in European Patent Publication No. 210,660 or US Patent No. 4,740,445.
The light-sensitive material of the present invention contains U.S. Pat. Nos. 3,347,675 and 3,667,9 for promoting thermal development.
No. 59 may be added.

When the light-sensitive material of the present invention is subjected to heat treatment, in order to promote development and / or diffusion transfer of the processing material,
Water, an aqueous solution containing an inorganic alkali metal salt or an organic base,
It is also preferable to include a low-boiling solvent or a mixed solvent of a low-boiling solvent and water or the above-mentioned basic aqueous solution in a light-sensitive material or a processing sheet and heat-treat it. Examples of the method using water include JP-A-63-144354 and JP-A-63-144.
355, 62-38460, JP-A-3-2105
No. 55, JP-A-62-253159 and 63-855
44, EP 210,660 and U.S. Pat. No. 4,740,445.

The present invention relates to JP-A-7-261336, JP-A-7-268045, JP-A-8-30103, and JP-A-8-46.
The invention can also be applied to the photothermographic materials and photothermographic image forming methods described in JP-A-822-822 and JP-A-8-97344.
The heating temperature in the thermal development step is about 50 ° C to 200 ° C,
Particularly, a temperature of 60 ° C to 150 ° C is useful.

The water-saving technology applied to the present invention is described in detail in Research Disclosure Item 36544 (19).
(September 1994), page 540, right column to page 541, left column.

[0129]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to only these examples. Example 1 (Preparation of photosensitive material) After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a subbing layer of a gelatin layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. Thus, a multilayer color photographic paper having the following layer configuration was produced. This is the sample (1
00). In addition, the weight ratio (II / I) of the optical brighteners (I) and (II) having the following structure was 20 /
At 80, the content was 15 mg / m ² , the content relative to polyethylene was 0.05% by weight.

[0130]

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A coating solution was prepared as follows. Preparation of first layer coating solution [Preparation of quaternary ammonium salt] tetraoctyl ammonium bromide (salt of T-2 and bromine ion) 15.
66 g and 17.34 g of the sodium salt of W-3 were added to 200 cc of a solution of ethyl acetate: distilled water = 1: 1 (volume ratio), shaken, and allowed to stand. After separation, the water in the aqueous phase was discarded, and the ethyl acetate phase was separated. did. This step is repeated three times, and the desired (T-2)
-W-3) The salt-containing ethyl acetate solution (QA) was obtained. [Preparation of emulsion] Cyan coloring coupler (ExC-1)
16.0 g and 13.6 g of the color-forming reducing agent (I-16) were mixed with 52 g of a solvent (Solv-4) and the above (T-2W-).
3) Dissolve in 93 cc of a salt-containing ethyl acetate solution (QA), and dissolve this solution in a 15% aqueous gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid.
Emulsion A was prepared by emulsifying and dispersing to 0 cc.

Separately, silver chlorobromide emulsion A (cubic, average grain size 0.18 μm, silver bromide 25 mol%) was prepared.
This emulsion contains red-sensitive sensitizing dyes A-1 and A-2. The chemical ripening of this emulsion was optimally performed 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 first layer coating solution having the following composition. Preparation of Second Layer-Seventh Layer Coating Solution The second layer-seventh layer coating solution was prepared in the same manner as the first layer coating solution. The coating solution for each of the above-mentioned layers was applied on a support to prepare a sample (100) of a photosensitive material having the following layer constitution. 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener for each of the above layers. Further, the total amount each layer Cpd-4 and Cpd-5, respectively, was added such that 25.0 mg / m ² and 50 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0133]

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[0134]

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Further, 1- (5-methylureidophenyl) was added to the red-sensitive emulsion layer, green-sensitive emulsion layer and blue-sensitive emulsion layer.
-5-mercaptotetrazole was added in an amount of 3.0 × 10 ^-4 mol, 2.0 × 10 ^-4 mol, and 8.0 × 10 ^-4 mol per mol of silver halide, respectively. With respect to the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 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. To prevent irradiation, the following dyes were added to the emulsion layer (the values in parentheses indicate the coating amount).

[0136]

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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.

[0138]

[Table 3]

[0139]

[Table 4]

[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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Incidentally, an auxiliary developing agent (ETA-6) was added to the intermediate layer of the second layer and the fourth layer in a state of solid dispersion of fine particles, respectively, at 1.4 × 10 ^-4 mol per 1 m ² . A comparative sample (101) identical to the sample (100) was prepared except that the quaternary ammonium salt (T-2 · W-3) was excluded from the blue-sensitive emulsion, the green-sensitive emulsion, and the red-sensitive emulsion. .
Similarly, a sample (E) was prepared except that an equimolar amount of tetraoctyl ammonium chloride (T-2.Cl) having an inorganic anion was added instead of (T-2.W-3) of the emulsion of each color-sensitive layer. A comparative sample (102) exactly the same as (100) was produced. Similarly, the comparative sample (1) was identical to the sample (100) except that an equimolar amount of water-soluble tetrabutylammonium chloride was added instead of (T-2 · W-3).
03). After cutting each of the samples prepared as described above, a sensitometer (manufactured by Fuji Photo Film Co., Ltd., type FW, color temperature of light source 3200 ° K) was used for each sample, and a three-color separation filter for sensitometry was used. Tone exposure was provided. The exposed samples were processed using the following processing steps and processing solution compositions.

Processing Step Temperature Replenishment amount Time Tank capacity (liter) Development 40 ° C. 30 ml 15 seconds 1.0 Bleaching and fixing 40 ° C. 30 ml 15 seconds 1.0 rinse 30 ° C. 3 seconds 0.3 rinse 30 ° C. −−− 3 seconds 0.3 rinse 30 ° C. 3 seconds 0.3 rinse 30 ° C. 3 seconds 0.3 rinse 30 ° C. 60 ml 5 seconds 0.3 dry to 80 ° C. 10 seconds (replenishment amount is 1 m ² of photosensitive material. (The amount per contact is shown.)

In the above treatment, the rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for treatment. In addition,
In order to reduce the crossover time between the rinses, a blade was installed between the tanks and passed between them.

For the development, the following activator solution was used. Activator liquid Tank liquid Water 800 ml Potassium hydroxide 14 g Benzotriazole 0.02 g Potassium chloride 2.5 g Hydroxyethylidene-1,1-diphosphonic acid 4 ml (30% solution) Add water 1 liter pH 13.0 Replenisher is tank The same liquid as the liquid was used.

Bleach-fixing solution Tank solution Replenisher Water 600 ml 150 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml Ammonium sulfite monohydrate 40 g 40 g Ammonium iron (III) ethylenediaminetetraacetate 77 g 154 g 5 g ethylenediaminetetraacetic acid 5 g 10 g Ammonium bromide 10 g 20 g Acetic acid (50%) 70 ml 140 ml 1 liter by adding water pH 5.5 5.0 rinse solution tap water

The yellow after processing under each condition,
M, magenta and cyan image densities B corresponding to each dye,
The measurement was performed through G and R filters, and the minimum density (Dmin) and maximum density (Dmax) were measured and the sensitivity was calculated. The sensitivity was shown as a relative sensitivity when the sample (101) was set to 100. Next, each of the prepared samples after treatment was stored at 80 ° C. in a thermo-hygrostat set at 70% for 4 days, and the same measurement as above was performed. ΔDmin and ΔDmax values were calculated by subtracting the density before storage (D ^f ) from the density after storage (D ^s ). ΔDmin = D ^s min over ^{D f min ΔDmax = D s max} -D f max then each was produced processed samples xenon light (10
, And the concentration after one day of irradiation was measured, and ΔDmax (light) was calculated in the same manner as described above. Next, each of the prepared samples after the treatment was immersed in a 1% acetic acid solution for 1 minute, and then dried. The concentrations of these samples were measured, and ΔDma
x (acid) was calculated. Table 5 shows the results.

[0151]

[Table 5]

As a result, in Comparative Sample (101), ΔD
The values of max and ΔDmax (light) both increased, and the image storability was poor. Further, the hue of the image when immersed in an acetic acid solution changed, and ΔDmax (acid) decreased. In Comparative Sample (102), the image storability and hue stability were greatly improved, but the Dmax after processing was low and the sensitivity was lowered. In Comparative Sample (103), the degree of improvement was small in both image preservability and hue stability, and the sensitivity was lowered.
On the other hand, it was revealed that the sample (100) using the non-diffusible quaternary ammonium salt of the present invention was excellent in both image storability and hue stability without lowering the Dmax and sensitivity of the processed image. .

Example 2 The quaternary ammonium salt of the sample (100) of Example 1 was converted to (T-2 · W-6), (T-2 · W-9), (T-2 · W-9).
W-11), (T-3 / W-3), (T-10 / W-)
3) or (T-14.W-3) in exactly the same manner except that the corresponding sample (20) was used.
0), (201), (202), (203), (20)
4) and (205) were produced. The same processing as in Example 1 was performed, and the same evaluation was performed. Table 6 shows the results. Dmax and Dmin similar to Sample (100) were shown.

[0154]

[Table 6]

As a result, as in the case of the non-diffusible quaternary ammonium salt of Example 1, there was no decrease in sensitivity, excellent hue stability, and an image having a high maximum density even after each image was stored. Was.

Example 3 The RL color-forming reducing agent of the sample (100) of Example 1 was replaced with (I
-1), (I-17), (I-23), (I-24),
The corresponding samples (30-30) were prepared in exactly the same manner except that (I-61) and (I-72) were used in equimolar amounts.
0), (301), (302), (303), (30)
4) and (305) were produced. In addition, samples from which the (T-2 · W-3) compound was removed from each sample were also prepared. The same processing as in Example 1 was performed, and the same evaluation was performed. Images with high Dmax and low Dmin, respectively, were obtained. Table 7 shows the results.

[0157]

[Table 7]

As a result, when the non-diffusible quaternary ammonium salt of the present invention was used in the same manner as in the color-forming reducing agent of Example 1, the hue stability and the image storability were excellent. In particular, when a carbamoylhydrazine compound was used as the color-forming reducing agent, an image having a small ΔDmin and a small color stain on a white background after image storage was obtained. (T-2
-In each sample containing W-3), the image quality after storage was remarkably improved without lowering the sensitivity as compared with the sample not containing W-3).

Example 4 (Preparation of photosensitive material) A fluorescent whitening agent (I) was added to the polyethylene layer.
And (II), and a white pigment (including TiO ₂ , 15% by weight) and a bluish dye (including ultramarine blue), except that the multilayered color photographic paper having the following layer constitution was formed on the same support as in Example 1. Was prepared. This is designated as sample (400).

The coating solution was prepared as follows. Preparation of First Layer Cloth Solution 19.1 g of yellow color-forming coupler (ExY-2) and 10.6 g of color-forming reducing agent (I-32) are mixed with a solvent (Solv-
4) Dissolve in 93 cc of ethyl acetate solution containing 52 g and (T-2.W-3) salt, and dissolve this solution in 15% sodium dodecylbenzenesulfonate and citric acid.
Emulsion D
Was prepared.

On the other hand, silver chlorobromide emulsion D (cubic, 3: 7 mixture of a large-size emulsion having an average grain size of 0.88 μm and a small-size emulsion having an average grain size of 0.70 μm (silver molar ratio); coefficient of variation of grain size distribution) Prepared 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide in each size emulsion was locally contained in a part of the surface of a grain having silver chloride as a base material). In this emulsion, blue-sensitive sensitizing dyes-1, 2 and 3 shown below were composed of silver 1
1.4 × 1 each for large size emulsions per mole
^0-4 moles, and for small size emulsions, 1.
7 × 10 ^-4 mol is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion D and this silver chlorobromide emulsion D were mixed and dissolved to prepare a first layer coating solution.

[0162]

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Coating solutions for the third layer and the fifth layer were prepared in the same manner as the coating solution for the first layer by the following method. That is, silver chlorobromide emulsion E for the third layer (cubic, 1: 4 mixture of large size emulsion having an average grain size of 0.50 μm and small size emulsion of 0.41 μm (silver molar ratio), fluctuation of grain size distribution). Coefficients were 0.09 and 0.11, respectively, and silver bromide of each size emulsion was 0.8.
Mol% was partially contained on the surface of the silver chloride-based grain). This emulsion contains the following green-sensitive sensitizing dye-1 per mol of silver: 3.0 × 10 ^-4 mol for a large-sized emulsion and 3.6 for a small-sized emulsion.
× 10 ⁻⁴ mol, and green-sensitizing sensitizing dye-2 per mol of silver, 4.0 × 10 ⁻⁵ mol for large-size emulsion, and 7.0 × 10 ⁻⁵ for small-size emulsion. Mole is added. Further, 2.0 × 10 ^-4 mol of green-sensitive sensitizing dye-3 was added per mol of silver, and 2.8 × 10 ^-4 mol was added per mol of silver. I have. Emulsion E containing magenta coloring coupler (ExM-2) prepared in the same manner as silver chlorobromide emulsion E and emulsion D
Were mixed and dissolved to prepare a third layer coating solution.

[0164]

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Silver chlorobromide emulsion F for the fifth layer (cubic, 1: 4 mixture (larger silver ratio) of a large-sized emulsion having an average grain size of 0.50 μm and a small-sized emulsion having a mean grain size of 0.41 μm, silver molar ratio). Coefficients of variation were 0.09 and 0.11, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the surface of silver chloride-based grains in each size emulsion). This emulsion contains the following red-sensitive sensitizing dye-1 per mol of silver, 5.0 × 10 ⁻⁵ mol for a large-sized emulsion and 6.0 × 10 ⁻⁵ mol for a small-sized emulsion. Moles of red-sensitizing sensitizing dye-2 per mole of silver, 5.0 × 10 ⁻⁵ moles for large-size emulsions and 6.0 for small-size emulsions.
× 10 ^-5 mol is added.

[0166]

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Further, the same A-2 compound as used in Example 1 was added to the fifth layer at 2.6 × 10 ^-3 mol per mol of silver. This silver chlorobromide emulsion F and an emulsion F containing a cyan coloring coupler (ExC-2) prepared in the same manner as the emulsion D were mixed and dissolved to prepare a fifth layer coating solution.

[0168]

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The second layer, the sixth layer and the seventh layer were also prepared so as to have the compositions described later. An auxiliary developing agent (ETA-6) was added to the intermediate layer of the second layer and the fourth layer in an amount of 1.4 × 10 ⁻⁴ mol in a state of fine particle solid dispersion. The same compounds as in Example 1 were used as the solvent, color image stabilizer, ultraviolet absorber, color mixture inhibitor, surfactant and the like. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s
-Triazine sodium salt was used. In addition, Cp is added to each layer.
The total amount of each of d-4 and Cpd-5 was 25 mg / m ^2.
And 50 mg / m ² .

The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ^-5 mol, 9.0 × 10 ^-4 mol per mol,
2.5 × 10 ^-4 mol was added. Further, 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. The same dye as that of the sample (100) of Example 1 was added to the emulsion layer to prevent irradiation. (Layer Structure) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). It represents the amount of silver halide emulsion and silver equivalent.

[0171]

[Table 8]

[0172]

[Table 9]

Next, a non-diffusible quaternary ammonium salt (T-type emulsion) in the blue-sensitive emulsion, the green-sensitive emulsion and the red-sensitive emulsion is used.
A comparative sample (401) was produced in exactly the same manner as the sample (400) except that 2.W-3) was removed. (T-2 ・ W-
A completely similar comparative sample (402) was prepared except that tetraoctylammonium chloride (T-2 · Cl) was added instead of 3). Similarly, (T-2 ・ W-3)
A comparative sample (403) was prepared by adding an equimolar amount of water-soluble tetotabutylammonium chloride instead of.
After cutting each of the samples prepared as described above, a sensitometer (manufactured by Fuji Photo Film Co., Ltd., type FW, color temperature of light source 3200 ° K) was used for each sample, and a three-color separation filter for sensitometry was used. Tone exposure was provided. The exposed samples were processed using the following processing steps and processing solution compositions. Processing process Temperature Time Current image 40 ° C for 30 seconds Bleaching and fixing 40 ° C for 15 seconds Stabilization 30 ° C for 10 seconds Drying 80 ° C for 10 seconds

Developing solution-2 (Alkali activating bath) Tank liquid Water 800 ml 5-sodium sulfosalicylate 29 g UVX (structure below) 5 g Potassium chloride 10 g Hydroxyethylidene-1,1-diphosphonic acid (30% solution) 4 ml Water was added. 1 liter pH 12.2

[0175]

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As the bleach-fix solution, the same tank solution as in Example 1 was used. Stabilizing solution water 900 ml citric acid 4.2 g hydroxyethylidene-1,1-diphosphonic acid (30% solution) 1.0 ml 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g Liters pH 6.0 The same evaluation as in Example 1 was performed. The results are shown in Table 10.

[0177]

[Table 10]

As a result, when the compound (T-2 · W-3) was used, Dmax and sensitivity were not reduced.
It was found that hue stability and image storability were greatly improved, and a high-quality image was maintained.

Example 5 The reducing agent for color development of BL of the sample (400) of Example 4 was replaced with (I
-27), (I-29), (I-31), (I-3
9), (I-40) and (I-67), except that they were used in equimolar amounts.
0), (501), (502), (503), (50)
4) and (505) were produced. In addition, samples from which the (T-2 · W-3) compound was removed from each sample were also prepared. The same processing as in Example 4 was performed, and the same evaluation was performed. Table 11 shows the results.

[0180]

[Table 11]

As a result, when the (T-2 · W-3) compound of the present invention was used in the same manner as in the color-forming reducing agent of Example 4, ΔD
An image having a small min and a small coloring stain after storing the image was obtained.

Example 6 The first layer, the third layer and the fifth layer of the sample (100) of Example 1 were coated with silver at 0.01 g / m ^{2 and} 0.1 g / m ² respectively.
A sample (600) having exactly the same components except that the amounts were 01 g and 0.015 g was prepared. This sample was exposed to light in the same manner as in Example 1, and then treated with an intensifying solution of a 0.3% aqueous solution of hydrogen peroxide at pH 12.0 in which hydrogen peroxide was added to the developer 2 of Example 4. A clear image having a high maximum density similar to that of Example 1 was obtained even when a photosensitive material having a significantly reduced silver content was used. Further, the hue stability of the image was good, and an image having a high density was obtained even after storage. It has been found that the light-sensitive material of the present invention is also preferable for amplified image formation by intensifying processing of a low silver light-sensitive material.

Example 7 Using the sample (400) of Example 4, the same processing and evaluation as in Example 4 were performed except that the following exposure was performed. (Exposure) A YAG solid laser (oscillation wavelength, 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as an excitation light source as a light source is SHG of KNb03.
A YVO ₄ solid-state laser (oscillation wavelength, 108.7 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.7 nm) as an excitation light source, having a wavelength of 473 nm, which has been taken out by wavelength conversion by a crystal.
532 nm, AlGaInP (oscillation wavelength, about 6 nm)
70 nm: Toshiba type No. TOLD9211) was used. Each of the laser beams is a device capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to a scanning direction by a rotating polyhedron. Using this apparatus, the relationship between the density (D) of the photosensitive material and the light amount (E) D-log E was obtained by changing the light amount. At this time, the amount of the laser light of three wavelengths was modulated using an external modulator to control the exposure amount. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ^−8.
Seconds. The temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress fluctuations in light quantity due to temperature.

As a result, even in an image formed by digital exposure with high illuminance, an image having a high maximum density and good hue stability was obtained. Further, even after storage, deterioration of the image was small, and an image of high density was obtained.

[0185]

The photosensitive material containing the color-forming reducing agent, the coupler and the non-diffusible quaternary ammonium salt of the present invention is treated with an alkaline bath to have a low minimum density, a high color density and a high hue stability. And a clear image can be obtained. Even when the image is stored for a long period of time, an image having improved color image fastness can be obtained.

Claims (8)

[Claims] 1. A silver halide light-sensitive material having a photographic layer containing at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of a dye-forming coupler and The following general formula (I)
Silver halide color photographic light-sensitive material comprising a co-emulsion with at least one color-forming reducing agent represented by formula (I) and a non-diffusible quaternary ammonium salt having an anionic organic compound as a counter ion. material. General formula (I) In the general formula (I), R ¹¹ is an aryl group or a heterocyclic group, and R ¹² is an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X is -SO
_{2 -, - CO -, -} COCO-, -CO-O -, - C
^{O-N (R 13) -} , - COCO-O -, - COCO-N
(R ¹³ ) — or —SO ₂ —N (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² . 2. The silver halide color photographic material according to claim 1, wherein the compound represented by the general formula (I) is represented by the general formula (II) or (III). Formula (II), Formula (III) In the formula, Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group,
Z ² represents a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and X ¹ , X ² , X
³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However,
Hammett's substituent constant σp value of X ¹ , X ³ and X ⁵ and X
² , the sum of Hammett's substituent constant σm values of X ⁴ is 0.80
Not less than 3.80. R ³ represents a heterocyclic group. 3. The silver halide color photograph according to claim 2, wherein the compound represented by formula (II) or (III) is represented by formula (IV) or (V), respectively. Photosensitive material. General formula (IV), General formula (V) In the formula, R ¹ and R ² represent a hydrogen atom or a substituent;
¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. Where Hammett's substituent constant σ of X ¹ , X ³ and X ⁵
The sum of the p value and the Hammett substituent constant σm of X ² and X ⁴ is 0.
It is 80 or more and 3.80 or less. R ³ represents a heterocyclic group. 4. The silver halide color photograph according to claim 3, wherein the compound represented by formula (IV) or (V) is represented by formula (VI) or (VII), respectively. Photosensitive material. Formulas (VI) and (VII) In the formula, R ⁴ and R ⁵ represent a hydrogen atom or a substituent;
⁶ , X ⁷ , X ⁸ , X ⁹ , and X ¹⁰ are a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, and a halogen. Represents an atom, an acyloxy group, an acylthio group or a heterocyclic group. However, the Hammett's substituent constant σp value of X ⁶ , X ⁸ , and X ^{10 and} the Hammett's substituent constant σm of X ⁷ , X ⁹
The sum of the values is not less than 1.20 and not more than 3.80. Q ¹ is C
Together with a non-metallic atomic group necessary to form a nitrogen-containing 5- to 8-membered heterocyclic ring. 5. The silver halide color photograph according to claim 1, wherein the quaternary ammonium salt having an anionic organic compound is represented by the following general formula (Q): Photosensitive material. General formula (Q) In the formula, n is 1 or 2. When n = 2, A is alkylene, arylene, alkenylene, —O—, —SO ₂
-, - SO -, - C (= O) -, - N (-R 15) - [R
₁₅ represents a hydrogen atom, an alkyl group or an aryl group] alone or in combination. When n = 1, A is the same as R ₁₁ , R ₁₂ and R ₁₃ and represents a substituted or unsubstituted alkyl group, aryl group or polymer chain, respectively. R ₁₁ , R ₁₂ and R ₁₃ may be linked to form a ring structure. R ₁₄ represents a substituted or unsubstituted alkyl group, aryl group, alkoxy group, aryloxy group or heterocyclic group. X ⁻ represents SO ₃ ⁻ and / or COO ⁻ . 6. A dye-forming coupler, a color-forming reducing agent and a quaternary ammonium salt which are dissolved in the same high-boiling solvent and dispersed in a photographic component layer as a coemulsion. Item 6. The silver halide color photographic light-sensitive material according to item 1, 2, 3, 4 or 5. 7. The method according to claim 1, wherein the total silver content of all coating layers contains 0.003 to 0.3 g / m ² of silver halide in terms of silver. 3, 4, 5
Or a silver halide color photographic light-sensitive material as described in 6 above. 8. The method of claim 1, 2, 3, 4, 5, 6, or 7.
9. An image forming method, comprising exposing the silver halide color photographic material described in 1) to a scanning exposure having an exposure time per pixel of 10 ^-8 to 10 ^-4 seconds.