JP2670880B2 - Silver halide photographic material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and particularly to a halogen containing a compound capable of making a photographically useful group available in a development processing step. The present invention relates to a silver halide photographic light-sensitive material.

(Prior Art) Conventionally, a group of compounds capable of releasing a photographically useful group via an oxidation-reduction reaction is known.

Recent examples include JP-A-61-213847 and JP-A-61-27847.
No. 8852 and the compounds described in US Pat. No. 4,684,604.

The compounds known so far as described in the above patents are used for various purposes depending on the type of each photographically useful group.

For example, in the field of silver halide photographic materials for photoengraving, in this field, the variety of printed matter,
In order to cope with the complexity, there is a demand for a photographic light-sensitive material having good original reproducibility, a stable processing solution, or a simple replenishment.

Particularly in the line drawing photographing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, originals contain images having different densities and line widths, and there is a strong demand for a plate-making camera, a photographic material, or an image forming method for finishing these originals with good reproducibility. On the other hand, in plate making of catalogs and large posters, enlargement (graining) or reduction (shrinking) of a halftone picture is widely performed, and in plate making using enlarged halftone dots, the number of lines becomes coarse and blurred points become blurred. Shooting. In the reduction, the number of lines / inch is larger than that of the original, and a thin point is photographed. Accordingly, there is a demand for an image forming method having a wider latitude in order to maintain the reproducibility of halftone.

A halogen lamp or a xenon lamp is used as a light source of a plate making camera. In order to obtain a photographic sensitivity with respect to these light sources, a photographic light-sensitive material is usually subjected to orthosensitization. However, it has been found that the ortho-sensitized photographic material is more strongly affected by the chromatic aberration of the lens, so that the image quality is liable to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

The lith-type silver halide photographic material composed of silver chlorobromide (with a silver chloride content of at least 50%) has a very low effective concentration of sulfite ions (usually 0.1 mol / or less). There is known a method of obtaining a line image or a halftone image having a high contrast and a high blackening density in which an image area and a non-image area are clearly distinguished by processing with a hydroquinone developer. However, in this method, since the concentration of sulfurous acid in the developer is low, development is extremely unstable against air oxidation, and various efforts and efforts have been made to keep the solution activity stable. Was extremely slow, and the work efficiency was reduced at present.

For this reason, an image forming system that eliminates instability of image formation by the above-described developing method (lith developing system), develops with a processing solution having good storage stability, and obtains ultra-high contrast photographic characteristics is provided. U.S. Pat. Nos. 4,166,742, 4,168,977, 4,221,857,
4,224,401, 4,243,739, 4,272,606, 4,31
As shown in No. 1,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound has been added contains 0.15 mol / or more of a sulfite preservative at pH 11.0 to 12.3 and has good storage stability. Is treated with a developer having
Systems have been proposed for forming over 10 ultra-high contrast negative images. This new image forming system can use only silver chlorobromide having a high silver chloride content in conventional ultra-high contrast image formation, but can also use silver iodobromide and silver chloroiodobromide. There is.

Although the above-mentioned image system shows excellent performance in terms of sharp halftone dot quality, processing stability quickness and original reproducibility, a system with improved original reproducibility to cope with the recent variety of printed matter. Is desired.

Attempts to improve image quality include, for example, JP-A-61-2138.
There is known a method of releasing a development inhibitor from a redox compound having a carbonyl group as disclosed in JP-A-47-47, etc. like a silver image. However, even when these compounds are used, the halftone gradation is insufficiently elongated.

Therefore, there has been a demand for development of a photosensitive material which forms a hard halftone dot image using a stable developer and has a wide tone control of the image.

On the other hand, in the work of plate collecting and reversing processes, work efficiency has been improved by working in a brighter environment, and therefore, it is necessary to work in an environment that can be substantially called a bright room The development of photosensitive materials for plate making and the development of exposure printers have been promoted.

The light-sensitive material for a bright room described in the present patent is a light-sensitive material which does not contain an ultraviolet light component and has a wavelength of substantially not less than 400 nm and which can be safely used as safe light for a long time.

The light-sensitive room light-sensitive material used in the plate-collecting and reversing processes is a film-developed film on which characters or halftone images are formed. A photosensitive material used to perform positive image conversion or positive image / positive image conversion. A halftone image / line image and character image are converted to a negative image / positive image according to their halftone dot area, line width and character image width, respectively. It is required to have image conversion performance. It is required to have the capability of adjusting the tone of a halftone dot image and the line width of a character line image.

However, in the advanced image conversion work of character extraction image formation by repetition, the conventional method using the light room reversing process using the light-sensitive material for the bright room uses the conventional dark room reversing process using the dark room reversing photosensitive material. Compared with the method, there is a disadvantage that the quality of the character-extracted image is deteriorated.

A more detailed description of the method of forming a character-extracted image by overlapping is as shown in FIG. 1, where a transparent or translucent pasting base (a) and (c) is used.
(A polyethylene terephthalate film having a thickness of about 100 μm is usually used) and a film on which a character or line image is formed (line drawing manuscript) (b)
And a film on which a dot image is formed (dot document)
(D) is superimposed on the original,
The exposure is performed by bringing the emulsion surface of the return photosensitive material (e) into close contact with the halftone dot document (d).

A post-exposure development process is performed to form a white part of a line image in a halftone dot image.

An important point in such a method for forming a character-extracted image is that the negative image / positive image conversion is ideally performed in accordance with the halftone dot area and the line width of each of the halftone original and the line drawing original. However, as clearly shown in FIG. 1, the halftone original is exposed in direct contact with the emulsion surface of the return photosensitive material, whereas the line drawing original is attached with the base (c) and the halftone original (d). ) Is exposed to the return photosensitive material via the middle.

Therefore, if an exposure amount for faithfully converting a halftone dot document into a negative image / positive image is given, the line image document becomes out-of-focus exposure via the spacer by the pasting base (c) and the halftone document (d). The width of the image in the white part of the image becomes narrow. This is the cause of the deterioration of the quality of the extracted character image.

In order to solve the above problems, systems using hydrazine are disclosed in JP-A-62-80640, JP-A-62-235938 and JP-A-62-235938.
No. 939, No. 63-104046, No. 63-103235, No. 63-29603
Nos. 1, 63-314541 and 64-13545, but they are not sufficient and further improvement is desired.

In color photographic light-sensitive materials, sharpness is improved,
Redox compounds that release a development inhibitor for the purpose of improving graininess and color reproducibility exhibit effective performance.
However, in recent years, conventional compounds have been unsatisfactory in improving the photographic properties of higher and wider variety, and further improvements are desired.

In other words, it is unavoidable that recently developed high-sensitivity color photographic light-sensitive materials sacrifice some sharpness and graininess in order to increase sensitivity. Also,
At present, disc-size films are inferior in graininess and sharpness due to the large magnification at the time of printing.

Further, there is a demand for a material capable of improving sharpness in a black-and-white photographic light-sensitive material for X-ray.

(Object of the Invention) Accordingly, an object of the present invention is to provide a photographic light-sensitive material which is excellent in image quality such as sharpness, granularity, resolution, color reproducibility and has a wide exposure latitude or high sensitivity.

In particular, in the field of silver halide photographic materials for photoengraving, the exposure latitude by line drawing is wide, and a photographic light-sensitive material having a super-high contrast (especially γ value of 10 or more) and high resolution is provided, or in halftone dot photography. It is a main object of the present invention to provide a super-high-contrast photographic light-sensitive material having a wide exposure latitude, a high density, a clear halftone dot contour and a uniform halftone dot quality.

(Constitution of Invention) Various objects of the present invention have been achieved by a silver halide photographic light-sensitive material characterized by containing a compound represented by the following general formula (1).

General formula (1) In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group, and Z represents a primitive group necessary for forming a nitrogen-containing heteroaromatic ring.

In addition, in the general formula (1) The nitrogen-containing heteroaromatic ring group represented by or the substituent on the nitrogen-containing heteroaromatic ring group is further substituted with one or more nitro groups.

Further, R in the general formula (1) is (Wherein R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and Y represents —SO ₂ — or —Y′—SO ₂ — or And Y ′ is —O— or —NH— or Is).

The compound represented by formula (1) will be described in more detail below.

In the general formula (1), the aliphatic group represented by R is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocyclic group for R is N, O, or S
It is a 3-10 membered saturated or unsaturated heterocycle containing at least one of the atoms, which may be a single ring or may form a condensed ring with another aromatic or heterocycle. . The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, for example, a pyridine group,
Those containing an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinonelinyl group, a thiazoline group or a benzthiazolyl group are preferable.

 Preferred as R is an aromatic group.

R may be substituted with a substituent. Examples of the substituent include, for example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group. Group, hydroxy group, halogen atom,
In addition to a cyano group, a sulfo group, a carboxyl group, an alkyl and aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a nitro group, an alkylthio group, an arylthio group, a group represented by the following general formula (3) Can be mentioned.

General formula (3) In formula (3), Y is , (Wherein R ₃ represents an alkoxy group or an aryloxy group), L is a single bond, —O—, —S—, or (In the formula, R ₄ represents a hydrogen atom, an aliphatic group, or an aromatic group.)
Represents

However, -L-Y-N (R 2) - is _{-O-SO 2 N (R 2} ) -,
-OP (= O) (- R 3) N (R 2) -, - N (R 4) SO 2 N
Except when (R ₂ )-, -N (R ₄ ) P (= O) (-R ₃ ) N (R ₂ )-.

R ₁ and R ₂ represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group, and may be the same or different, or may be bonded to each other to form a ring.

R may contain one or more groups represented by the general formula (3).

In the general formula (3), the aliphatic group represented by R ₁ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group, such as a phenyl group and a naphthyl group.

The heterocycle represented by R ₁ is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocyclic ring is preferably a 5- to 6-membered aromatic heterocyclic group, for example, a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thizonyl group,
Those containing a benzthiazolyl group are preferred.

R ₁ may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted.

For example, alkyl, aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, acylamino, sulfonylamino, ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio Group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group or carboxyl group, alkyl and aryloxycarbonyl group, acyl group,
Examples thereof include an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamido group, a nitro group, an alkylthio group, and an arylthio group.

When possible, these groups may be linked to each other to form a ring.

The aliphatic group represented by R ₂ in the general formula (3) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R ₂ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group.

R ₂ may be substituted with a substituent. Examples of the substituent include those enumerated as the substituents of R ₁ in the general formula (3).

If possible, R ₁ and R ₂ may be linked to each other to form a ring.

R ₂ is more preferably a hydrogen atom.

As Y in the general formula (3), —SO ₂ — is particularly preferable, and L is a single bond and Is preferred.

The aliphatic group represented by R ₄ in the general formula (3) is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R ₄ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group.

R ₄ may be substituted with a substituent. Examples of the substituent include those enumerated as the substituents of R ₁ in the general formula (3).

R ₄ is more preferably a hydrogen atom.

Further, R may have a group containing a group promoting adsorption to silver halide as a substituent.

The adsorption-promoting group on silver halide that can be substituted for R is X
It can be represented by L' _t , X is an adsorption promoting group to silver halide, and L'is a divalent linking group. t is 0 or 1.

Preferred examples of the adsorption-promoting group represented by X on the silver halide include a thioamide group, a mercapto group, a group having a disulphide bond and a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by X is A divalent group represented by amino-, which may be a part of the ring structure or an acyclic thioamide group. Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
030,925, 4,031,127, 4,080,207, 4,245,0
No. 37, 4,255,511, 4,266,013, and 4,276,36
No. 4, and "Research Disclosure (Resea
rch Disclosure) Vol. 151 No. 15162 (November 1976),
And those disclosed in Vol. 176, No. 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, a thioureido group, a thiourethane group, a dithiocarbamate group, and a specific example of the cyclic thioamide group.
For example, 4-thiazoline-2-thione-4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4
-Triazoline-3-thione, 1,3,4-thiodiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione and benzothiazoline- 2-thione and the like can be mentioned, which may be further substituted.

The mercapto group of X is an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the --SH group is bonded is a nitrogen atom next to it, a cyclic thioamide group having a tautomer relationship with this) And specific examples of this group are the same as those listed above).

The 5- to 6-membered nitrogen-containing heterocyclic group represented by X is composed of a combination of nitrogen, oxygen, sulfur and carbon.
And a 6- to 6-membered nitrogen-containing heterocycle. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine and the like.
These may be further substituted with a suitable substituent.

As the substituent, those mentioned as the substituent of R can be mentioned. Among those represented by X, preferred are cyclic thioamide groups (that is, mercapto-substituted nitrogen-containing heterocycles such as 2-mercaptothiadiazole group, 3-
Mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1-3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or a nitrogen-containing heterocyclic group (for example, (Benzotriazole group, benzimidazole group, indazole group, etc.)
Is the case. Further, two or more XL ′ _t groups may be substituted and may be the same or different.

The divalent linking group represented by L'includes C, N,
It is an atom or an atomic group containing at least one of S and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-,
-NH -, - N =, - CO -, - SO 2 -, it is made of a single or combination of such (optionally these groups having a substituent).

Specific examples include, for example, -CONH-, -NHCONH-, -SO
₂ NH-, -COO-, -NHCOO-, _{-CH 2 -, CH 2 2,} CH 2 3, −NHCONHCH ₂ CH ₂ CONH−, _{-CH 2 CH 2 SO 2 NH -} , - CH 2 CH 2 CONH- , and the like.

These may be further substituted with a suitable substituent. As the substituent, those mentioned as the substituent of R can be mentioned.

Further, R may contain therein a ballast group which is commonly used in a non-moving photographic additive such as a coupler.

The ballast group is an organic group giving a molecular weight sufficient to prevent the compound represented by the general formula (1) from substantially diffusing into another layer or the treatment liquid, and an alkyl group, an aryl group, a heterocyclic group, Ether group, thioether group, amide group, ureido group, urethane group, sulfonamide group,
And one or more other combinations. The ballast group is more preferably a ballast group having a substituted benzene ring, and particularly preferably a ballast group having a benzene ring substituted with a branched alkyl group.

In general formula (1) The heteroaromatic ring represented by is preferably a 5- to 6-membered ring, and may be a single ring, may be condensed with another ring, and may be substituted.

Representative examples of preferred heteroaromatic rings include, for example, pyrrole, imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, 2-thioxathiazoline, 2-oxathiazoline, 2-thio Oxoxazoline, 2-oxoxazoline, 2-thioximidazoline, 2-oximidazoline, 3-thioxa-
1,2,4-triazoline, 3-oxa-1,2,4-triazoline, 1,2-oxazoline-5-thione, 1,2-thiazoline-5-thione, 1,2-oxazoline-5-one, 1,2-thiazolin-5-one, 2-thioxa-1,3,4-thiadiazoline, 2-oxa-1,3,4-thiadiazoline, 2-thioxa-1,3,4-oxadiazoline, 2- Oxa-1,3,4
-Oxadiazoline, 2-thioxadihydropyridine,
2-oxadihydropyridine, 4-thioxadihydropyridine, 4-oxadihydropyridine, isoindole, indole, indazole, benzotriazole,
Benzimidazole, 2-thioxabenzimidazole, 2-oxabenzimidazole, benzoxazoline-2-thione, azaindenes, benzoxazoline-2-one, benzothiazoline-2-thione, benzothiazolin-2-one, carbazole, purine , Carboline, phenoxazine, phenothiazine, pyrazolopyridines at various condensed ring positions, pyrazolopyrimidines, pyrazolopyrroles, pyrazololazoles, pyrazoloimidazoles, pyrazolooxazoles, pyrazolothiazoles, pyrazolotriazoles , Imidazolopyridines,
Examples thereof include imidazolopyrimidines, imidazolopyrroles, imidazoloimidazoles, imidazolooxazoles, imidazolothiazoles and imidazolotriazoles.

More preferred heteroaromatic rings include, for example, pyrrole,
Imidazole, pyrazole, triazole, tetrazole, 2-thioxathiazoline, 2-thioxoxazoline, indole, indazole, benzimidazole,
2-thioxa-1,3,4-thiadiazoline, azaindene, 5-thioxa-tetrazoline, 2-thioxa-1,3,
There are 4-oxadiazolines, 3-thioxa-1,2,4-triazolines, pyrazolopyridines at various condensed ring positions, pyrazoloimidazoles, and the like. Particularly preferred are pyrazole, indazole, and pyrazolopyridine. It is a heteroaromatic ring containing a pyrazole skeleton.

These heterocyclic compounds may have a substituent.
As a substituent, for example, a mercapto group, a nitro group, a carboxyl group, a sulfo group, a phosphono group, a hydroxy group, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group,
Aryl group, alkoxy group, aryloxy group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, sulfamoyl group, carbamoyl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, halogen atom, cyano group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group,
Examples thereof include a phosphonamido group and the like, and are preferably substituted with one or more nitro groups.

Specific examples of the compound represented by the general formula (1) are shown below. However, the present invention is not limited to the following compounds.

The compound represented by the general formula (1) of the present invention is It can be obtained by reacting trichloromethyl chloroformate with base in the presence of a base. Was prepared by reacting with the corresponding hydrazine.

 A typical synthesis example is shown below.

(Synthesis example 1 ... Synthesis of compound 4) Trichloromethyl chloroformate (6.0 ml) was added dropwise to a mixture of 5-nitroindazole (32.6 g) and tetrahydrofuran (500 ml) over 30 minutes under ice cooling, and then triethylamine ( 28 ml) was added dropwise over 30 minutes. After returning to room temperature and stirring for 2 hours, the mixture was cooled with ice, p-tolylhydrazine hydrochloride (15.9 g) was added, and triethylamine (14 ml) was slowly added. After returning to room temperature and stirring overnight, the insoluble matter was filtered off, and the volatile matter was distilled off under reduced pressure. The desired product was obtained by purification by silica gel column chromatography. (Yield 18.7 g) The chemical structure was confirmed by nmr spectrum, ir spectrum and elemental analysis.

(Synthetic cold 2 ... Synthesis of compound 17) Concentrated hydrochloric acid (4.0 ml) was added to a mixture of methanol (100 ml) and the mixture was stirred at room temperature for 3 hours, and then volatile components were distilled off under reduced pressure.
This was reacted with carbonyl-di- (6-nitroindazole) synthesized by the same method as in Synthesis Example 1 in tetrahydrofuran in the presence of triethylamine, and then purified by column chromatography to obtain the desired product. . (Yield 6.2 g) The chemical structure was confirmed by nmr spectrum, ir spectrum and elemental analysis.

(Synthesis example 3 ... Synthesis of compound 8) Concentrated hydrochloric acid (4.0 ml) was added to a mixture of ethanol (80 ml), and the mixture was stirred at room temperature for one day and then volatile components were distilled off under reduced pressure.
DMF (100 ml) on the residue, (7.9 g, synthesized by reacting p-nitrophenyl chlorocarbonate with 6-nitroindazole in the presence of DBU) and triethylamine (3.4 ml), and the mixture was stirred overnight in a nitrogen atmosphere. Pour into 1N hydrochloric acid, extract with ethyl acetate, dry,
After concentration, the target product was obtained by purifying by silica gel column chromatography. (Yield 8.4g) Chemical structure is nm
It was confirmed by r spectrum, ir spectrum and elemental analysis.

In order to incorporate the compound of the present invention into a photographic emulsion layer or a hydrophilic colloid layer, the compound of the present invention is dissolved in water or a water-miscible organic solvent (if necessary, alkali hydroxide or trihydric acid). May be dissolved by adding a secondary amine to form a salt), a hydrophilic colloid solution (for example, a silver halide emulsion,
The pH may be adjusted by adding an acid or an alkali, if necessary.

The compounds of the present invention may be used alone or in combination of two or more. The addition amount of the compound of the present invention is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, per 1 mol of silver halide. An appropriate value can be selected according to the properties of the silver halide emulsion.

The compound of the present invention is preferably used in combination with a hydrazine derivative represented by the following general formula (2).

General formula (2) In the formula, R ₃₁ represents an aliphatic group or an aromatic group, R ₃₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group, and G ₁ Represents a thiocarbonyl group or an iminomethylene group, A ₁ ,
A ₂ represents a hydrogen atom or a hydrogen atom on one side and a substituted or unsubstituted alkylsulfonyl group on the other side, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (2), the aliphatic group represented by R ₃₁ preferably has 1 to 3 carbon atoms, particularly 1 to 1 carbon atoms.
20 linear, branched or cyclic alkyl groups. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. The alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

In the general formula (2), the aromatic group represented by R ₃₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring,
Among them, there are benzothiazole rings and the like, and among them, those containing a benzene ring are preferable.

Particularly preferred as R ₃₁ is an aryl group.

The aryl group or unsaturated heterocyclic group represented by R ₃₁ may be substituted, and examples of the typical substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and a ureido. Group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl Group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide group, And the like. Preferred substituents are a straight-chain, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or 2-alkyl group having 1 to 3 carbon atoms in the alkyl portion). Ring), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 20 carbon atoms) 30), a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), a phosphoric amide group (preferably having 1 to 30 carbon atoms) Things).

The alkyl group represented by R ₃₂ in the general formula (2) is preferably an alkyl group having 1 to 4 carbon atoms and includes a halogen atom, a hydroxyl group, a cyano group, a carboxy group,
Sulfo group, alkoxy group, phenyl group, alkyl or arylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group,
Sulfamoyl group, nitro group, heteroaromatic group, And the like, and these groups may be further substituted.

As the aryl group, a monocyclic or bicyclic aryl group is preferable, and for example, those containing a benzene ring. The aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, a sulfonyl group, or the like.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably a monocyclic one, and the substituent includes a halogen atom.

As the amino group, an unsubstituted amino group and a group having 1 to 10 carbon atoms
Are preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group having 1 to 10 carbon atoms or an aryloxycarbonyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Preferred among the groups represented by R ₃₂ are those wherein G ₁ is In the case of, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group, a phenylsulfonylmethyl group, etc.), an aralkyl group (for example, o
-Hydroxybenzyl group), an aryl group (for example,
Phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), and a hydrogen atom is particularly preferable.

When G ₁ is a —SO ₂ — group, R ₃₂ represents an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group), or A substituted amino group (for example, a dimethylamino group) is preferred.

When G ₁ is a —SO— group, preferred R ₃₂ is a cyanobenzyl group, a methylthiobenzyl group or the like, and G ₁ is In this case, R ₃₂ is preferably a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group, and particularly preferably a phenoxy group.

When G ₁ is an N-substituted or unsubstituted iminomethylene group,
Desirable R ₃₂ is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

The substituent for R _32, a can be applied substituents listed for R _31.

As G _{1 in the} general formula (2), Is most preferred.

Also, R ₃₂ disrupts the G ₁ -R ₃₂ moiety from the remainder molecule, -G ₁
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the —R ₃₂ moiety, and specifically, one that can be represented by the general formula (a).

In the general formula (a) -R ₃₃ -Z ₃₁ Formula, Z ₃₁ is nucleophilically attacked to _{G 1, G 1 -R 33 -Z} 31
Is a group capable of splitting a portion from the remainder molecule, R ₃₃ is one obtained by removing one hydrogen atom from R _32, Z ₃₁ is a nucleophilic attack to G _1, cyclic in G _1, R _33, Z ₃₁ The structure can be generated.

More specifically, Z ₃₁ easily undergoes a nucleophilic reaction with G ₁ when the hydrazine compound represented by the general formula (2) is oxidized to produce the following reaction intermediate: R ₃₁ —N═N—G ₁ — R ₃₃ —Z ₃₁ R ₃₁ —N═N is a group capable of splitting N group from G ₁ , and specifically includes OH, SH or NHR ₃₄ (R ₃₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₃₅ , Or --SO ₂ R ₃₅ , where R ₃₅
May represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.) or a functional group which directly reacts with G ₁ such as COOH (wherein OH, SH, NHR ₃₄ , —COOH May be temporarily protected to form these groups by hydrolysis of alkali etc.) or (Wherein R ₃₆ and R ₃₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) by reacting a nucleophile such as a hydroxyl ion or a sulfite ion with G _1.
It may be a functional group capable of reacting with.

The ring formed by G ₁ , R ₃₃ and Z ₃₁ is preferably a 5- or 6-membered ring.

Among the compounds represented by the general formula (a), preferred are the compounds represented by the general formulas (b) and (c).

General formula (b) In the formula, R _b ^{1 to} R _b ⁴ are a hydrogen atom, an alkyl group, (preferably having 1 to 12 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms), an aryl group (preferably carbon) Number 6 ~
12 items) etc., and may be the same or different. B
Is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, m and n are 0 or 1, and (n
+ M) is 1 or 2.

As the 5- or 6-membered ring formed by B, for example,
A cyclohexene ring, a cyclopentene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like.

Z ₃₁ has the same meaning as in formula (a).

General formula (c) In the formula, R _c ¹ and R _c ² represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom or the like, and may be the same or different. R _c ³ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. p represents 0 to 2. q represents 1-4. R _c ¹ , R _c ² and R _c ³ are Z ₃₁
May combine with each other to form a ring as long as they have a structure capable of intramolecular nucleophilic attack on G ₁ .

R _c ¹ and R _c ² are preferably a hydrogen atom, a halogen atom, or an alkyl group, and R _c ³ is preferably an alkyl group or an aryl group.

q preferably represents 1-3, and when q is 1, p is 1
Or 2, when q is 2, p represents 0 or 1, when q is 3, p represents 0 or 1, and when q is 2 or 3, a plurality of (CR _c ¹ R _c ² ) are the same, It may be different.

Z ₃₁ has the same meaning as in formula (a).

A ₁ and A _{2 each} represent a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably phenylsulfonyl group or phenylsulfonyl substituted such that the sum of the substituent constants of Hammett is -0.5 or more Group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more; or a straight-chain, branched or cyclic unsubstituted group; Substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group). A ₁ and A ₂ are most preferably hydrogen atoms. preferable.

R ₁ or R _{2 in} the general formula (2) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (2) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, U.S. Patent Nos. 4,385,108 and 4,459,347;
-195,233, 59-200,231, 59-201,045, 5
Nos. 9-201,046, 59-201,047, 59-201,048,
59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, Japanese Patent Application No. 62-67,508, No. 62-67,501
And the groups described in JP-A-62-67,510.

Specific examples of the compound represented by the general formula (2) are shown below. However, the present invention is not limited to the following compounds.

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item23516 (1983
November, p. 346) and references cited therein,
U.S. Pat.Nos. 4,080,207, 4,269,929, 4,276,364
No. 4,278,748, No. 4,385,108, No. 4,459,347,
4,560,638, 4,478,928, UK Patent 2,011,391B,
JP-A-60-179934, JP-A-62-270,948, JP-A-63-29,751
Nos. 61-170,733, 61-270,744, 62-948
No., EP217,310, or US 4,686,167, JP-A-62-17
No. 8,246, No. 63-32,538, No. 63-104,047, No. 63-12
Nos. 1,838, 63-129,337, 63-223,744, 63-2
Nos. 34,244, 63-234,245, 63-234,246, 63-
294,552, 63-306,438, JP-A-1-100,530,
No. 1-105,941, No. 1-105,943, JP-A-64-10,233
No., JP-A-1-90,439, Japanese Patent Application No. 63-105,682, 63
-114,118, 63-110,051, 63-114,119, 6
3-116,239, 63-147,339, 63-179,760,
63-229,163, Japanese Patent Application No. 1-18,377, 1-18,378
Nos. 1-18,379, 1-15,755, 1-16,814
Nos. 1-40,792, 1-42615, 1-42616
And those described in Nos. 1-123,693 and 1-126,284 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1.times.10.sup.- ⁶ mol to 5.times.10.sup.- ² mol, more preferably 1.times.10.sup.- ⁵ mol to 2.times.10.sup.- ⁵ mol per mol of silver halide.
A range of × 10 ^-2 mol is a preferable addition amount.

When the compound represented by the general formula (1) of the present invention is used in combination with the hydrazine derivative represented by the general formula (2) and a negative emulsion, a negative image with high contrast can be formed. On the other hand, it can be used in combination with an internal latent image type silver halide emulsion. The compound represented by the general formula (1) of the present invention is used in combination with the hydrazine derivative represented by the general formula (2) and a negative emulsion.
It is preferably used for forming a negative image with high contrast.

When used for forming negative images with high contrast,
The average grain size of the silver halide used is preferably fine grains (for example, 0.7 μm or less), particularly preferably 0.5 μm or less. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% of the weight or the number of particles is ±
It is composed of particles having a size within 40%.

Silver halide grains in photographic emulsions are cubic, octahedral, diamond
It may have a regular crystal such as a dodecahedron or a tetradecahedron, or may have an irregular crystal such as a sphere or a flat plate, or a composite form of these crystal forms. You may have one.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases.

The silver halide emulsion used in the present invention contains a cadmium salt during the formation or physical ripening of silver halide grains.
A sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, and the like may coexist.

The silver halide used in the present invention is 10 ^-8 to 1 mol per mol of silver.
It is a silver haloiodide prepared in the presence of 10 ^-5 mol of an iridium salt or a complex salt thereof and having a silver iodide content on the grain surface larger than the average silver iodide content of the grains. Use of an emulsion containing such a silver haloiodide provides photographic characteristics with higher sensitivity and higher gamma.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and rhodium may be contained. Specific examples are U.S. Patent No. 2,448,060,
It is described in, for example, British Patent No. 618,016. As a sulfur sensitizer, in addition to sulfur compounds contained in gelatin,
Various sulfur compounds, such as thiosulfates, thioureas,
Thiazoles, rhodanines and the like can be used.

In the above, it is preferable to use an iridium salt or a rhodium salt before the completion of physical ripening in the production process of the silver halide emulsion, particularly at the time of grain formation.

In the present invention, the silver halide emulsion layer is disclosed in Japanese Patent Application No. 60-6419.
No. 9 and Japanese Patent Application No. 60-232086 preferably contain two types of monodisperse emulsions having different average grain sizes from the viewpoint of increasing the maximum density (Dmax). It is preferably sensitized, and the method of chemical sensitization is most preferably sulfur sensitization. The large-size monodisperse emulsion may not be chemically sensitized, but may be chemically sensitized. Generally, large-sized monodispersed particles are not subjected to chemical sensitization because black spots are easily generated. However, when chemically sensitized, it is particularly preferable to apply the grains so shallow that black spots are not generated. Here, "shallow application" refers to shortening the time for applying chemical sensitization, lowering the temperature, or reducing the amount of chemical sensitizer added as compared with chemical sensitization of small-sized grains. The difference in sensitivity between the large-sized monodispersed emulsion and the small-sized monodispersed emulsion is not particularly limited, but ΔlogE is 0.1 to 1.0, more preferably 0.2 to 0.7, and the higher the large-sized monodispersed emulsion, the more preferable. Here, the sensitivity of each emulsion was such that a hydrazine derivative was contained and coated on a support, and sulfite ion was added at 0.15 mol / min.
It is obtained when processing is carried out using a developer having a pH of from 10.5 to 12.3 containing the above components. The average size of small size monodisperse grains is the average size of large size silver halide monodisperse grains.
It is 90% or less, preferably 80% or less. The average grain size of the silver halide emulsion grains is preferably 0.02μ ~
The average particle size of large size and small size monodisperse particles is preferably within the range of 1.0 μ to 0.5 μ, more preferably 0.1 μ to 0.5 μ.

When two or more kinds of emulsions having different sizes are used in the present invention, the silver coating amount of the small size monodispersed emulsion is preferably 40 to 90 wt%, more preferably 50 to 80 wt%, based on the total silver coating amount. is there.

In the present invention, monodisperse emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into different layers. When introduced into separate layers, it is preferred that the large size emulsion be the upper layer and the small size emulsion be the lower layer.

As the total amount of coated ^{silver, 1g / m 2 ~8g / m} 2 is preferred.

In the light-sensitive material used in the present invention, sensitizing dyes (for example, cyanine dyes, merocyanine dyes, etc.) described in JP-A-55-52050, pp. 45-53 for the purpose of increasing the sensitivity.
Can be added. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Research Disclosure).
Disclosure) Volume 176 17643 (Issued December 1978) Page 23 IV
Section J.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindene) ), Pentaazaindenes; and many other compounds known as antifoggants or stabilizers, such as benzenethiosulfonate, benzenesulfonate, benzenesulfonamide, and the like. Rukoto can. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

Examples of development accelerators suitable for use in the present invention or accelerators for developing nucleation transmission include JP-A-53-77616 and JP-A-54-77616.
7732, 53-137133, 60-140340, 60-1495
In addition to the compounds disclosed in No. 9, various compounds containing an N or S atom are effective.

The optimum amount of these accelerators varies depending on the type of the compound, but is 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^−3.
It is desirable to use it in the range of 0.1 g / m ² .

The light-sensitive material of the present invention may contain a desensitizer in the photographic emulsion layer and other hydrophilic colloid layers.

The organic desensitizer used in the present invention is defined by its polarographic half-wave potential, that is, the oxidation-reduction potential determined by polarography, and the sum of the polaro anodic potential and the cathodic potential becomes positive. A method for measuring the oxidation-reduction potential of a polarograph is described in, for example, US Pat. No. 3,501,307. The organic desensitizer preferably contains at least one water-soluble group, and specific examples thereof include a sulfonic acid group, a carboxylic acid group, and a sulfonic acid group. These groups include an organic base (eg, ammonia, pyridine , Triethylamine, piperidine, morpholine, etc.) or an alkali metal (eg, sodium, potassium, etc.).

As organic desensitizers, Japanese Patent Application No. 61-280998, p. 55-
Those represented by the general formulas (III) to (V) described on page 72 are preferably used.

The organic desensitizer in the present invention is contained in the silver halide emulsion layer.
1.0 × 10 ^{-8 to} 1.0 × 10 ^-4 mol / m ² , especially 1.0 × 10 ^{-7 to} 1.0 × 1
0 it is preferable ^{to -5} mol / m ² made present.

In the emulsion layer of the present invention, or other hydrophilic colloid layer,
A water-soluble dye may be contained as a filter dye or for various purposes such as prevention of irradiation.
As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the inherent sensitivity range of silver halide, and safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the region of 380 nm to 600 nm are used to increase the light absorption.

These dyes are added to the emulsion layer depending on the purpose,
Alternatively, it is preferable to add and fix a non-photosensitive hydrophilic colloid layer above the silver halide emulsion layer, that is, a non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with the mordant before use.

Depending on the molar extinction coefficient of the UV absorber, usually 10
^-2 is added in a range of ^{g / m 2 ~1g / m 2} . Preferably 50mg-5
00 mg / m ² .

The ultraviolet absorber can be dissolved in an appropriate solvent (eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof) and added to the coating solution.

As the ultraviolet absorber, for example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorbing polymer can be used.

Specific examples of UV absorbers are described in U.S. Pat.
3,314,794, 3,352,681, JP-A-46-2784, U.S. Pat.Nos. 3,705,805, 3,707,375, 4,045,229,
3,700,455, 3,499,762 West German Patent Application Publication 1,547,86
It is described in No. 3 etc.

Filter dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cytanine dyes and azo dyes. From the viewpoint of reducing residual color after the development, a dye which is water-soluble or decolorizes by alkali or sulfite ions is preferred.

Specifically, for example, pyrazolone oxonol dye described in U.S. Pat.No. 2,274,782, diarylazo dye described in U.S. Pat.No. 2,956,879, U.S. Pat.
No. 3,384,487, styryl dyes and butadienyl dyes, U.S. Pat.No.2,527,583, merocyanine dyes described in U.S. Pat.No. 3,486,897, U.S. Pat.No. 3,486,897, No. U.S. Pat.Nos. 3,976,661 enaminohemioxonol dyes and British Patents 584,609 and 1,17
No. 7,429, JP-A-48-85130, JP-A-49-99620, JP-A-49-1
No. 14420, U.S. Pat.Nos. 2,533,472, 3,148,187,
No. 3,177,078, No. 3,247,127, No. 3,540,887
And the dyes described in JP-A Nos. 3,575,704 and 3,653,905.

The dye is dissolved in an appropriate solvent (eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof), and the coating solution for the non-photosensitive hydrophilic colloid layer of the present invention. Is added during.

The amount of the specific dye is generally ^{10 -3 g / m 2 ~1g /} m 2,
In particular it is possible to find the preferred amount in the range of ^{10 -3 g / m 2 ~0.5g /} m 2.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts, aldehydes, (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), active vinyl compounds (1,3,
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc., an active halogen compound (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids, etc. alone Alternatively, they can be used in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained. Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. Here, when used as an antistatic agent, a surfactant containing fluorine (see US Pat. No. 4,201,586 for details)
And JP-A-60-80849 and JP-A-59-74554 are particularly preferred.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide and polymethyl methacrylate for the purpose of preventing adhesion to the photographic emulsion layer and other hydrophilic colloid layers.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, use is made of a polymer having, as a monomer component, an alkyl (meth) acrylate, an alkoxyacryl (meth) acrylate, a glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like. be able to.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid, maleic acid,
Examples thereof include polymers or copolymers having an acid monomer such as phthalic acid as a repeating unit. These compounds are disclosed in Japanese Patent Application Nos. 60-66179 and 60-68873.
No., JP-A-60-163856 and JP-A-60-195655 can be referred to. Among these compounds, particularly preferred are ascorbic acid as a low molecular compound, and a high molecular compound composed of an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It is a water-dispersible latex of a copolymer.

In order to obtain ultra-high contrast and high sensitivity photographic characteristics using the silver halide light-sensitive material of the present invention, it is necessary to use a conventional infectious developer or a highly alkaline developer close to pH 13 described in U.S. Patent No. 2,419,975. And a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / or more of sulfite ions as a preservative, and has a pH / 0.5
With a developer having a pH of from 1.0 to 12.3, particularly pH / 1.0 to 12.0, a negative image having a sufficiently high contrast can be obtained.

There is no particular limitation on the developing agent used in the developing solution used in the present invention, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl-3- Combinations of pyrazolidones or combinations of dihydroxybenzenes and P-aminophenols may be used. Developer is usually 0.05
It is preferably used in an amount of mol / .about.0.8 mol /. Dihydroxybenzenes and 1-phenyl-3-
When a combination with pyrazolidones or p-amino-phenols is used, the former is used in an amount of 0.05 mol / to 0.5 mol /.
The latter is preferably used in an amount of 0.06 mol / or less.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The sulfite is preferably at least 0.4 mol / mol, particularly preferably at least 0.5 mol / mol.

The developing solution of the present invention is disclosed in JP-A-56-2 as a silver stain inhibitor.
The compounds described in 4,347 can be used. Compounds described in Japanese Patent Application No. 60-109,743 can be used as a solubilizing agent to be added to the developer. Furthermore, compounds described in JP-A-60-93,433 or compounds described in Japanese Patent Application No. 61-28,708 can be used as a pH buffer used in the developer.

The compound represented by the general formula (I) is used in combination with a negative emulsion as described above for a high-contrast photosensitive material.
Although it can be combined with an internal latent image type silver halide emulsion, its mode is described below. In this case, the compound represented by the general formula (I) is preferably contained in the internal latent image type silver halide emulsion layer, but is contained in the hydrophilic colloid layer adjacent to the internal latent image type silver halide emulsion layer. Is also good. Such layers include colorant layers, intermediate layers, filter layers,
A layer having any function, such as a protective layer or an anti-halation layer, may be used as long as it does not prevent the nucleating agent from diffusing into the silver halide grains.

The content of the compound represented by formula (I) in the layer is such that a sufficient maximum density (for example, a silver density of 1.0 or more) is obtained when the internal latent image type emulsion is developed with a surface developer. It is desirable. In practice, the appropriate content can vary over a wide range because it depends on the characteristics of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions. About 1 mole of silver in silver emulsion
A range from 0.005 mg to 500 mg is practically useful, with about 0.01 mg to about 100 mg per mole silver being preferred. When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as described above may be contained with respect to the amount of silver contained in the same area of the internal latent image type emulsion layer. The definition of the internal latent image type silver halide emulsion is described in JP-A-61-170733, page 10, upper column and British Patent 2,089,057, pages 18-20.

Preferred internal latent image emulsions usable in the present invention are described in JP-A-61-253716, page 28, line 14 to page 31, line 2.
The preferred silver halide grains are described on page 31, line 3 to page 32, line 11 of the same specification.

In the light-sensitive material of the present invention, the internal latent image type emulsion may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by using a sensitizing dye. As sensitizing dyes,
Cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye, hemicyanine dye,
Oxonol dyes, hemioxonol dyes and the like can be used. These sensitizing dyes include, for example,
And cyanine dyes and merocyanine dyes described in JP-A Nos. 40,638, 59-40,636 and 59-38,739.

In the present invention, a developing agent such as hydroxybenzenes (for example, hydroquinones), aminophenols, and 3-pyrazolidones may be contained in the emulsion or the light-sensitive material.

The photographic emulsion used in the present invention is combined with a dye sensitizing donor compound (coloring material) for a color diffusion transfer method which releases a diffusible dye in response to the development of silver halide, and is subjected to an appropriate development treatment. Thereafter, it can be used to obtain a desired transfer image on the image receiving layer. Many color materials for such a color diffusion transfer method are known. Among them, a non-diffusible color material is initially used, but is formed by an oxidation-reduction reaction with an oxidation product of a developing agent (or an electron transfer agent). It is preferable to use a coloring material of the type that releases a diffusible dye by cleavage (hereinafter abbreviated as DRR compound). Among them, a DRR having an N-substituted sulfamoyl group
Compounds are preferred. Particularly preferred in combination with the nucleating agent of the present invention, U.S. Pat.Nos. It is a DRR compound having a redox nucleus as described in JP-A-53-149,328. When used in combination with such a DRR compound, the temperature dependence of treatment and the like is remarkably small.

After imagewise exposure using the light-sensitive material of the present invention, after or while performing fog treatment with light or a nucleating agent, a surface developer having a pH of 11.5 or less containing an aromatic primary amine-based color developing agent It is preferable to directly form a positive color image by performing color development, bleaching and fixing. The pH of this developer is
More preferably, it is in the range of 11.1 to 10.0.

The fogging treatment in the present invention includes a method of applying a second exposure to the entire surface of a photosensitive layer called a so-called "light fogging method" and a method of developing in the presence of a nucleating agent called a "chemical fogging method". Either may be used. Development processing may be performed in the presence of a nucleating agent and fog light. Also,
Fog exposure may be performed on a photosensitive material containing a nucleating agent.

The light fogging method is described in the above-mentioned Japanese Patent Application No. 61-253716, page 47, line 4 to page 49 to line 5, and regarding the nucleating agent usable in the present invention, page 49 of the same specification. Line 6 to page 67, line 2, particularly the general formulas [N-1] and [N-
Use of the compound represented by 2] is preferred. Specific examples thereof include [NI-] described on pages 56 to 58 of the same specification.
[1] to [NI-10] and [N-II-1] to [N-II-12] described on pages 63 to 66 of the same specification are preferred.

Regarding nucleation accelerators that can be used in the present invention,
It is described on page 68, line 11 to page 71, line 3, and specific examples thereof include (A-1) to (A-1) described on page 69 to page 70.
Use of 3) is preferred.

The color developing solution used in the development processing of the light-sensitive material of the present invention is described in the specification, page 71, line 4 to page 72, line 9, and is particularly useful for aromatic primary amine color developing agents. As a specific example, a p-phenylenediamine-based compound is preferable, and a typical example thereof is 3-methyl-4-amino-
N-ethyl-N- (β-methanesulfonamidoethyl)
Aniline, 3-methyl-4-amino-N-ethyl-N-
(Β-hydroxyethyl) aniline, 3-methyl-4-
Examples thereof include amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfate and hydrochloride.

In order to form a positive color image directly by the color diffusion transfer method using the photosensitive material of the present invention, a black-and-white developing agent such as a phenidone derivative can be used in addition to the above color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching treatment may be performed by one-bath bleach-fixing simultaneously with the fixing treatment, or may be performed individually. In order to further speed up the processing, a method of performing bleach-fixing after bleaching or a method of performing bleach-fixing after fixing may be used.
In the bleaching solution or the bleach-fixing solution of the present invention, an aminopolycarboxylic acid iron complex is usually used as a bleaching agent. As the additives used in the bleaching solution or the bleach-fixing solution of the present invention, various compounds described in JP-A-61-32462, pages 22 to 30, can be used. After the desilvering step (bleach fixing or fixing), processing such as washing with water and / or stabilization is performed. It is preferable to use softened water for the washing water or the stabilizing solution. Examples of the water softening treatment include a method using an ion exchange resin or a reverse osmosis device described in Japanese Patent Application No. 61-131632. As a specific method thereof, it is preferable to carry out the method described in Japanese Patent Application No. 131632/1986.

Further, as the additive used in the washing and stabilizing steps, various compounds described in Japanese Patent Application No. 61-32462, pp. 30-36 can be used.

It is preferable that the amount of replenisher in each processing step is small.
The amount of the replenisher is preferably 0.1 to 50 times, more preferably 3 to 3 times the amount of the pre-bath brought in per unit area of the photosensitive material.
It is 0 times.

When the light-sensitive material of the present invention is a color light-sensitive material, at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer is provided on the support. The number and order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748 and JP-A-59-113438.
No. 59-113440, No. 61-20037, couplers as described in the specification of JP 61-20038, DIR compounds and the like may be contained, and contains a color mixing inhibitor as usually used. You may go out.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, 62-127
As described in 200350, 62-206541, 62-206543, etc., a low-speed emulsion layer may be provided on the side remote from the support and a high-speed emulsion layer may be provided on the side near the support.

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
It can be installed in the order of GL / GH / RH / RL or in the order of BH / BL / GH / GL / RL / RH.

Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL is selected from the side farthest from the support.
Can be arranged in this order. JP-A-56-25738
As described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged,
There is an array composed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even in the case of three layers having different sensitivities, Japanese Patent Application Laid-Open No.
As described in JP-A-202464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side remote from the support.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

The arrangement may be changed as described above even in the case of four or more layers.

No. 4,663,271 to improve color reproduction
No. 4,705,744, 4,707,436, JP-A-62-16
No. 4,448,63-89850, a donor layer (CL) having a multilayer effect having a different spectral sensitivity distribution from the main photosensitive layer such as BL, GL, RL is disposed adjacent to or close to the main photosensitive layer. Is preferred.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, a preferable silver halide contained in the photographic emulsion layer is silver iodobromide, iodobromide containing about 30 mol% or less of silver iodide. It is silver chloride or silver iodochlorobromide. Particularly preferred is from about 2 mol% to about 25 mol%
Silver iodobromide or silver iodochlorobromide containing up to silver iodide.

When the photographic material of the present invention is a color photographic paper,
As the silver halide contained in the photographic emulsion layer, those composed of silver chlorobromide or silver chloride substantially free of silver iodide can be preferably used. Here, the phrase "contains substantially no silver iodide" means that the silver iodide content is 1 mol%.
Or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride emulsion can be used. Although this ratio can take a wide range depending on the purpose, the silver chloride ratio is 2 mol%.
Those described above can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used as a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%, more preferably at least 95 mol%. For the purpose of reducing the replenishment amount of the developing solution, an emulsion of substantially pure silver chloride having a silver chloride content of 98 to 99.9 mol% is also preferably used.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparatio
n and types) ”, and No. 18716 (November 1979), 64
8, Grafkid, "Physics and Chemistry of Photography," published by Paul Montell (P. Glafkides, Chemie et Phisique Photograp
hique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi).
c Emulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VLZelikman et al., Making and Coating Photo).
graphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is not exposed during imagewise exposure to obtain a dye image,
It is preferable that the silver halide fine particles are not substantially developed in the developing process and are not fogged in advance.

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably 0.5 to 10 mol% of silver iodide
It contains.

The fine grain silver halide preferably has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01 to 0.5 μm, and 0.02 to 0.2 μm.
μm is more preferred.

Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, US Pat. No. 4,411,987 and US Pat. No. 4,435,503 for preventing deterioration of photographic performance due to formaldehyde gas.
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 3,968, 4,314,023, 4,511,649, and EP 249,473A.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-35
No. 730, No. 51-118034, No. 60-185951, U.S. Pat.
Particularly preferred are those described in 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,269,000,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453A.
No. 3,446,622, U.S. Pat.No. 4,333,999, U.S. Pat.
No. 775,616, No. 4,451,599, No. 4,427,767, No.
Those described in 4.690,889, 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in No. 1,146,328 are preferable. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181 and a dye that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
It is described in 2,137 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
And those described in U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427 and the like, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-1
No. 85950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A and 313,
No. 308A, couplers for releasing dyes that recolor after release, RD Nos. 11494 and 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, U.S. Pat.No. 4,555,477
And the like, and a ligand releasing coupler described in JP-A-63-75747.
US Patent No.
Couplers that release a fluorescent dye described in 4,774,181 are exemplified.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027.

Specific examples of the high boiling point organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-tert)
-Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl- 2-butoxy-5-ter
t-octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer to form a hydrophilic polymer. It can be emulsified and dispersed in a water-soluble colloid aqueous solution.

Preferably, International Publication No.WO88 / 00723, twelfth
Homopolymers or copolymers described on pages 30 to 30 are used. In particular, use of an acrylamide-based polymer is preferred for stabilizing a color image.

In the color light-sensitive material of the present invention, JP-A-63-257747 is used.
1,2-benzisocyazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethyl described in JP-A No. 62-272248 and JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as phenol, 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 645 of No.18716
It is described in the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example,
Photographic Science and Engineering by A. Green et al. (Photogr.
Sci. Eng.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a serometer (swelling meter) of the type described below.
T _1/2 is defined as 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds.
Defined as the time to reach 2.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is
150-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ Can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
The development can be carried out by a usual method described in 17643, pp. 28-29, and No. 18716, 615 left column to right column.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphates, chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains a development inhibitor or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide,
Various preservatives such as triethanolamine and catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers , Chelating agents such as auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N , N, N, N It may be mentioned di (o-hydroxyphenylacetic acid) and salts thereof as a typical example - tetramethylene phosphonic acid, ethylenediamine.

When the reversal process is performed, color development is usually performed after black development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the photographic material, and 500 ml by reducing the bromide ion concentration in the replenishing solution.
It can also be: When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below.

That is, The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned.
The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III) such as amino diamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, iron (III) aminodiaminetetraacetate, iron (III) complex salt of 1,3-diaminopropanetetraacetate and other aminopolycarboxylic acid iron (II)
I) Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
No. 53-72623, No. 53-95630, No. 53-95631,
Nos. 53-104232, 53-124424, 53-141623,
53-28426, Research Disclosure No.17129
Having a mercapto group or a disulfide group described in JP-A No. (July 1978); thiazolidine derivatives described in JP-A-50-140129;
No. 20832, No. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, JP-A-5
8-16,235; iodide salts described in West German Patent No. 966,410;
Polyoxyethylene compounds described in 2,748,430;
Polyamine compounds described in JP-B-45-8836; and JP-A-49-40,943; JP-A-49-59,644; JP-A-53-94,927;
Compounds described in Nos. 54-35,727, 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable in view of a large accelerating effect, and in particular, US Patent No. 3,893,858
And compounds described in West German Patent No. 1,290,812 and JP-A-53-95,630. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
And acetic acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Sulfites, bisulfites, carbonyl bisulfite adducts or the sulfinic acid compounds described in EP-A-294769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids or organic sulfonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ℃ ~ 50
° C, preferably 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring,
JP-A-62-183460 describes a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material, JP-A-62-183461, a method of increasing a stirring effect by using a rotating means, A method of moving the photosensitive material while bringing the emulsion surface into contact with the provided wiper blade to make the emulsion surface turbulent to improve the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such an agitation improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improved stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in
It is preferable to have the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, calcium ion described in JP-A-62-288838,
The method of reducing magnesium ions can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry"
(1986) Mitsui Shuppan, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, metal salts described in U.S. Patent No. 3,719,492. Complex, JP-A-5
Examples thereof include urethane compounds described in 3-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and JP-A-58-144547.
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-6
It is also applicable to the photothermographic materials described in 1-238056, European Patent 210,660A2, and the like.

The compound of the present invention can be used for a photothermographic material. Regarding photothermographic materials, U.S. Pat.
No. 4,474,867, No. 4,478,927, No. 4,507,38
No. 4,500,626, 4,483,914, JP-A-58-1
49046, 58-149047, 59-152440, 59-154
No. 445, No. 59-165054, No. 59-180548, No. 59-16843
No. 9, No. 59-174832, No. 59-174833, No. 59-174834
Nos. 59-174835, 61-232451, 62-65038
No. 62-253159, No. 63-316848, No. 64-13546
And European Patent Publication Nos. 210,660A2 and 220,746A2.

The photothermographic material basically has a photosensitive silver halide, a binder, a dye-donating compound, and a reducing agent (a dye-donating substance may also serve as a reducing agent) on a support, Further, an organic silver salt and other additives can be contained as required.

The photothermographic material may give a negative image or a positive image upon exposure. The method of giving a positive image is a method using a direct positive emulsion (a method using a nucleating agent or a light fogging method) as a silver halide emulsion, and a dye that emits a positive diffusible dye image. Any of the methods using a donor compound can be adopted.

There are various methods for transferring a diffusible dye, for example, a method of transferring to a dye fixing layer with an image forming solvent such as water, a method of transferring to a dye fixing layer with a high boiling organic solvent, and a method of transferring to a dye fixing layer with a hydrophilic heat solvent. A method of transferring, a method of transferring to a dye-fixing layer having a dye-receptive polymer by utilizing thermal diffusivity or sublimability of a diffusible dye has been proposed,
Any of them may be used.

Further, as the image forming solvent, for example, there is water,
This water is not limited to so-called pure water, but includes water in a widely and customarily used sense. Also, pure water and methanol, DMF,
A mixed solvent with a low boiling point solvent such as acetone and diisobutyl ketone may be used. Further, a solution containing an image formation accelerator, an antifoggant, a development terminator, a hydrophilic heat solvent, and the like may be used.

 Hereinafter, the present invention will be further described with reference to Examples.

Example 1 (Preparation of photosensitive emulsion) 4 × 10 ⁻⁷ per mol of silver was added to an aqueous gelatin solution kept at 50 ° C.
In the presence of moles of iridium (III) potassium chloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide are added simultaneously for 60 minutes, and the pAg between them is kept at 7.8. A cubic monodispersed emulsion having an average silver iodide content of 0.3 mol% was prepared. The emulsion was desalted by flocculation, and then 40 g of inert gelatin per mole of silver was added.
5,5'-dichloro-9-ethyl- as sensitizing dye
3,3'-Bis (3-sulfopropyl) oxacarbocyanine and a KI solution of 10 ^-3 mol per mol of silver were added, and the mixture was aged for 15 minutes and then cooled.

(Coating of photosensitive emulsion layer) This emulsion was redissolved, and the following hydrazine derivative was added at 40 ° C. Furthermore, the compounds of the present invention shown in Table 1 and the compounds of Comparative Examples were added, and further 5-methylbenztriazole, 2-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene, and Polyethylene having an undercoat layer (0.5μ) made of vinylidene chloride copolymer by adding 30 wt% of polyethyl acrylate to compound (a), (b) and gelatin and the following compound (c) as a gelatin hardening agent It was coated on a terephthalate film (150 μ) so that the silver amount was 3.8 g / m ² .

(Coating of Protective Layer) As a protective layer, 1.5 g / m ^{2 of} gelatin and 0.3 g / m ² of polymethyl methacrylate particles (average particle size 2.5 μm) were coated thereon using the following surfactant.

(Evaluation of performance) These samples were subjected to an optical wedge and a contact screen (Fujifilm, 150L) with 3200 ° K tungsten light.
After exposure through a chain dot type), 34 ℃ with the next developer
It was developed for 30 seconds, fixed, washed with water and dried.

Table 1 shows the measurement results of the dot quality and the halftone of the obtained sample. The halftone was expressed by the following equation.

* Exposure that gives halftone dot area control of 95% halftone = ΔE (log E95%)-5% exposure that gives halftone dot area ratio (log E5%) evaluated. In the five-point evaluation, "5" indicates the best quality and "1" indicates the worst quality.
"5" and "4" are practically usable as halftone dots for plate making, "3" is a practically usable limit level, and "2",
"1" is a quality that cannot be used.

 The results are shown in Table 1.

As can be seen from the results in Table 1, the compounds of the present invention have remarkably wide halftones and improved halftone dot quality as compared with the comparative compounds.

Example 2 An automatic developing machine for post-exposure plate-making FG660F type (manufactured by Fuji Photo Film Co., Ltd.) in the same manner as in Example 1 except that the sample of Example 1 was used
Then, the developing machine-I of Example-1 was filled in
Developed at 30 ° C for 30 seconds, fixed, washed with water and dried.

[A] Immediately after the temperature of the developer filled in the automatic developing machine reaches 34 ° C., the developing process is performed. (Development with a fresh solution) [B] A development process is performed using a solution left for 4 days while the developer is filled in an automatic developing machine. (Development with air-fatigue solution) [C] After being filled with the developer of an automatic processor, Fuji Film GRANDEX GA-100 film is exposed with a size of 50.8 cm x 61.0 cm so that 50% of the area is developed. 20 a day
0 sheets are processed, and development processing is performed with the liquid repeated for 5 days. Replenish 100 cc of developer-I per processed sheet. (Development with a large amount of processing fatigue solution) The obtained photographic properties are shown in Table-2. It is desirable that the photographic properties obtained in [B] and [C] have no difference from the photographic properties in [A] in terms of the processing running stability. As can be seen from the results in Table 2, the use of the compound of the present invention unexpectedly improved the process running stability.

Example 3 An aqueous gelatin solution maintained at 50 ° C. was added in an amount of 5.0 × 10
^An aqueous solution of silver nitrate and an aqueous solution of sodium chloride are simultaneously mixed in the presence of ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , and after removing soluble salts by a method well known in the art, gelatin is added, followed by chemical 2-methyl-4 as a stabilizer without aging
-Hydroxy-1,3,3a, 7-tetraazaindene was added. This emulsion was a cubic monodispersed emulsion having an average grain size of 0.15 μm.

The following hydrazine compound was added to this emulsion. Further, the compounds of the present invention shown in Table 3 were added to the mixture, and polyethyl acrylate latex was added to gelatin in a solid content of 30 wt.
%, And as a hardening agent, 1,3-vinylsulfonyl-2
-Add propanol, 3.8 g / m on polyester support
^It was applied so that the Ag amount was ² . The amount of gelatin was 1.8 g / m ² . On top of this, 1.5 g / m ² of gelatin as a protective layer and polymethylmethacrylate particles (average particle size 2.
5μ) 0.3 g / m ² , and the following surfactant as a coating aid,
Apply a protective layer containing a stabilizer and a UV absorbing dye,
Dried.

This sample was image-exposed with a bright room printer p-607 manufactured by Dainippon Screen Co., Ltd. through a document as shown in FIG. 1, developed at 38 ° C. for 20 seconds, developed, fixed, washed with water and dried, and the character quality of the extracted characters was removed. Was evaluated.

Character extraction quality 5 means that a 30 μm wide character is reproduced when an appropriate exposure is performed so that a halftone dot area of 50% becomes 50% halftone dot area on a return photosensitive material using an original as shown in FIG. The image quality is very good and the image quality is very good. On the other hand, the extracted character image quality 1 is an image quality that can reproduce only characters having a width of 150 μm or more when the same appropriate exposure is given. Rank was set. Three or more is a practical level.

The results are shown in Table 3. The sample of the present invention has excellent character image quality.

Example 4 Preparation of Sample 401 A multilayer color light-sensitive material having a core layer of the following composition was prepared on a cellulose triacetate film support having a thickness of 127 μm and provided as a sample 401. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

1st layer: Anti-halation layer Black colloidal silver 0.25 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g UV absorber U-6 0.1 g High boiling organic Solvent Oil-1 0.1 g Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-D 10 mg High boiling point organic solvent Oil-3 40 mg Third layer: Intermediate layer Fogging fine grain silver iodobromide emulsion (average grain size 0.06 μ, AgI
1 mol%) Silver amount 0.05 g Gelatin 0.4 g Fourth layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4 μm, AgI 1: 1 of 4.5 mol% monodisperse cube and 0.3 μg average particle size, AgI 4.5 mol% monodisperse cube
Mixture of silver) 0.7 g Gelatin 0.8 g Coupler C-1 0.20 g Coupler C-9 0.05 g Compound Cpd-D 10 mg High boiling organic solvent Oil-2 0.1 g Fifth layer: middle-sensitive red-sensitive emulsion layer Sensitizing dye S -1 and S-2 spectrally sensitized silver iodobromide emulsion (monodisperse cube with average grain size 0.5μ and AgI content 4mol%)
Silver amount 0.5 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Sixth layer: high-sensitivity red-sensitive emulsion layer Sensitizing dye S-1 And silver iodobromide emulsion spectrally sensitized with S-2 (monodisperse twin grains having an average grain size of 0.7 μm and an AgI content of 2 mol%) Silver amount 0.5 g Gelatin 1.1 g Coupler C-3 0.7 g Coupler C- 1 0.3g 7th layer: Intermediate layer Gelatin 0.6 g Dye D-1 0.02g 8th layer: Intermediate layer Fogging silver iodobromide emulsion (average grain size 0.06μ, AgI content
0.3 mol%) 0.02 g Gelatin 1.0 g Anti-color mixing agent Cpd-A 0.2 g Ninth layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain 1: 1 of a monodisperse cube with a diameter of 0.4μ and an AgI content of 4.5mol% and an average particle size of 0.2μ and an AgI content of 4.5mol%
Mixture of 0.5 g Silver 0.5 g Gelatin 0.5 g Coupler C-4 0.10 g Coupler C-7 0.10 g Coupler C-8 0.10 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02g Compound Cpd-H 0.02g Compound Cpd-D 10mg High-boiling organic solvent Oil-1 0.1g High-boiling organic solvent Oil-2 0.1g 10th layer: Middle speed green sensitive emulsion layer Sensitizing dyes S-3 and S- Silver iodobromide emulsion spectrally sensitized by 4 (monodisperse cube with an average grain size of 0.5 μm and an AgI content of 3 mol%) Silver amount 0.4 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.1 g Coupler C- 8 0.1 g Compound Cpd-B 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g Compound Cpd-H 0.05 g High boiling organic solvent Oil-2 0.01 g Layer 11: High sensitivity green sensitivity Emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average particle size in terms of spheres 0.6 μ, AgI content 1.3 mol%, diameter /
Monodisperse flat plate having an average thickness value of 7) Silver amount 0.8 g Gelatin 1.0 g Coupler C-4 0.4 g Coupler C-7 0.2 g Coupler C-8 0.2 g Compound Cpd-B 0.08 g Compound Cpd-E 0.02 g Compound Cpd -F 0.02g Compound Cpd-G 0.02g Compound Cpd-H 0.02g High boiling organic solvent Oil-1 0.02g High boiling organic solvent Oil-2 0.02g 12th layer: Intermediate layer Gelatin 0.6 g Dye D-2 0.05g No. 13 layers: Yellow filter layer Yellow colloidal silver 0.1 g Gelatin 1.1 g Anti-color mixing agent Cpd-A 0.01 g High boiling organic solvent Oil-1 0.01 g 14th layer: Intermediate layer Gelatin 0.6 g 15th layer: Low sensitivity blue sensitivity Emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (a monodisperse cube having an average particle size of 0.4 µ and an AgI content of 3 mol% and an average particle size of 0.2 µ and an AgI content of 3 mol%). 1: 1 mixture of monodisperse cubes) Silver amount 0.6 g Gelatin 0.8 g Coupler C-5 0.6 g High boiling organic solvent Oil-2 0.02 g 16th layer: Medium Sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (monodisperse cube having an average grain size of 0.5 μm and AgI content of 2 mol%) Silver amount 0.3 g Gelatin 0.9 g Coupler C-5 0.3 g Coupler C-6 0.3 g High boiling point organic solvent Oil-2 0.02 g 17th layer: High-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (Average particle size in terms of sphere 0.7μ, AgI content 1.5mol%, diameter /
Average particle thickness of 7) Silver amount 0.5g Gelatin 1.2g Coupler C-6 0.7g 18th layer: 1st protective layer Gelatin 0.7 g UV absorber U-1 0.04g UV absorber U-3 0.03g UV absorber U-4 0.03g UV absorber U-5 0.05g UV absorber U-6 0.05g High boiling point organic solvent Oil-1 0.02g Formalin scavenger Cpd-C 0.8 g Dye D-3 0.05g 19th layer : Second protective layer Fogged fine grain silver iodobromide emulsion (average grain size 0.06μ, AgI
Silver content 0.1 g Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average) Particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg In addition to the above composition, gelatin hardener H-1 and surfactants for coating and emulsification were added to each layer.

In the emulsion used herein, monodispersion means that the coefficient of variation is 20% or less.

Oil-1 Dibutyl phthalate Oil-2 Tricresyl phosphate Preparation of Samples 402 to 405 Sample 402 was prepared in the same manner as Sample 401, except that the CpdD added to the second, fourth and ninth layers of Sample 401 was changed as shown in the table below.
~ 405 was made.

After the silver halide color photographic light-sensitive material prepared as described above was exposed, it was processed according to the following steps. Further, the processing was performed while replenishing a replenisher of a fixed area in accordance with the processing amount of the photosensitive material.

[Treatment process] Treatment process Time Temperature Tank capacity Replenishment amount Black and white development 6 minutes 38 ℃ 12 2.2 / m ² First water washing 2〃 38〃 4〃 7.5〃 Inversion 2〃 38〃 4〃 1.1〃 Color development 6〃 38 〃 12 〃 2.2 〃 Adjust 2 〃 38 〃 4 〃 1.1 〃 Bleach 6 〃 38 〃 12 〃 0.22 〃 Fixed Cloth 4 〃 38 〃 8 〃 1.1 〃 Second Water Wash 4 〃 38 〃 1 〃 Cheap 7.5 25 〃 2 〃 1.1 〃 The composition of each processing solution was as follows.

pH was adjusted with hydrochloric acid or potassium hydroxide.

pH was adjusted with hydrochloric acid or potassium hydroxide.

pH was adjusted with hydrochloric acid or potassium hydroxide.

pH was adjusted with hydrochloric acid or potassium hydroxide.

pH was adjusted with hydrochloric acid or potassium hydroxide.

The pH was adjusted with hydrochloric acid or aqueous ammonia.

The sample of the present invention was significantly improved in sharpness as compared with the sample of the comparative example, and was also excellent in color reproducibility.

Example 5 A paper support (thickness: 10) laminated on both sides with polyethylene
A color photographic light-sensitive material was prepared by coating the following first to fourteenth layers on the front side (0 micron) and the fifteenth to sixteenth layers on the back side. Titanium oxide (4 g / m ² ) is used as a white pigment in the polyethylene on the first layer coating side, and a very small amount (0.003
g / m ² ) of ultramarine blue was included as a bluing dye (the chromaticity of the surface of the support was 88.0, −0.20, −0.75 in the L ^* , a ^* , b ^* system).

(Composition of photosensitive layer) The components and coating amounts (g / m ² units) are shown below. For silver halide, the coating amount is shown in terms of silver. The emulsion used for each layer was prepared according to the method for preparing emulsion EM1. However, the emulsion of the fourteenth layer was a Lippmann emulsion which was not chemically sensitized on the surface.

1st layer (anti-halation layer) Black colloidal silver ・ ・ ・ 0.10 Gelatin ・ ・ ・ 0.70 2nd layer (intermediate layer) Gelatin ・ ・ ・ 0.70 3rd layer (low sensitivity red sensitive layer) Red sensitizing dye (ExS-1,2) , 3) spectrally sensitized with silver bromide (average grain size 0.25μ, size distribution [variation coefficient] 8
%, Surface-emitting body) ...... 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1,2,3) (5 mol% silver chloride, average particle size 0.40μ, size distribution)
10%, octahedron) …… 0.08 Gelatin …… 1.00 Cyan coupler (ExC-1,2,3 at 1: 1: 0.2) …… 0.30 Anti-fading agent (Cpd-1,2,3,4 equivalent) …… ... 0.18 Anti-staining agent (Cpd-5) ... 0.003 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler solvent (Solv-1,2,3 equivalent) ... 0.12 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1,2,3) (average grain size 0.60μ, size distribution 15%, octahedron) ...
… 0.14 Gelatin …… 1.00 Cyan coupler (ExC-1,2,3 1: 1: 0.2) …… 0.30 Anti-fade agent (Cpd-1,2,3,4 equivalent) …… 0.18 Coupler dispersion medium (Cpd −6) …… 0.03 Coupler solvent (Solv-1,2,3 equivalent) …… 0.12 Fifth layer (interlayer) Gelatin …… 1.00 Color mixing inhibitor (Cpd-7) …… 0.08 Color mixing inhibitor solvent (Solv -4,5 equivalents) ...... 0.16 Polymer latex (Cpd-8) ...... 0.10 6th layer (low sensitivity green sensitive layer) Silver bromide spectrally sensitized with green sensitizing dye (ExS-4) ( Average particle size 0.25μ, size distribution 8%, octahedron) …… .0.
04 Silver chlorobromide spectrally sensitized with green sensitizing dye (ExS-4) (silver chloride 5 mol%, average grain size 0.40μ, size distribution)
0.06 Gelatin ... 0.80 Magenta coupler (ExM-1,2,3 equivalent) ... 0.11 Anti-fading agent (Equivalent to Cpd-9,26) ... 0.15 Stain inhibitor (Cpd) −10,11,12,13 in 10: 7: 7: 1 ratio)…
... 0.025 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4,6 equivalent) ... 0.15 7th layer (highly sensitive green-sensitive layer) Spectral sensitization with green sensitizing dye (ExS-4) Silver bromide (average grain size 0.65μ, size distribution 16%, octahedron) …… 0.
10 Gelatin …… 0.80 Macenta coupler (ExM-1,2,3 equivalent) …… 0.11 Antifade agent (Cpd-9,26 equivalent) …… 0.15 Antistain agent (Cpd-10,11,12, 13 to 10: 7: 7: 1 ratio) ...
… 0.025 Coupler dispersion medium (Cpd-6) …… 0.05 Coupler solvent (Solv-4,6 equivalents) …… 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloidal silver (Particle size 100Å) …… 0.12 Gelatin …… 0.70 Color mixing inhibitor (Cpd-7) …… 0.03 Color mixing inhibitor solvent (Solv-4,5 equivalents) ・ ・ ・ 0.10 Polymer latex (Cpd-8) …… 0.07 10th layer (intermediate layer) Same as 5th layer 11th layer (low sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5,6) (average grain size 0.40μ, size Distribution 8%, octahedron) ...
… 0.07 Silver chlorobromide spectrally sensitized with blue sensitizing dye (ExS-5,6) (silver chloride 8 mol%, average grain size 0.60μ, size distribution)
11%, octahedron) ...... 0.14 Gelatin ...... 0.80 Yellow coupler (ExY-1,2 equivalent) ...... 0.35 Anti-fading agent (Cpd-14) ...... 0.10 Anti-staining agent (Cpd-5,15 1: 0.007 Coupler dispersion medium (Cpd-6) …… 0.05 Coupler solvent (Solv-2) …… 0.10 12th layer (high-sensitivity blue-sensitive layer) Blue-sensitizing dye (ExS-5,6) Silver bromide spectrally sensitized by (average grain size 0.85μ, size distribution 18%, octahedron) …… .0.
15 Gelatin: 0.60 Yellow coupler (ExY-1,2 equivalent): 0.30 Anti-fading agent (Cpd-14): 0.10 Anti-staining agent (Cpd-5,15 in 1: 5 ratio) :: 0.007 Coupler Dispersion medium (Cpd-6) …… 0.05 Coupler solvent (Solv-2) …… 0.10 13th layer (ultraviolet absorbing layer) Gelatin …… 1.00 Ultraviolet absorber (Cpd-2,4,16 equivalents) …… 0.50 Mixed color Inhibitor (Cpd-7,17 equivalents) ...... 0.03 Dispersion medium (Cpd-6) ...... 0.02 UV absorber solvent (Solv-2,7 equivalents) ...... 0.08 Anti-irradiation dye (Cpd-18,19, 20,21,27 to 10:
10: 13: 15: 20 ratio) ...... 0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride: 97 mol%, average size: 0.1μ)
…… 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight
50,000) …… 0.01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) Equivalent …… 0.05 Gelatin …… 1.80 Gelatin hardening agent (H-1, H-2 equivalent) …… 0.18 15th layer (back layer) Gelatin …… 2.50 UV absorption Agent (Cpd-2,4,16 equivalents) …… 0.50 Dye (Cpd-18,19,20,21,27 equivalents) …… 0.06 16th layer (backside protective layer) Polymethylmethacrylate particles (average particle) Size 2.4
μ) and silicon oxide (average particle size 5μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardening agent (H-1, H-2 equivalent) 0.14 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate is gelatinized. The mixture was simultaneously added to the aqueous solution at 75 ° C. for 15 minutes with vigorous stirring to obtain octahedral silver bromide grains having an average grain size of 0.40 μm. At this time silver 1
0.3 g of 3,4-dimethyl-1,3-thiazoline-2 per mole
-Thion was added. To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol of silver were sequentially added, and heated at 75 ° C. for 80 minutes to perform chemical sensitization. Using the particles thus obtained as a core, the particles were further grown in the same precipitation environment as in the first time, and finally had an average particle diameter of 0.7 μm.
Octahedral monodispersed core / shell silver bromide emulsion was obtained. The coefficient of variation of the particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver were added, and heated at 60 ° C. for 60 minutes to perform chemical sensitization to obtain an internal latent image type silver halide emulsion. Obtained.

In each photosensitive layer, ExZK-1 and ExZK-2 were used as nucleating agents at 10 ^-3 and 10 ^-2 % by weight, respectively, of silver halide, and Cpd-22 was used as a nucleating accelerator at 10 ^-2 % by weight. . Further, alkanol XC (Dupon) and sodium alkylbenzene sulfonate were used as emulsifying and dispersing aids for each layer, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-23, 24, 25) was used as a stabilizer in the layer containing silver halide and colloidal silver. This sample was designated as sample number 501. The compounds used in the examples are shown below.

Solv-1 Di (2-ethylhexyl) sebacate Solv-2 Trinonyl phosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricresyl phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate Solv- 7 Di (2-ethylhexyl) phthalate H-1 1,2-bis (vinylsulfonylacetamide)
Ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt ExZK-1 7- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-prohagyl-1,2, 3,4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxycarbonylethoxyethoxycarbonyl ) Phenylcarbamoyl] -4-hydroxy-1
-Naphtylthio} tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide} phenyl] -1-
Formylhydrazine In exactly the same manner as Sample 501 except that the compound 4 of the present invention was added at 3 mg / m ² per layer to all the third, fourth, sixth, seventh, eleventh and twelfth layers of Sample 501. Sample 502 was created.

Sample 503 was prepared by changing the compound 41 of the present invention of the sample 502 to the compound 42 of the present invention.

The silver halide color photographic light-sensitive materials 501 to 503 prepared as described above were imagewise exposed and then processed by the method described below using an automatic processor.

The replenishment method of the washing water was a so-called countercurrent replenishment method in which the washing solution (2) was replenished, and the overflow solution of the washing bath (2) was led to the washing bath (1). At this time, the amount of the bleach-fix solution brought into the washing bath (1) from the bleach-fix bath by the photosensitive material is as follows.
It was 35 ml / m ² , and the ratio of the replenishment amount of the washing water to the carry-in amount of the bleach-fix solution was 9.1 times.

 The composition of each processing solution was as follows.

Rinse water Both mother liquor and replenisher are mixed-bed type where tap water is filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) Water was passed through the column to adjust the concentration of calcium and magnesium ions to 3 mg / or lower, and then 20 mg / sodium isocyanurate dichloride and 1.5 g / sodium sulfate were added. The pH of this solution ranged from 6.5 to 7.5.

As a result, the samples 502 and 503 according to the present invention were significantly superior in color reproducibility to the comparative sample 501.

Example 6 Samples 601 as a multilayer color light-sensitive material were prepared by coating layers of the following composition on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 601) First layer; anti-halation layer Black colloidal silver ...... Silver 0.18 gelatin ...... 0.40 Second layer; Intermediate layer 2,5-di-t-pentadecylhydroquinone ...... 0.18 EX-1 ...... 0.07 EX- 3 ...... 0.02 EX-12 ...... 0.002 U-1 ...... 0.06 U-2 ...... 0.08 U-3 ...... 0.10 HBS-1 ...... 0.10 HBS-2 ...... 0.02 Gelatin ...... 0.80 Third layer (1st layer) Red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size: 0,1)
6μ, coefficient of variation for particle size 0.15) …… Silver 0.55 Sensitizing dye I …… 6.9 × 10 ^-5 Sensitizing dye II …… 1.8 × 10 ^-5 Sensitizing dye III …… 3.1 × 10 ^-4 Sensitizing dye IV …… 4.0 × 10 ^-5 EX-2 …… 0.350 EX-3 …… 0.015 EX-10 …… 0.020 Comparative example-b …… 0.030 Gelatin …… 0.80 Fourth layer (second red-sensitive emulsion layer) Tabular iodide Silver bromide emulsion (silver iodide 10 mol%, average grain size 0.
7μ, average aspect ratio 5.5, average thickness 0.2μ) …… Silver 1.0
Sensitizing dye IX …… 5.1 × 10 ^-5 Sensitizing dye II …… 1.4 × 10 ^-5 Sensitizing dye III …… 2.3 × 10 ^-4 Sensitizing dye IV …… 3.0 × 10 ^-5 EX-2 …… 0.400 EX-3 ...... 0.050 Comparative example-b ...... 0.025 EX-10 ...... 0.015 Gelatin ...... 0.90 Fifth layer (third red emulsion layer) Silver iodobromide emulsion (16 mol% silver iodide, average grain size) 1.1μ)
…… Silver 1.60 Sensitizing dye IX …… 5.4 × 10 ^-5 Sensitizing dye II …… 1.4 × 10 ^-5 Sensitizing dye III …… 2.4 × 10 ^-4 Sensitizing dye IV …… 3.1 × 10 ^-5 EX− 10 …… 0.007 EX-3 …… 0.240 EX-4 …… 0.120 Comparative example-b …… 0.010 HBS-1 …… 0.10 HBS-2 …… 0.10 Gelatin …… 0.95 6th layer (intermediate layer) EX-5 …… 0.040 HBS-1 0.020 Gelatin 0.80 7th layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.
6μ, average aspect ratio 6.0, average thickness 0.15) …… Silver 0.40
Sensitizing dye V …… 3.0 × 10 ^-5 Sensitizing dye VI …… 1.0 × 10 ^-4 Sensitizing dye VII …… 3.8 × 10 ^-4 EX-6 …… 0.260 EX-1 …… 0.021 EX-7 …… 0.030 Comparative Example-c ...... 0.005 EX-8 ...... 0.025 HBS-1 ...... 0.100 HBS-11 ...... 0.010 Gelatin ...... 0.75 Eighth layer (second green emulsion layer) Monodisperse silver iodobromide emulsion (iodine Silver halide 12 mol%, average grain size 0.
8μ, coefficient of variation for particle size 0.16) …… Silver 0.80 Sensitizing dye V …… 2.1 × 10 ^-5 Sensitizing dye VI …… 7.0 × 10 ^-5 Sensitizing dye VII …… 2.6 × 10 ^-4 EX-6… … 0.180 Comparative example-c …… 0.010 EX-8 …… 0.010 EX-1 …… 0.008 EX-7 …… 0.012 HBS-1… 0.160 HBS-11 …… 0.008 Gelatin …… 0.85 9th layer (3rd green color) Emulsion layer) Silver iodobromide emulsion (silver iodide 18 mol%, average grain size 1.0μ)
…… Silver 1.2 Sensitizing dye V …… 3.5 × 10 ^-5 Sensitizing dye VI …… 8.0 × 10 ^-5 Sensitizing dye VII …… 3.0 × 10 ^-4 EX-6 …… 0.065 EX-11 …… 0.030 EX -1 ...... 0.025 HBS-1 ...... 0.25 Comparative example-c ...... 0.005 Gelatin ...... 1.00 10th layer (yellow filter layer) Yellow colloidal silver ...... Silver 0.05 EX-5 ...... 0.08 HBS-1 ...... 0.03 Gelatin …… 0.60 11th layer (first blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (4 mol% silver iodide, average grain size of 0.
6μ, average aspect ratio 7.3, average thickness 0.14) …… Silver 0.24
Sensitizing dye VIII …… 3.5 × 10 ^-4 EX-9 …… 0.85 EX-8 …… 0.059 HBS-1 …… 0.28 Gelatin …… 1.40 12th layer (2nd blue-sensitive emulsion layer) Monodispersed silver iodobromide Emulsion (silver iodide 8 mol%, average grain size 0.
8μ, coefficient of variation for particle size 0.18) …… Silver 0.45 Enhancer dye VIII …… 2.1 × 10 ^-4 EX-9 …… 0.20 EX-10 …… 0.015 HBS-1 …… 0.03 Gelatin …… 0.30 13th layer ( Third blue-sensitive emulsion layer) Silver iodobromide emulsion (14 mol% silver iodide, average grain size 1.3μ)
…… Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 …… 0.20 HBS-1 …… 0.07 Gelatin …… 0.69 14th layer (first protective layer) Silver iodobromide emulsion (1 mol% silver iodide) , Average particle size 0.07μ)
...... Silver 0.5 U-4 ...... 0.11 U-5 ...... 0.17 HBS-1 ...... 0.90 Gelatin ...... 0.80 15th layer (second protective layer) Polymethyl acrylate particles (diameter about 1.5 μm) ...... 0.5
4 S-1 ...... 0.15 S-2 ...... 0.05 Gelatin ...... 0.60 In addition to the above components, a gelatin hardening agent H-1 and a surfactant were added to each layer.

(Samples 602 and 603) Comparative Example-b used in Example 1 of the third layer, the fourth layer and the fifth layer of Sample 601 was replaced with the compounds 42 and 43 of the present invention in equimolar amounts to obtain Samples 602 and 603, respectively. It was 603.

(Sample 604) Sample 604 was prepared by substituting the compound 43 of the present invention in equimolar amounts for Comparative Example-c used in Example 1 of the seventh layer, the eighth layer, and the ninth layer of Sample 603.

Expose the MTF measurement pattern to these samples with white light,
The following color development processing was performed, and the MTF value of the magenta image was measured. The MTA value is measured by The Theory of the Photogr
Followed the method described in aphic Process, 3rd ed.

Also, expose and develop the RMS granularity measurement pattern to 48μ
The RMS granularity with an m-diameter aperture was measured.

Further, red imagewise exposure and development are performed [magenta density of exposure amount at cyan density (fog +0.2)] −
[Magenta density of unexposed area] was evaluated as the degree of color turbidity.

In the color development processing, the following processing was performed at 38 ° C. by an automatic developing machine.

Color development 3 minutes 15 seconds Bleaching 1 minute Bleaching and fixing 3 minutes 15 seconds Rinse 40 seconds Rinse 1 minute Stable 40 seconds Dry (50 ° C) 1 minute 15 seconds In the above process, rinsing is countercurrent water The washing method was adopted. Next, the composition of each processing solution will be described.

The replenishment amount of each processing solution was 1200 ml for color development per 1 m ² of the color photographic material, and 800 ml for all others including washing with water. The pre-bath carry-amount to the water washing step was found to be a color light-sensitive material 1 m ² per 50 ml.

<< Bleaching solution >> Common for mother liquor and replenishing solution Ethylenediaminetetraacetic acid ferric ammonium salt 120.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium nitrate 10.0g Ammonium bromide 100.0g Bleaching accelerator 5 × 10 ^-3 mol Ammonia water is added and pH is added to 6.3. 1.0 bleach-fixing solution Common for mother liquor and replenishing solution Ethylenediaminetetraacetic acid ferric ammonium salt 50.0 g Ethylenediaminetetraacetic acid disodium salt 5.0 g Sodium sulfite 12.0 g %) 240ml Ammonia water is added and pH7.3 Water is added 1 << Rinsing water >> Calcium ion 32mg /, Magnesium ion 7.3mg
/ Containing tap water was passed through a column filled with H-type strongly acidic cation exchange resin and OH-type strongly basic anion exchange resin, and calcium ion 1.2 mg /, magnesium ion 0.
20 mg of sodium isocyanurate dichloride was added to 4 mg / treated water.

<< Stabilizer >> Mother liquor / replenisher common formalin (37% w / v) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Ethylenediaminetetraacetic acid di-sodium salt 0.05 g Water added 1 pH 5.8 << drying >> The drying temperature was 50 ° C.

From the above table, it is clear that the sample using the compound of the present invention is excellent in sharpness represented by MTF value, granularity represented by RMS value, and color reproducibility represented by color turbidity.

Compound used in Example 6 HBS-1 Tricresyl phosphate HBS-2 Dibutyl phthalate Example-7 A corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and a first undercoating liquid having the following composition was applied using a wire bar coater so that the coating amount was 5.1 cc / m ^2. It was applied and dried at 175 ° C. for 1 minute. Next, the first undercoat layer was similarly provided on the opposite surface.

0.4 wt% based on the latex solid content.

On the first undercoat layer on both sides of the above, a second
The undercoating liquid was applied on both sides one by one so that the coating amount was 8.5 cc / m ^2, and dried to complete an undercoated film.

Second undercoat liquid Preparation of Emulsion Layer Coating Solution In water 1, potassium bromide 5 g, potassium iodide 0.05 g, gelatin 30
g, 5 of the thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
% Aqueous solution (2.5 cc) and maintained at 73 ° C. While stirring, an aqueous solution of silver nitrate 8.33 g and an aqueous solution containing 5.94 g of potassium bromide and 0.726 g of potassium iodide were added in 45 seconds by the double jet method. . Subsequently, after adding 2.5 g of potassium bromide, an aqueous solution containing 8.33 g of silver nitrate was added over 7 minutes and 30 seconds so that the flow rate at the end of the addition was twice that at the start of the addition. Subsequently, an aqueous solution of 153.34 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added over 25 minutes by the control double jet method while maintaining the potential at pAg8.1. The flow rate at this time was accelerated so that the flow rate at the end of the addition was eight times the flow rate at the start of the addition. After the addition was completed, 15 cc of 2N potassium thiocyanate solution was added, and 50 cc of 1% potassium iodide aqueous solution was added to 30 cc.
It was added over seconds. After that, the temperature was lowered to 35 ° C and soluble salts were removed by the precipitation method, then the temperature was raised to 40 ° C and 68 g of gelatin, 2 g of phenol and 7.5 g of trimethylolpropane were added.
PH 6.55, pAg8.1 with caustic soda and potassium bromide.
Adjusted to 0.

After the temperature was raised to 56 ° C., 175 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 625 mg of a sensitizing dye having the following structure were added. Ten minutes later, sodium thiosulfate pentahydrate 5.5 mg potassium thiocyanate 163 mg, chloroauric acid 3.6 m
g was added and quenched after 5 minutes to solidify. In the obtained emulsion, 93% of the total projected area of all grains consisted of grains having an aspect ratio of 3 or more. The average projected area diameter of all grains having an aspect ratio of 2 or more was 0.95 μm, and the standard deviation was 23.
%, The average thickness was 0.155 μm, and the aspect ratio was 6.1.

The following chemicals were added to this emulsion per mole of silver halide to prepare a coating solution.

Compound of the invention (see Table 5) 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 80 mg Ethyl acrylate / acrylic acid / methacrylic acid = 95
/ 2/3 composition ratio Copolymer plasticizer 20.0 g Nitron 50 mg The emulsion layer coating solution thus obtained was coated on both sides of the support in the same manner by a simultaneous extrusion method with the surface protective layer solution. At this time, the coating amount per one side of the emulsion layer and the surface protective layer was as follows.

<Emulsion layer> Coating silver amount 1.9g / m ² Coating gelatin amount 1.5g / m ² <Surface protection layer> Gelatin 0.81g / m ² Dextran (average molecular weight 39,000) 0.81g / m ² Matting agent (average particle size 3.5 μm) Polymethyl methacrylate / methacrylic acid = 9/1 copolymer 0.06 g / m ² 4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene 15.5 mg / m ² sodium polyacrylate (average molecular weight 41,000) 70 mg /
As the m ² hardener, 1,2-bis (sulfonylacetamido) ethane was applied so as to be 56 mg / m ² per side. Thus,
The photographic material of the present invention was obtained.

Evaluation of photographic performance Fuji Photo Film Co., Ltd. GRENEX Orthoscreen HR-4 was attached to both sides using a cassette,
X-ray sensitometry was performed. To adjust the exposure,
This was performed by changing the distance between the X-ray tube and the cassette. After the exposure, the film was processed by an automatic processor according to the following processing steps.

Dry-to-dry processing time 45 seconds The developer and fixer used had the following composition.

(Developer) potassium hydroxide 29 g potassium sulfite 44.2 g sodium hydrogen carbonate 7.5 g boric acid 1.0 g diethylene glycol 12 g ethylenediaminetetraacetic acid 1.7 g 5-methylbenzotriazole 0.06 g hydroquinone 25 g glacial acetic acid 18 g triethylene glycol 12 g 5 -Nitroindazole 0.25 g 1-phenyl-3-pyrazolidone 2.8 g glutaraldehyde (50 wt / wt%) 9.86 g sodium metabisulfite 12.6 g potassium bromide 3.7 g Water added 1.0 (fixer) ammonium thiosulfate (70 wt / 200% Ethylenediaminetetraacetic acid disodium salt dihydrate 0.02g Sodium sulfite 15g Boric acid 10g Sodium hydroxide 6.7g Glacial acetic acid 15g Aluminum sulfate 10g Sulfuric acid (36N) 3.9g Add water to bring the total volume to 1.

(The pH was adjusted to 4.25.) The results are shown in Table 5. From Table 5, it was found that the sample using the compound of the present invention had a high maximum density and excellent image quality.

Example 8 Emulsion of each layer, dispersion of zinc hydroxide, dispersion of activated carbon, dispersion of electron transfer agent, yellow, magenta,
A dispersion of cyan and a dispersion for the intermediate layer were prepared to prepare a photosensitive material 801 shown in Table 6.

 Further, the image receiving materials shown in Table 7 were prepared as described below.

Gelatin 20g aqueous gelatin solution (in water 800cc the stirred emulsion for good blue-sensitive layer, potassium bromide 3g, the following compound 0.03 g, and _{HO (CH 2) 2 S (} CH 2) 2 S (CH 2) 2 OH The following (1) solution and (2) solution were simultaneously added to 0.25 g of the solution kept at 50 ° C.) over 30 minutes. Then, the following (3) solution and (4)
The liquid was added simultaneously over 20 minutes. After the addition of the solution (3) was started, the following dye solution was added for 18 minutes from 5 minutes.

After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. And chloroauric acid was added for optimal chemical sensitization. Thus, 600 g of a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.40 μm was obtained.

Emulsion for green-sensitive layer A well-stirred aqueous gelatin solution (shown in the table below) was kept at 50 ° C, and solutions (I) and (II) were added over 30 minutes. Next, the solution (III) and the solution (IV) were added over 30 minutes, and one minute after the completion of the addition, the dye solution was added.

After washing with water and desalting, 20 g of gelatin was added to adjust the pH and pAg, and chemical optimization was optimally performed using triethylthiourea, chloroauric acid and 4-hydroxy-6-methyl-1,3,3a-7-tetrazaindene. I felt.

The resulting emulsion was a 0.40μ monodispersed cubic emulsion with a yield of 63.
0g.

Emulsion for red-sensitive layer A well-mixed aqueous gelatin solution (20g gelatin, 0.3g potassium bromide, 6g sodium chloride, and 30g chemical A in the following) were added to 800ml water and kept at 50 ° C. Solution (II) and solution (II) were added simultaneously at the same flow rate over 30 minutes. Thereafter, the following solution (III) and solution (IV) are simultaneously
Added over 0 minutes. Also, 3 minutes after the start of the addition of the liquids (III) and (IV), the following dye solutions were added over 20 minutes.

After washing and desalting, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and the pAg to 7.7, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. Then, chloroauric acid was added and the mixture was optimally sensitized at 60 ° C. Thus, a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.38 μ was obtained. The yield was 635 g.

Dye solution The following dye (a) 67mg and dye (b) 133mg were added to methanol 1
Dissolved in 00ml.

A method for preparing a dispersion of zinc hydroxide will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethylcellulose as a dispersant, and 0.1 g of sodium polyacrylate are added to 100 cc of a 4% aqueous gelatin solution, and crushed for 30 minutes using glass beads having an average particle size of 0.75 mm in a mill. did. The glass beads were separated to obtain a dispersion of zinc hydroxide.

 Next, a method for preparing a dispersion of activated carbon will be described.

2.5 g of activated carbon powder (reagent, special grade) manufactured by Wako Pure Chemical Industries, Ltd., Demol N / g manufactured by Kao Soap Co., Ltd. as a dispersant, and 0.25 g of polyethylene glycol nonylphenyl ether were added to 100 cc of 5% gelatin aqueous solution, and the mixture was milled The glass beads having an average particle size of 0.75 mm were used for pulverization for 120 minutes. The glass beads were separated to obtain a dispersion of activated carbon having an average particle size of 0.5 μm.

 Next, a method for preparing a dispersion of the electron transfer agent will be described.

10 g of the following electron transfer agent, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersing agent, and 0.5 g of the following anionic surfactant are added to a 5% aqueous gelatin solution, and the mixture is milled using glass beads having an average particle diameter of 0.75 mm. Milled for minutes. The glass beads were separated to obtain a dispersion of an electron transfer agent having an average particle diameter of 0.3 μm.

Next, a method for preparing a gelatin dispersion of the dye-providing compound will be described.

Each of yellow, magenta, and cyan was added to 50 cc of ethyl acetate and dissolved by heating at about 60 ° C. to form a uniform solution as described below. This solution was mixed with 100 g of a 10% aqueous solution of lime-processed gelatin, 0.6 g of sodium dodecylbenzenesulfonate and 50 cc of water, and then mixed with a homogenizer for 10 minutes.
Dispersed at 10,000 rpm. This dispersion is called a gelatin dispersion of the dye-providing compound.

Next, a method for preparing a gelatin dispersion of the electron donor for the intermediate layer will be described.

The following electron donor 23.6 g and the above high boiling solvent 8.5 g
Was added to 30 cc of ethyl acetate to obtain a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 0.25 g of sodium bisulfite, 0.3 g of sodium dodecylbenzenesulfonate and 30 cc of water are mixed with stirring, and then homogenized for 10 minutes.
Dispersed at 10,000 rpm. This dispersion is referred to as a gelatin dispersion of the electron donor.

Electron donor In the light-sensitive material 801, the light-sensitive materials 802 to 806 were added to the second and fourth layers by dispersing the compound of the present invention in gelatin by an oil dispersion method and adding each layer so as to have a concentration of 3 × 10 ⁻⁵ mol / m ^2. It was created (Table 8).

The light-sensitive materials 801 to 806 were exposed to light through a wedge whose density was continuously changed in the direction perpendicular to the wavelength using a spectrograph.

15 ml / m ² of water was supplied to the emulsion surface of the exposed color photographic material by immersing it in warm water of 35 ° C. for 3 seconds, and then superposed such that the image receiving material and the film surface were in contact with each other.

The film was heated for 15 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film became 78 ° C. Next, when the image receiving material was peeled off from the photosensitive material, blue, green, and red spectralgrams were obtained on the image receiving material in accordance with the wavelength.

The density of yellow, magenta, and cyan of each color is determined by X-rite.
It was measured with a model 310 densitometer. Table 8 shows the results.

From the above results, it can be seen that the addition of the compound of the present invention increases the density of each of the blue, green and red colors and reduces the complementary color components, thereby increasing the color purity. That is, it was proved that the compound of the present invention had an excellent ability to improve color reproduction.

The same processing was performed after the above-mentioned photographic material was stored at 30 ° C. and 70% for 1 month, but the results were the same as those shown in Table 3 above, and the photographic material using the compound of the present invention had no adverse effect on the aging property. Was not given.

Example 9 Compounds 9, 11, 17 and 21 of the present invention were added to the timing layer of the cover sheet of Example 1 of JP-A-63-289551 in an amount of 0.
825 mmol / m ² added cover sheets 9-1, 9-2,
9-3 and 9-4 were produced. These cover sheets were overlapped with the photosensitive sheet 102 of the embodiment, and processed in the same manner as in the embodiment. The development treatment temperature was 10 ° C, 25 ° C and 35 ° C.

As a result, each sample showed excellent photographic performance with low processing temperature dependency, high Dmax, and low Dmin.

Example 10 Third sample 102 of Example-1 of JP-A-1-112241,
The compound -12, -36 and -42 of the present invention was added to the 4th, 6th, 7th, 9th and 10th layers, respectively, in an amount of 3 mg / m < ² >, and a sample 11-
1, 11-2 and 11-3 were produced.

When this sample was processed as described in the same example,
It was confirmed that the color reproducibility was excellent.

[Brief description of the drawings]

FIG. 1 shows a configuration at the time of exposure in the case where a character extraction image is formed by overlapping, and the reference numerals indicate the following. (A) Transparent or translucent pasted base (b) Line drawing original (black part shows line drawing) (c) Transparent or translucent pasted base (d) Halftone original (black part is halftone (E) Photosensitive material for return (note that the hatched area indicates the photosensitive layer)

Continuation of front page (56) References JP-A-64-72139 (JP, A)

Claims (2)

(57) [Claims] 1. A silver halide photographic material comprising a compound represented by the following general formula (1). General formula (1) In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group, and Z represents a primitive group necessary for forming a nitrogen-containing heteroaromatic ring. In addition, in the general formula (1) The nitrogen-containing heteroaromatic ring group represented by or the substituent on the nitrogen-containing heteroaromatic ring group is further substituted with one or more nitro groups. Further, R in the general formula (1) is (Wherein R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group, and Y represents —SO ₂ — or —Y′—SO ₂ — or And Y ′ is —O— or —NH— or Is). 2. A silver halide photographic light-sensitive material of the general formula (2), which contains a compound represented by the following general formula (2). In the formula, R ₃₁ represents an aliphatic group or an aromatic group, R ₃₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group or an oxycarbonyl group, and G ₁ is -C- group, -SO ₂ - group, -SO- group, Represents a thiocarbonyl group or an iminomethylene group, A ₁ ,
A ₂ represents a hydrogen atom or a hydrogen atom on one side and a substituted or unsubstituted alkylsulfonyl group on the other side, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.