JP2663038B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material and a method for forming an ultra-high contrast negative image using the same, and particularly to a silver halide photographic material used in a photomechanical process. The present invention relates to a super-high contrast negative type photographic light-sensitive material suitable for a light-sensitive material.

(Prior Art) In the field of photoengraving, there is a demand for a photographic photosensitive material having good original reproducibility, a stable processing solution, or a simple replenishment in order to cope with the variety and complexity of printed matter.

Particularly in the line drawing photographing process, the manuscript is made by pasting typesetting characters, handwritten characters, illustrations, halftone pictures, and the like. Therefore, images having different densities and line widths are mixed in an original, and a plate-making camera, a photographic photosensitive material, or an image forming method for finishing these originals with good reproducibility is strongly desired. On the other hand, in plate making of catalogs and large posters, enlargement (enlargement) or reduction (shrinkage) of a halftone picture is widely performed, and in plate making using enlarged halftone dots, the number of lines becomes coarse and blurred. Shooting. In reduction, the number of lines / ink is larger than that of the original, and a thin point is photographed. Therefore, 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.

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, and
4,224,401, 4,243,739, 4,272,606, 4,3
As shown in No. 11,781, the surface latent image type silver halide photographic material to which a specific acylhydrazine compound is added contains a sulfurous acid preservative of 0.15 mol / or more 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 imaging system shows excellent performance in terms of sharp halftone dot quality, processing stability, speed and original reproducibility, the original reproducibility has been further improved to cope with the recent variety of printed matter. A system is desired.

JP-A-61-213847 and US Pat. No. 4,684,604 show a photosensitive material containing a redox compound which releases a photographically useful group by oxidation, and an attempt to extend the gradation reproduction range is disclosed. However, in a super-high contrast processing system using a hydrazine derivative, these redox compounds have a harmful effect of hindering the contrast, and their characteristics cannot be utilized.

In a silver halide photographic light-sensitive material characterized by containing hydrazine, the swelling rate has an important effect on photographic properties, and is described in JP-A-62-237444, JP-A-62-133017 and JP-A-63-12.
074.

(Object of the Invention) Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material containing a hydrazine derivative, which has a wide halftone gradation and less occurrence of black spots.

(Constitution of the Invention) The object of the present invention is to provide a first photosensitive silver halide emulsion layer containing at least a hydrazine derivative and a second photosensitive silver halide emulsion layer on the same surface of a support. A photosensitive silver halide emulsion layer or a silver halide photographic material containing a redox compound capable of releasing a development inhibitor by being oxidized to a hydrophilic colloid layer other than those described above. And the swelling ratio on the side with the hydrophilic colloid layer is 100% or more 2
Achieved by a silver halide photographic light-sensitive material characterized in that the content is not more than 00%.

The swelling ratio of the silver halide photographic light-sensitive material of the present invention is 100%
It is sufficient if it is not less than 200% and it is particularly preferable that it is 120 to 170%. The total amount of gelatin on the side having the photosensitive silver halide emulsion layer and the hydrophilic colloid layer was 7 g.
/ m ² or less, and particularly preferably 5.5 g / m ² or less.

If the swelling ratio is less than 100%, black spots are likely to occur,
On the other hand, when the swelling ratio exceeds 200%, the halftone gradation becomes narrow and the image quality deteriorates.

The swelling ratio of the hydrophilic colloid layer in the present invention is determined by the steps a, b and c as follows.

B) Measure the thickness of the hydrophilic colloid layer in the silver halide photographic light-sensitive material, b. Immerse the silver halide photographic light-sensitive material in distilled water at 25 ° C. for 1 minute, and compare with the layer thickness measured in step c. The percentage change in layer thickness is then measured.

Therefore, the swelling ratio of the hydrophilic colloid layer in the present invention refers to the swelling ratio of all the hydrophilic colloid layers existing on one side of the silver halide emulsion layer with respect to the support (for example, silver halide emulsion layer, surface protective layer, intermediate layer) The percentage of swelling caused by immersion in distilled water at 25 ° C. for 1 minute is expressed as a percentage.

As the hydrophilic colloid binder used in the hydrophilic colloid layers such as the emulsion layer and the surface protective layer of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used.

The amount of gelatin as a protective layer is preferably in the range of 0.5 g to 2.0 g / m ² .

For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate, dextran and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and the Pretty Tin of the Society of Scientific Photography Japan (Bull.S
Enzyme-treated gelatin as described in oc. Sci. Phot. Japan, No. 16, page 30 (1966) may be used, or a hydrolyzate or enzymatic degradation product of gelatin may also be used.

In the present invention, as a specific method for arbitrarily controlling the swelling ratio of the hydrophilic colloid layer including the silver halide emulsion layer and the non-photosensitive layer, various organic or inorganic gelatin hardeners (alone Or in combination). Examples of typical curing agents include mucochloric acid,
Aldehyde compounds such as formaldehyde and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 1,3,5-triacryloyl-hexahydro-s-triazine, 1,3,5-trivinylsulfonyl-hexahydro-s-triazine, bis ( Vinylsulfonylmethyl)
Ether, 1,3-bis (vinylsulfonyl) -propanol-2, bis (α-vinylsulfonylacetamide)
Ethane, 1,2-bis (vinylsulfonyl) ethane, 1,1 '
Active vinyl compounds such as -bis (vinylsulfonyl) methane; active halogen compounds such as 2,4-dichloro-6-hydroxy-s-triazine; and gelatin hardeners well known in the art. Also JP
Polymer hardeners described in U.S. Pat. No. 3,627,256 and U.S. Pat. No. 3,671,256 can also be used.

It is desirable to select the optimal amount of the gelatin hardener depending on the type of hardener, the type of gelatin, etc.
The amount is suitably from 0.5 to 50 × 10 ^-3 mol, preferably from 2 to 20 × 10 ^-3 mol, per 100 g of gelatin.

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

General formula (I) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group,
G ₁ -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.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. This alkyl group may have a substituent.

In the general formula (I), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.
Here, the unsaturated heterocyclic group may be condensed with the aryl group.

Preferred as R ₁ is an aryl group, particularly preferably a group containing a benzene ring.

The aliphatic group or aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an arakenyl group, an alkynyl group, an alkoxy group,
Aryl group, substituted amino group, ureido group, urethane group,
Aryloxy, sulfamoyl, carbamoyl, alkyl or arylthio, alkyl or arylsulfonyl, alkyl or arylsulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl An acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, an imide group, And the like. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), and 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 30 carbon atoms),
Examples thereof include a sulfonamide group (preferably having 1 to 30 carbon atoms), a ureido group (preferably having 1 to 30 carbon atoms), and a phosphoric amide group (preferably having 1 to 30 carbon atoms).

In formula (I), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group (for example, those containing a benzene ring ).

G ₁ In the case of, preferred among the groups represented by R ₂ are 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 and the like). ), Aralkyl groups (eg, o-hydroxybenzyl group), aryl groups (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl) And the like), and a hydrogen atom is particularly preferable.

R ₂ may be substituted, and as the substituent, the substituents listed for R ₁ can be applied.

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

Further, R ₂ disrupts the portion of the G ₁ -R ₂ from the remainder molecule, -G ₁
-R ₂ moiety of atoms may be such as to occur a cyclic structure cyclization reaction to form a containing, include those described in, for example, JP 63-29751 as an example.

A ₁ and A ₂ are most preferably hydrogen atoms.

R ₁ or R _{2 in} the general formula (I) 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 (I) 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 Nos. 62-67,510.

Specific examples of the compound represented by the general formula (I) 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. 64-105,682, 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
No., No. 1-40,792, No. 1-42,615, No. 1,42,616,
Those described in JP-A 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.

The redox compound of the present invention that can release a development inhibitor by being oxidized will be described.

The redox group of the redox compound is preferably a hydroquinone, a catechol, a naphthohydroquinone, an aminophenol, a pyrazolidone, a hydrazine, a hydroxylamine, or a reductone, and more preferably a hydrazine.

The hydrazines used as a redox compound capable of releasing a development inhibitor by being oxidized according to the present invention are preferably those represented by the following general formulas (R-1) and (R-2).
It is represented by the general formula (R-3). The compound represented by formula (R-1) is particularly preferred.

General formula (R-1) General formula (R-2) General formula (R-3) In these formulas, R ₁ represents an aliphatic group or an aromatic group. G ₁ -SO- group, -SO ₂ - group or Represents G ₂ is a mere bond, -O-, -S- or And R ₂ represents a hydrogen atom or R ₁ .

A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is synonymous with A ₁ or Represents

A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G ₁ -G ₂ -R _1.

Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor.

General formulas (R-1), (R-2) and (R-3) will be described in more detail.

In the general formulas (R-1), (R-2) and (R-3), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 20 carbon atoms. Is a linear, branched or cyclic alkyl group. This alkyl group may have a substituent.

In formulas (R-1), (R-2) and (R-3), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with an aryl group to form a heteroaryl group.

For example, among those having a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, etc., those containing a benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, hydroxy, halogen, cyano, sulfo, aryloxycarbonyl, acyl, alkoxycarbonyl Groups, an acyloxy group, a carbonamide group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, and the like. Preferred substituents are a linear, branched, or cyclic alkyl group (preferably having 1 to 20 carbon atoms). Aralkyl group (preferably having 7 to 30 carbon atoms), aralkyl group Coxy group (preferably having 1 to 30 carbon atoms), substituted amino group (preferably having 1 to 30 carbon atoms)
An amino group substituted with 30 alkyl groups), an acylamino group (preferably having 2 to 40 carbon atoms), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having A compound having 1 to 40, a phosphoric acid amide group (preferably having 1 to 40 carbon atoms) and the like.

As G _{1 in the} general formulas (R-1), (R-2) and (R-3), -SO ₂ - group are preferred, Is most preferred.

A ₁ and A ₂ are preferably hydrogen atoms, A ₃ is a hydrogen atom, Is preferred.

In the general formulas (R-1), (R-2) and (R-3)
Time represents a divalent linking group, and may have a timing adjusting function.

The divalent linking group represented by Time represents a group that releases PUG from Time-PUG released from the oxidized form of the redox nucleus through one or more steps of reaction.

As the divalent linking group represented by Time, for example, an intramolecular ring closure reaction of a p-nitrophenoxy derivative described in U.S. Pat. No. 4,248,962 (Japanese Patent Application Laid-Open No. 54-145,135) and the like can be used.
U.S. Pat. No. 4,310,612 (Japanese Unexamined Patent Publication No.
Which release PUG by an intramolecular ring-closure reaction after ring opening described in, for example, US Pat. Nos. 4,330,617, 4,446,216, 4,483,919, and JP-A-59-121,328. No. 4,409,323, U.S. Pat. No. 4,421,845, which releases PUG with the formation of an acid anhydride by an intramolecular ring closure reaction of the carboxyl group of the succinic acid monoester or an analog thereof described in Research Disclosure No. 21,228 (December 1981), U.S. Patent No.
4,416,977 (JP-A-57-135,944), JP-A-58-209,
No. 736, No. 58-209,738, etc., which produce quinomonomethane or an analog thereof by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group to release PUG; US Pat. No. 4,420,554 (Japanese Unexamined Patent Publication No.
57-136,640), JP-A-57-135,945 and JP-A-57-188,03.
No. 5,58-98,728 and 58-209,737, which release PUG from the γ-position of enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocyclic ring;
7-56,837 which releases PUG by an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated to a nitrogen atom of a nitrogen-containing heterocyclic ring; U.S. Pat. -90932), JP-A-59-93,4
No. 42, JP-A-59-75475, JP-A-60-249148, with formation of aldehydes described in JP-A-60-249149 and the like.
Those which release PUG; JP-A-51-146,828, 57-179,
No. 842, No. 59-104,641, which release PUG with decarboxylation of carboxyl group; -O-COOCR _a R _b -PUG
(R _a and R _b represent monovalent groups), which release PUG with decarboxylation and subsequent formation of aldehydes; isocyanates described in JP-A-60-7,429 And PUG is released by the coupling reaction of a color developer with an oxidized product described in U.S. Pat. No. 4,438,193.

Specific examples of these divalent linking groups represented by Tier are also described in detail in JP-A-61-236,549 and Japanese Patent Application No. 63-98,803.

PUG represents a group having a development inhibiting effect as (Time _t PUG or PUG).

The development inhibitor represented by PUG or Time _t PUG is a known development inhibitor having a hetero atom and bonded through a hetero atom, and examples thereof include CEKMess and TAKMess.・ THJames, The Theory of Photographic P
rocesses), 3rd edition, 1966, published by Macmillan, pages 344-346.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include those exemplified as the substituent of R ¹ , and these groups may be further substituted.

Preferred substituents are a nitro group, a sulfo group, a carboxyl group, a sulfamoyl group, a phosphono group, a phosphinico group, and a sulfonamide group.

In the general formulas (R-1), (R-2), and (R-3), R ₁ or Time _t PUG is a ballast group commonly used in immobile photographic additives such as couplers. A group which promotes the compounds represented by formulas (R-1), (R-2) and (R-3) to be adsorbed to silver halide may be incorporated.

The ballast group has the general formula (R-1), (R-2), (R-
An organic group that gives a molecular weight sufficient to prevent the compound represented by 3) from substantially diffusing into another layer or the processing solution, and includes an alkyl group, an aryl group, a heterocyclic group, an ether group, a thioether group, It comprises one or more combinations of an amide group, a ureido group, a urethane group, a sulfonamide group and the like. The ballast group is 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.

Specific examples of the group for promoting adsorption to silver halide include 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 Cyclic thioamide groups such as oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine, 1,3-imidazoline-2-thione, and chain thioamides Group, aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (when the carbon atom to which the -SH group is bonded is a nitrogen atom, this is synonymous with a cyclic thioamide group having a tautomeric relationship with the nitrogen atom) Specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, triazole, tetrazo Le, indazole, benzimidazole, imidazole, benzothiazole,
Nitrogen, oxygen, such as thiazole, thiazoline, benzoxazole, oxazole, oxazoline, thiadiazole, oxathiazole, triazine, azaindene,
Examples thereof include a 5- or 6-membered nitrogen-containing heterocyclic group composed of a combination of sulfur and carbon, and a heterocyclic quaternary salt such as benzimidazolinium.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent of R ₁ .

Hereinafter, specific examples of the compound used in the present invention are listed, but the present invention is not limited thereto.

As the redox compound used in the present invention, in addition to the above, for example, JP-A-61-213,847 and JP-A-62-260,1
No. 53, Japanese Patent Application No. 1-102,393, No. 1-102,394, No. 1-
Nos. 102,395 and 1-114,455 can be used.

The method for synthesizing the redox compound used in the present invention is described in, for example, JP-A-61-213,847 and JP-A-62-260,153, U.S. Pat.
No. 4,684,604, Japanese Patent Application No. 63-98,803, U.S. Pat.
No. 29, 3,620,746, 4,377,634, 4,332,878
No., JP-A-49-129,536, JP-A-56-153,336, JP-A-56-15
No. 3,342.

The redox compound of the present invention is used in an amount of 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ per mol of silver halide.
It is used in the range of １1 × 10 ^-2 mol.

The redox compound of the present invention may be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like.

In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, a redox compound powder can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The layer containing the redox compound of the present invention is provided above or below the photosensitive emulsion layer containing a hydrazine nucleating agent. The layer containing the redox compound of the present invention may further contain photosensitive silver halide emulsion grains. An intermediate layer containing gelatin or a synthetic polymer (polyvinyl acetate, polyvinyl alcohol, etc.) may be provided between the layer containing the redox compound of the present invention and the photosensitive emulsion layer containing a hydrazine nucleating agent.

The first and second photosensitive silver halide emulsions used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, and silver iodochlorobromide.

The average grain size of the first and second photosensitive silver halides (for example, 0.7 μm or less) used in the present invention is more 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% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size.

The first and second photosensitive silver halide grains in the photographic emulsion may have regular crystals such as cubic or octahedral, or irregular (such as spherical, plate-like, etc.). It may have an irregular crystal or a compound of these crystal forms.

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. Two or more kinds of silver halide emulsions formed separately may be used as a mixture.

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.

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 intrinsic sensitivity range of silver halide, or safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the range of 350 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.

Different by the molar extinction coefficient of the dye, but usually 10 ^-2 g / m ² ~
It is added in the range of 1 g / m ² . Preferably 50mg~500mg / m ²
It is.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169, some of which are as follows.

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] for the non-photosensitive hydrophilic colloid layer of the present invention. It is added to the coating solution.

These dyes can be used in combination of two or more kinds.

The dye of the present invention is used in an amount necessary to enable handling in a bright room.

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 first and second photosensitive silver halide emulsions used in the method of the present invention need 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 iridium may be contained. Specific examples are U.S. Patent No. 2,448,060,
It is described in British Patent 618,061 and the like.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin.

Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention, but it is better not to add it to the second silver halide emulsion layer.

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.

Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

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.

Further, a polymer latex such as polyalkyl acrylate can be contained for dimensional stability.

Examples of development accelerators suitable for use in the present invention or accelerators for nucleation transmission development include JP-A-53-77616 and JP-A-54-377.
In addition to the compounds disclosed in Nos. 32, 53-137, 133, 60-140,340, and 60-14959, various compounds containing an N or S atom are effective.

 Next, specific examples are listed.

n-C ₄ H ₉ N (C ₂ H ₄ OH) ₂ These accelerators have an optimum addition amount depending on the kind of the compound, but 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^−3.
Preferably employed in the range of to 0.1 g / m ^2.

To obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or U.S. Pat.
It is not necessary to use a highly alkaline developer close to pH 13 described in No. 5, 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 ion as a preservative, and has a pH of 10.5
With a developer having a pH of from 12.3 to 12.3, particularly from 11.0 to 12.0, a negative image having a sufficiently high contrast can be obtained.

There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-). 3-pyrazolidone), aminophenols (for example, N
-Methyl-p-aminophenol) or the like can be used alone or in combination.

The silver halide light-sensitive material of the present invention particularly contains dihydroxybenzenes as a main developing agent and 3
-Suitable for processing with a developer containing pyrazolidones or aminophenols. Preferably, the developer contains 0.05 to 0.5 mol / dihydroxybenzenes / mol.
, 3-pyrazolidones or aminophenols are 0.
It is used in the range of 06 mol / or less.

Further, as described in U.S. Pat. No. 4,269,929, the development speed can be increased by adding amines to a developer to shorten the development time.

Other developers include pH buffers such as sulfites, carbonates, borates and phosphates of alkali metals, bromides,
It can contain a development inhibitor such as iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. Also, if necessary, a water softener, a dissolution aid, a color tone agent,
It may contain a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, and a silver stain inhibitor for a film (for example, silver 2-mercaptobenzimidazole sulfonate).

As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound known to have an effect as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C.

Although it is preferable to use an automatic developing machine for photographic processing, according to the method of the present invention, even if the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is set to 90 seconds to 120 seconds. Thus, a photographic characteristic of a negative tone with a sufficiently high contrast can be obtained.

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. Further, compounds described in JP-A-60-93,433 or compounds described in JP-A-62-186259 can be used as a pH buffer used in the developer.

Hereinafter, the present invention will be described in detail with reference to Examples. The following formulation was used for the developer.

Example 1. (Preparation of hydrazine-containing layer emulsion) Emulsion A: 0.37 mol of silver nitrate aqueous solution, 1 mol / mol of silver
(NH ₄ ) ₃ RhCl ₆ corresponding to × 10 ⁻⁷ mol and 5 × 10 ⁻⁷
An aqueous solution of a halogen salt containing 0.11 mol of potassium bromide and 0.27 mol of sodium chloride containing K ₃ IrCl ₆ equivalent to mol is stirred into a gelatin aqueous solution containing sodium chloride and 1,3-dimethyl-2-imidazolidinthione. The mixture was added at 45 ° C. for 12 minutes by a double jet method to obtain silver chlorobromide grains having an average grain size of 0.20 μm and a silver chloride content of 70 mol%, thereby forming nuclei. Then likewise 0.
03 mol silver nitrate aqueous solution, 0.19 mol potassium bromide,
A halogen salt aqueous solution containing 0.47 mol of sodium chloride was added by a double jet method over 20 minutes.

Thereafter, 1 × 10 ⁻³ mol of KI solution was added to perform conversion, washed with flocculation method according to a conventional method, washed with 40 g of gelatin, adjusted to pH 6.5 and pAg 7.5, and furthermore thiol per mol of silver was added. Sodium sulfate 5mg, chloroauric acid 8
and sodium benzenethiosulfonate 7 mg, heated at 60 ° C. for 45 minutes, subjected to a chemical sensitization treatment, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 150 mg as a stabilizer. Further, proxel and phenoxyethanol were added, and 1 × per mole of silver was added as a sensitizing dye.
10 ^-3 moles of 5-{[3- (4-sulfobutyl) -5-chloro-2-benzooxazolidylidene] ethylidene}-
1-hydroxyethoxyethyl-3- (2-pyridyl)
-2-Thiohydantoin potassium salt was added. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 9%).

Emulsion B: 4 parts per mole of silver in gelatin aqueous solution kept at 50 ° C
An aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were added simultaneously for 60 minutes in the presence of × 10 ^-7 mol of potassium iridium (III) chloride and ammonia, and the pAg between them was added.
By keeping the ratio at 7.8, a cubic monodispersed emulsion having an average grain size of 0.28 μm and an average silver iodide content of 0.3 mol% was prepared. The emulsion was desalted by a flocculation method, and after adding 40 g of inert gelatin per mol of silver, the emulsion was kept at 50 ° C. and 4-hydroxy-6-methyl-1,3,3a was added per mol of silver. , 7-tetrazaindene (150 mg), proxel and phenoxyethanol were added, and 1 × 10 ^-3 mol of 5,5'-dichloro-9-mol / silver was used as a sensitizing dye.
Ethyl-3,3'-bis (3-sulfopropyl) oxacarbocyanine sodium salt 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. (Coefficient of variation: 10%) These emulsions were divided into 2 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and 5 × 10 ^-4 mol per mol of silver.
Moles of a short-wave cyanine dye represented by the following structural formula (a), and a water-soluble latex represented by (b) (200 mg / m ² )
Hydroquinone (50 mg / m ² ) and a dispersion of polyethyl acrylate (200 mg / m ² ) 1,2-bis (vinylsulfonylacetamido) ethane as a hardener and a hydrazine compound of the present invention were added as shown in Table 1. .

(Preparation of Redox Compound-Containing Layer Emulsion) Emulsion A: 1.0 M silver nitrate aqueous solution and 3 × 10 ⁻⁷ per mol of silver
Containing (NH ₄ ) ₃ RhCl ₆ and 0.3 M potassium bromide
An aqueous halogen salt solution containing 0.74 M sodium chloride was added to sodium chloride and an aqueous gelatin solution containing 1,3-dimethyl-2-imidazolidinethione at 45 ° C. while stirring.
For 30 minutes by a double jet method to obtain silver chlorobromide grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. Thereafter, the mixture was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added to adjust the pH to 6.5 and pAg7.5. The mixture was heated and subjected to a chemical sensitization treatment, and 150 mg of 1,3,3a, 7-tetrazaindene was added as a stabilizer. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.28 μm and a silver chloride content of 70 mol%. (Coefficient of variation 10%).

This emulsion was divided and used as a sensitizing dye in an amount of 1 per mole of silver.
× 10 ^-3 mol of 5- [3- (4-sulfobutyl) -5-chloro-2-oxazolidylidene] -1-hydroxyethyl-3- (2-pyridyl) -2-thiohydantoin was added, and A dispersion of 2 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and polyethyl acrylate was added to 50
mg / m ² , 1,2-bis (vinylsulfonylacetamido) ethane 40 mg / m ² and a redox compound represented by the general formula (II) of the present invention were added as shown in Table 1.

Hydrazine content in the lowermost layer (Ag 3.6 g / m ² , gelatin 2 g /
m ² ) and a layer containing a redox compound (Ag 0.4 g / m ² , gelatin 0.5 g / m ² ) via an intermediate layer (gelatin 0.5 g / m ² ).
m ² ) and gelatin 1.0 g / m ² as a protective layer thereon, an amorphous SiO ₂ matting agent 40 mg / m ² having a particle size of about 3.5 μm, methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² ,
Hydroquinone 200 mg / m ² and silicone oil and fluorine surfactant represented by the following structural formula as a coating aid And a layer containing sodium dodecylbenzenesulfonate were simultaneously applied to prepare samples as shown in Table 1.

The back layer and the back protective layer were applied according to the following formulation.

(Back protective layer)

Gelatin 0.8g / m ² Polymethyl methacrylate fine particles (average particle size 4.5μ) 30m
g / m ² dihexyl -α- sulfo succinate inert sodium salt 15 mg / m
² Dodecylbenzenesulfonic acid sodium salt 15 mg / m ² Fluorine surfactant 5 mg / m ² Sodium acetate 40mg / m ² FIG. 1 schematically shows the layer structure.

After storing the obtained sample under the condition of 25 ° C. and 65% RH for 10 days, the swelling ratio was evaluated.

 The evaluation method is as follows.

<Swelling Ratio> The swelling percentage was determined by measuring the thickness of the hydrophilic colloid layer in the silver halide photographic material, and immersing the silver halide photographic material in distilled water at 25 ° C. for 1 minute. By measuring the percentage change in layer thickness as compared to the layer thickness measured in. ) These samples were exposed to tungsten light at 3200 ° K through an optical wedge and a contact screen (Fuji film, 150L chain dot type), developed at 34 ° C for 30 seconds, fixed, washed and dried.

Table 1 shows the measurement results of the photographic properties, black spots, and swelling ratio of the obtained samples. The halftone and γ were represented by the following equations.

* Halftone = Exposure to give 95% halftone dot area ratio (logE95
%)-Exposure to give a dot area ratio of 5% (logE5%) The black pots were evaluated on a 5-point scale by microscopic observation.
"5" represents the best and "1" represents the worst quality.
“5” or “4” is practical, and “3” is poor, but barely practical and “2” or “1” is impractical.
Those between "4" and "3" were rated "3.5".

The sample of the present invention maintains high contrast, has a wide halftone gradation, and has improved black spots. In comparison, the samples of comparative examples having a low swelling ratio (1 to 4,16 to 18,25,30,35,40)
Black spots are remarkably bad and lack high contrast. In addition, the sample of the comparative example having a high swelling ratio (13 to 15,22 to 24,29,34,39,44)
The black dots are good, but the halftone is much narrower than the sample of the present invention.

Example 2 (Preparation of a hydrazine-containing layer emulsion) Emulsion C: An aqueous gelatin solution kept at 50 ° C. in an amount of 5.
After simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of 0 × 10 ⁻⁶ mol of (NH ₄ ) ₃ RhCl ₆ , gelatin is removed after removing soluble salts by a method well known in the art. In addition, 2-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer without chemical aging. This emulsion was a cubic monodispersed emulsion having an average size of 0.15 μm.

The following hydrazine compound was added to this emulsion. A dispersion of polyethyl acrylate was added at 200 mg / m ² , and 1,2-bis (vinylsulfonylacetamide) ethane as a hardener was added as shown in Table 2.

(Preparation of Redox Compound-Containing Layer Emulsion) Emulsion C was mixed with 50 mg of a dispersion of polyethyl acrylate.
/ m ² , 40 mg / m ^{2 of} 1,2-bis (vinylsulfonylacetamido) ethane and a redox compound represented by the general formula (II) of the present invention were added as shown in Table 2.

Polyester film (150 mu) of hydrazine-containing layer on a support bottom layer (Ag3.6g / m ^2, gelatin 2 g / m ²⁾ in addition, a layer via an intermediate layer (gelatin 0.5 g / m ²⁾ containing a redox compound (Ag 0.4 g / m ² , gelatin 0.5 g / m ² )
On this, gelatin 1.0 g / m ² as a protective layer and polymethyl methacrylate particles (average particle size 2.5
μ) 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.

As shown in FIG. 2, this sample was exposed through a manuscript, developed at 38.degree. C. for 20 seconds, fixed, washed with water, dried, and then printed to obtain the image quality of the printed characters. An evaluation was performed.

Character image quality of 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 a halftone dot area of 50% 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 cannot be said to be 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 swelling ratio was measured in the same manner as in Example 1.

The results are shown in Table 2. The sample of the present invention has excellent character image quality.

[Brief description of the drawings]

FIG. 1 is a schematic view of a cross section of a sample in Example 1 of the present invention. FIG. 2 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 pasting base (b) Line drawing original (black part shows line drawing) (c) Transparent or translucent pasting base (d) Halftone original (black part shows line drawing) (E) Photographic material for return (the shaded area indicates the photosensitive layer)

Claims (4)

(57) [Claims] A first photosensitive silver halide emulsion layer containing at least a hydrazine derivative and a second photosensitive silver halide emulsion layer on the same surface of a support, wherein the second photosensitive silver halide emulsion layer comprises An emulsion layer, or a silver halide photographic material containing a redox compound capable of releasing a development inhibitor by being oxidized to a hydrophilic colloid layer other than the above, having a photosensitive silver halide emulsion layer and a hydrophilic colloid layer The swelling ratio on the side is 100% or more 2
A silver halide photographic light-sensitive material characterized by being at most 00%. 2. The redox compound according to claim 1, wherein said redox group includes hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones. The silver halide photographic light-sensitive material according to the above 1). 3. The silver halide photographic material according to claim 1, wherein the redox compound has a hydrazine as a redox group. 4. A redox compound represented by the following general formula (R-
The silver halide photographic light-sensitive material according to claim 1, wherein the material is represented by (1), (R-2) or (R-3). General formula (R-1) General formula (R-2) General formula (R-3) In these formulas, R ₁ represents an aliphatic group or an aromatic group.
G ₁ -SO- group, -SO ₂ - group or Represents G ₂ is a mere bond, -O-, -S- or And R ₂ represents a hydrogen atom or R ₁ . A ₁ and A ₂ represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In the general formula (R-1), at least one of A ₁ and A ₂ is a hydrogen atom. A ₃ is synonymous with A ₁ or Represents A ₄ represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G ₁ -G ₂ -R _1. Time represents a divalent linking group, and t represents 0 or 1. PUG represents a development inhibitor.