JP2694570B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a high contrast negative image, a high sensitivity negative image and a good halftone dot image quality. The present invention relates to a silver halide photographic 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.

Especially in the line drawing process, manuscripts are created by pasting typesetting characters, handwritten characters, illustrations, and half-tone dots. 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 the reduction, the number of lines / inch 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 light-sensitive material is more strongly affected by the chromatic aberration of the lens, so that the image quality is likely to deteriorate. This deterioration is more remarkable for a xenon lamp light source.

As a system that meets the demands of a wide latitude, the effective concentration of sulphite ions in a lithographic silver halide photosensitive material composed of silver chlorobromide (at least silver chloride content of 50% or more) is extremely low (usually 0.1 mol / l 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 portion and a non-image portion are clearly distinguished by processing with a hydroquinone developer. However, in this method, the concentration of sulfurous acid in the developer is low, so the development is extremely unstable against air oxidation. Various efforts and efforts have been made to keep the solution activity stable, and the processing speed has been increased. However, the current situation is that the work efficiency is reduced due to the extremely slow speed.

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, 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 / l or more at pH 11.0 to 12.3, and has good storage stability. Is treated with a developing solution 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.

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 material for the bright room used in the plate collecting and reversing processes is a developed film on which characters or halftone images are formed as an original, and these originals and the reversing photosensitive material are contact-exposed to form a negative image / It is a light-sensitive material used for positive image conversion or positive image / positive image conversion. However, halftone images, line images, and character images are negative images / positive images according to their halftone dot area, line width, and character image width. It is required to have the ability to perform image conversion, the ability to adjust the tone of a halftone dot image and the width of a character line image, and a light-sensitive material for a bright room maple has been provided that meets these requirements.

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) A film on which characters or line images are formed (line drawing original) (b)
And a film on which a halftone image is formed (halftone original)
(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.

As an attempt to improve the original reproducibility and the outline image, JP-A-61-213847 and JP-A-64-72,139 disclose a method of releasing a development inhibitor in a silver image manner from a redox compound having a carbonyl group. However, all of the features of the system using hydrazine are sharp halftone dot quality, processing stability, and less fluctuation of the image due to changes in the developer composition such as pH and sodium sulfite. It was not sufficient for the purpose of being compatible with the above.

Therefore, there has been a demand for the development of a means having a sharp halftone dot quality, excellent original reproducibility, and a blank image with a stable developing solution and little fluctuation in the composition of the processing solution.

(Object of the Invention) A first object of the present invention is to provide a photographic light-sensitive material having a wide exposure latitude in line drawing, a super-hard contrast (particularly, a γ value of 10 or more) and a high resolution.

It is a second object of the present invention to provide a photographic light-sensitive material which can be handled in a bright room, has particularly good quality of extracted characters, and has no trace of tape sticking.

A third object of the present invention is to provide a super-high-contrast photographic light-sensitive material capable of reproducing a line drawing well and having a high background density (Dmax).

A fourth object of the present invention is to provide a super-high-contrast photographic light-sensitive material in which the variation of the obtained image is small even if the composition of the developing solution varies.

(Constitution of the Invention) The objects of the present invention have at least one silver halide photographic emulsion layer, and the photographic emulsion layer or at least one other hydrophilic colloid layer is represented by the following general formula (I). The present invention has been achieved by a silver halide photographic light-sensitive material characterized by containing at least one redox compound capable of releasing a development inhibitor by being oxidized with the compound, each compound having a hydrazine group as a redox group.

General formula (I) In the general formula (I), R ¹ and R ² are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group or an acyl group.

R ¹⁰ is an alkyl group, aralkyl group, alkoxy group, arylamino group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group,
Sulfo group, phosphoric acid amide group, carboxyl group or L
_l represents an X group. k represents 0, 1 or 2.

R ¹¹ represents a group having the same meaning as R ³ below or an L ₁ X group.

Y ¹ is -CONH-, -SO ₂ NH-, (Y ² is -O-, -NH- or Represents R ³ represents a group selected from the group consisting of an aliphatic group, an aromatic group and a heterocyclic group).

R ⁴ represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an oxycarbonyl group and a carbamoyl group.

G is a carbonyl group, a sulfonyl group, a sulfinyl group,
Imino methylene group and Represents a divalent group selected from the group consisting of:

However, in the above general formula (I) At least one of the portion and R ⁴ has an adsorption promoting group on the silver halide grain represented by L ₁ X. Where X
Is a group containing a cyclic thioamide group, a group containing a mercapto group,
It represents a group selected from the group consisting of a group containing a disulfide bond and a 5- to 6-membered nitrogen-containing heterocyclic group, L represents a divalent linking group, and l represents an integer of 0 to 1.

Hereinafter, the compound represented by formula (I) will be described in detail.

R ¹ and R ² are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group or an acyl group.

The sulfonyl group represented by R ¹ and R ² above,
Examples thereof include an alkylsulfonyl group having 20 or less carbon atoms or an allolsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of the substituent constants according to Hammett's rule becomes -0.5 or more).

The sulfonyl group represented by R ¹ and R ² is
Specifically, it is described in US Pat. No. 4,478,928.

Examples of the acyl group represented by R ¹ and R ² include an acyl group having 20 or less carbon atoms. The preferred acyl group is a benzoyl group, a benzoyl group substituted so that the sum of the substituent constants according to Hammett's rule is −0.5 or more, a linear or branched aliphatic acyl group, or a cyclic aliphatic acyl group. Can be mentioned. Each group represented by R ¹ and R ² may further have a substituent. Examples of these substituents include a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group.

In the present invention, it is preferable that both R ¹ and R ² are hydrogen atoms.

R ³ represents a group selected from the group consisting of an aliphatic group, an aromatic group and a heterocyclic group.

Examples of the aliphatic group represented by R ³ include a linear, branched or cyclic alkyl group, alkenyl group and alkynyl group.

The aromatic group represented by R ³ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocyclic group represented by R ³ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of nitrogen atom, oxygen atom and sulfur atom. These may be a single ring or may form a condensed ring with another aromatic ring or a heterocycle. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, for example, pyridyl group, imidazolyl group, quinolyl group, benzimidazolyl group, pyrimidyl group, pyrazolyl group, isoquinolinyl group, thiazolyl group, benzthiazolyl group. Groups, etc.

The above R ³ may be further substituted (may be substituted with two or more substituents, or may be linked to each other to form a ring). Such substituents include
Alkyl group, aralkyl group, alkoxy group, arylamino group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, arylalkylthio group, arylthio group, sulfonyl group , A sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a phosphoric acid amide group and a carboxyl group.

In the present invention, R ³ is preferably an aromatic group, and more preferably a phenyl group.

R ⁴ represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an oxycarbonyl group and a carbamoyl group.

Further, G is a carbonyl group, a sulfonyl group, a sulfinyl group, an iminomethylene group, and Represents a divalent group selected from the group consisting of

Of the substituents represented by R ⁴ , when G is a carbonyl group, R ⁴ is a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfone). Amidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group), aryl group (eg, phenyl group, 3,
A 5-dicrylophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group), a carbamoyl group (eg, an unsubstituted carbamoyl group, a methylcarbamoyl group, a phenylcarbamoyl group) and the like are preferable. Among these, a hydrogen atom is more preferable.

When G is a sulfonyl group, R ⁴ is preferably an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxyphenylmethyl group) or an amino group (eg, dimethylamino group).

When G is a sulfinyl group, R ⁴ is preferably a cyanobenzyl group or a methylthiobenzyl group.

The above G is In the case of, R ⁴ 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 is an N-substituted or unsubstituted iminomethylene group, R ⁴ is preferably a methyl group, an ethyl group or a phenyl group.

Note that R ⁴ may have a substituent. As the substituent, in addition to the above-mentioned substituents capable of substituting for R ³ , for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group and a nitro group can be applied.

G in the general formula (I) is most preferably a carbonyl group.

R ⁴ also splits the G-R ⁴ moiety from the rest of the molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the R ⁴ moiety, and specifically, one that can be represented by the general formula (a).

In formula (a) —R ⁵ —Z, Z is a group capable of nucleophilically attacking G and splitting the G—R ⁵ —Z moiety from the residual molecule,
R ⁵ is obtained by removing one hydrogen atom from R ⁴ , and Z can nucleophilically attack G to form a cyclic structure with G, R ⁵ , and Z.

More specifically, Z easily undergoes a nucleophilic reaction with G when the hydrazine compound of the general formula (I) produces the next reaction intermediate due to oxidation or the like. R ³ —N═N—G—R ⁵ — Z R ³ —N═N is a group capable of splitting N group from G, and specifically, OH, SH or NHR ⁶ (R ⁶ is a hydrogen atom, an alkyl group, an aryl group, —COR ⁷ , or —SO ₂ R is ^7, R ⁷ is a hydrogen atom, an alkyl group, an aryl group, and heterocyclic group), it may be a functional group which reacts directly with G, such as COOH, (wherein, OH, SH, NHR ⁶ and -COOH may be temporarily protected so as to generate these groups by hydrolysis with alkali etc.) (R ⁸ and R ⁹ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and react with G by reacting with a nucleophile such as a hydroxide ion or a sulfite ion. It may be a functional group capable of

The ring formed by G, R ⁵ and Z 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) Wherein, R _b ¹ ~R _b ⁴ is 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 a carbon number 6
~ 12), 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,
(N + m) is 1 or 2.

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

 Z 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 or a halogen atom, 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, 1 or 2. q represents 1-4. R _c
¹ , R _c ² and R _c ³ may combine with each other to form a ring as long as Z is capable of intramolecular nucleophilic attack on G.

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, p is 1 or 2 when q is 1, p is 0 or 1 when q is 2, p is 0 or 1 when q is 3, and q is 2 Or 3 for CR _c ¹
R _c ² may be the same or different.

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

At least one of R ³ and R ⁴ has a hydrogen atom contained in the group thereof substituted by an adsorption promoting group to the silver halide grain.

The above-mentioned adsorption promoting group for silver halide can be represented by the following formula.

XL _{1 In the} above formula, X is a group containing a cyclic thioamide group,
Represents a group selected from the group consisting of a group containing a mercapto group, a group containing a disulfide bond, and a 5- to 6-membered nitrogen-containing heterocyclic group, L represents a divalent linking group, and l represents 0 to 1 Represents an integer.

Specific examples of the cyclic thioamide group represented by X include 4-thiazoline-2-thione and 4-imidazoline-
2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, 1,3,4-thiadiazoline-
2-thione, 1,3,4-oxadiazoline-2-thione,
Mention may be made of benzimidazoline-2-thione, benzoxazoline-2-thione, and benzothiazoline-2-thione. These may further have a substituent. Note that useful thioamide groups include, for example, U.S. Patent Nos. 4,030,925, 4,031,127, 4,080,207, and 4,2.
45,037, 4,255,511, 4,266,031, 4,276,36
No. 4 and "Research Disclosure" (Resea
rch Disclosure) Volume 151, No.15162 (November 1976)
Also, it can be selected from those disclosed in Vol. 176, No. 17626 (December 1978).

Examples of the group containing a mercapto group represented by X above include
For example, a mercapto-substituted aliphatic group, a mercapto-substituted aromatic group, or a mercapto-substituted heterocyclic group (when the carbon atom to which the mercapto group is bonded is a nitrogen atom next to it, it has a thioamide group having a tautomeric relationship with this It has the same meaning as a cyclic group, and specific examples thereof are the same as those listed above.).

Examples of the 5- to 6-membered nitrogen-containing heterocyclic group represented by X include 5- to 6-membered nitrogen-containing heterocyclic rings composed of a combination of nitrogen atom, oxygen atom, sulfur atom and carbon atom. Preferred specific examples include benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole and triazine. These may further have a substituent. Examples of the substituent include the substituents that can be substituted with the above-mentioned substituents represented by R ³ .

In the present invention, a mercapto-substituted nitrogen-containing heterocyclic group (a cyclic group containing a thioamide group) or a 5- to 6-membered nitrogen-containing heterocyclic group is preferable. Specific examples of the mercapto-substituted nitrogen-containing heterocyclic group include 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group and 5-
Mercaptotetrazole group, 2-mercapto-1,3,4-
Examples thereof include an oxadiazole group and a 2-mercaptobenzoxazole group. Specific examples of the 5- or 6-membered nitrogen-containing heterocyclic group include a benzotriazole group, a benzimidazole group and an imidazole group.

The divalent linking group represented by L is a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom, or an atomic group containing at least one atom of these. Examples of these are alkylene groups, alkenylene groups, alkynylene groups, arylene groups, -O-, -S-, -NH-,
Examples of the group include —CO— and —SO ₂ — (these groups may have a substituent) alone or in a heterocyclic bond.

 Specific examples of the linking group are shown below.

_{-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-, or more linking groups may be substituted with more suitable substituents. Examples of the substituent include the substituents that can be substituted with the above-mentioned substituents represented by R ³ .
The adsorption promoting group on the silver halide grain is preferably a group substituted with R ³ .

In the general formula (I), R ¹⁰ represents a substituent or XL ₁ , and specifically has the same meaning as the substituent of R ³ . k is 0, 1,
Or 2, and when k is 2, R ¹⁰ may be the same or different.

R ¹¹ represents the same or L _l X and R ³ described above, preferably L _l X.

Y ¹ is −CONH−, −SO ₂ NH−, (Y ² is -O-, -NH-, Represents ), Y ¹ is —SO ₂ NH, Is particularly preferred.

More preferably, the R ¹¹ -Y ¹ group is O to the hydrazino group.
Alternatively, it is substituted at the P position.

As the adsorption promoting group on the surface of the silver halide grain, in addition to the above-mentioned patents, U.S. Patent Nos. 4,385,108 and 4,459,3
47, JP-A-59-195233, 59-200231, 59-20
No. 1047, No. 59-201048, No. 59-201049, No. 61-1707
33, 61-170744, 62-948, JP-A-63-234,24
4, ibid. 63-234,245, ibid. 62-234,246, Japanese Patent Application No. 62-247,47
8, 〃63-105,682, 〃63-116,239, 〃63-147,339, 〃
The publications and specifications such as 63-179,760 and 63-229,163 can be mentioned.

Hereinafter, specific examples of the hydrazine derivative represented by the general formula [I] will be described. However, it is not limited to these.

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. 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 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 a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.

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 1 to 20 carbon atoms in the alkyl portion) Monocyclic or bicyclic)),
An alkoxy group (preferably having 1 to 30 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 30 carbon atoms), 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 1 to 40 carbon atoms), a phosphoric amide group (preferably having 1 to 40 carbon atoms) and the like. .

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

A ₁ and A ₂ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) 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 becomes -0.5 or more, or a linear or branched or cyclic unsubstituted or substituted fatty acid) A group acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, or a sulfonic acid group) is preferable.

A ₁ and A ₂ are most preferably hydrogen atoms.

A ₃ is a hydrogen atom, Is most 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. t represents 0 or 1.

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.
Nos. 5,58,98,728 and 58,209,737, etc., which release PUG from the γ-position of an enamine by electron transfer of a portion having an enamine structure of a nitrogen-containing heterocycle described in JP-A-57 / 1982
-56,837, which releases PUG by an intramolecular ring-closing reaction of an oxy group formed by electron transfer to a carbonyl group conjugated with a nitrogen atom of a nitrogen-containing heterocycle; US Pat.
4,146,396 (JP-A-52-90932), JP-A-59-93,442
JP-A-59-75475, JP-A-60-249148, JP-A-6
No. 0-249149, etc. accompanied by formation of aldehydes, PUG
Which release the following: JP-A-51-146,828 and JP-A-57-179,842
Releasing PUG with decarboxylation of the carboxyl group described in Nos. 59-104,641; -O-COOCR _a R _b -PUG (R _a , R _b
Represents a monovalent group. ), Releasing PUG with decarboxylation and subsequent formation of aldehydes; releasing PUG with formation of an isocyanate described in JP-A-60-7429; U.S. Pat. No. 4,438,193 PU by the coupling reaction with the oxidant of the color developer described in No.
Examples thereof include those that release G.

The divalent group represented by Time in the general formulas (R-1), (R-2) and (R-3) is preferably the following general formula (T-
From 1), it is represented by the general formula (T-6). In these, ** indicates the site where Time binds to PUG, and * indicates the other site.

General formula (T-1) Wherein W is an oxygen atom, a sulfur atom or R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2. When t is 2, two Represents the same or different. R ₁₁ and R ₁₂
Is a substituent, and typical examples of R ₁₃ are each R ₁₄
Group, R ₁₄ CO- group, R ₁₄ SO ₂ -group, Or And the like. Here, R ₁₄ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₁₅ represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom.

Each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group, and includes the case where they are linked to form a cyclic structure. General formula (T
Specific examples of the group represented by -1) include the following groups.

General formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and Nu represents an electrophilic group. Link is a group that can undergo a more nucleophilic attack and cleave the bond with the ** mark.
Nu represents a linking group that sterically relates to E so that an intramolecular nucleophilic substitution reaction can occur. General formula (T-2)
Specific examples of the group represented by are, for example, the following.

General formula (T-3) In the formula, W, R ₁₁ , R ₁₂ and t have the same meanings as described for (T-1). Specific examples include the following groups.

General formula (T-4) General formula (T-5) General formula (T-6) In the formula, W and R ₁₁ have the same meaning as described in formula (T-1). Specific examples of the group represented by the general formula (T-6) include the following groups.

Further, as the Time, the general formula (T-1) to the general formula (T-
Groups formed by combining a plurality of groups represented by 6) are also useful. Preferred examples thereof are shown below. *, *
* Has the same meaning as in formulas (T-1) to (T-6).

Specific examples of these divalent linking groups represented by Time are also described in detail in JP-A-61-236,549, JP-A-64-88451, 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 inhibitors represented by PUG or (Time _t PUG are known development inhibitors having a heteroatom and bonded through a heteroatom, such as CEKMess and "The Theory of Photographic Process" by THJames
Processes, 3rd Edition, 1966, Macmilla
n) It is described in pages 344 to 346 of the company. Specifically, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, mercaptopyrimidines, mercaptobenzimidazoles, mercaptobenzthiazoles, mercaptobenzoxazoles,
Mercaptothiadiazoles, benztriazoles,
Benzimidazoles, indazoles, adenines,
Guanines, tetrazoles, tetraazaindenes,
Triazaindenes, mercaptoarenes and the like can be mentioned.

The development inhibitor represented by PUG may be substituted. Examples of the substituent include the following, but 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, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, sulfooxy group, phosphono group A phosphinico group, a phosphoric acid amide group and the like.

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.

 The main development inhibitors are shown below.

1 Mercaptotetrazole derivative (1) 1-ferul-5-mercaptotetrazole (2) 1- (4-hydroxyphenyl) -5-mercaptotetrazole (3) 1- (4-aminophenyl) -5-mercaptotetrazole (4) 1- (4-carboxyphenyl) -5-mercaptotetrazole (5) 1- (4-chlorophenyl) -5-mercaptotetrazole (6) 1- (4-methylphenyl) -5-mercaptotetrazole (7) 1- ( 2,4-dihydroxyphenyl) -5-mercaptotetrazole (8) 1- (4-sulfamoylphenyl) -5-mercaptotetrazole (9) 1- (3-carboxyphenyl) -5-mercaptotetrazole (10) 1 -(3,5-Dicarboxyphenyl) -5-mercaptotetrazole (11) 1- ( -Methoxyphenyl) -5-mercaptotetrazole (12) 1- (2-methoxyphenyl) -5-mercaptotetrazole (13) 1- [4- (2-hydroxyethoxy) phenyl] -5-mercaptotetrazole (14) 1 -(2,4-Dichlorophenyl) -5-mercaptotetrazole (15) 1- (4-dimethylaminophenyl) -5-mercaptotetrazole (16) 1- (4-nitrophenyl) -5-mercaptotetrazole (17) 1 , 4-Bis (5-mercapto-1-tetrazolyl) benzene (18) 1- (α-naphthyl) -5-mercaptotetrazole (19) 1- (4-sulfophenyl) -5-mercaptotetrazole (20) 1- (3-Sulfophenyl) -5-mercaptotetrazole (21) 1- (β-naphthyl) -5-mercaptotetrazole (22) 1-methyl-5-mercaptotetrazole (23) 1-ethyl-5-mercaptotetrazole (24) 1-propyl-5-mercaptotetrazole (25) 1-octyl-5-mercaptotetrazole (26) 1-dodecyl -5-mercaptotetrazole (27) 1-cyclohexyl-5-mercaptotetrazole (28) 1-palmityl-5-mercaptotetrazole (29) 1-carboxyethyl-5-mercaptotetrazole (30) 1- (2,2-di Ethoxyethyl) -5-mercaptotetrazole (31) 1- (2-aminoethyl) -5-mercaptotetrazole hydrochloride (32) 1- (2-diethylaminoethyl) -5-mercaptotetrazole (33) 2- (5- Mercapto-1-tetrazolyl) ethyltrimethylammonium chloride (34) 1- ( - phenoxycarbonyl) -5
-Mercaptotetrazole (35) 1- (3-maleimidophenyl) -6-mercaptotetrazole 2 mercaptotriazole derivative (1) 4-phenyl-3-mercaptotriazole (2) 4-phenyl-5-methyl-3-mercaptotriazole (3) 4,5-Diphenyl-3-mercaptotriazole (4) 4- (4-carboxyphenyl) -3-mercaptotriazole (5) 4-methyl-3-mercaptotriazole (6) 4- (2-dimethylamino Ethyl) -3-mercaptotriazole (7) 4- (α-naphthyl) -3-mercaptotriazole (8) 4- (4-sulfophenyl) -3-mercaptotriazole (9) 4- (3-nitrophenyl)- 3-mercaptotriazole 3 mercaptoimidazole derivative (1) -Phenyl-2-mercaptoimidazole (2) 1,5-diphenyl-2-mercaptoimidazole (3) 1- (4-carboxyphenyl) -2-mercaptoimidazole (4) 1- (4-hexylcarbamoyl) -2- Mercaptoimidazole (5) 1- (3-nitrophenyl) -2-mercaptoimidazole (6) 1- (4-sulfophenyl) -2-mercaptoimidazole 4 Mercaptopyrimidine derivative (1) Thiouracil (2) Methylthiouracil (3) Ethylthiouracil (4) Propylthiouracil (5) Nonylthiouracil (6) Aminothiouracil (7) Hydroxythiouracil 5 Mercaptobenzimidazole derivative (1) 2-Mercaptobenzimidazole (2) 5-Carboxy-2-mercapto Benz imida (3) 5-amino-2-mercaptobenzimidazole (4) 5-nitro-2-mercaptobenzimidazole (5) 5-chloro-2-mercaptobenzimidazole (6) 5-methoxy-2-mercaptobenzimidazole (7) 2-mercaptonaphthoimidazole (8) 2-mercapto-5-sulfobenzimidazole (9) 1- (2-hydroxyethyl) -2-mercaptobenzimidazole (10) 5-caproamide-2-mercaptobenzimidazole (9) 11) 5- (2-Ethylhexanoylamino) -2-mercaptobenzimidazole 6-mercaptothiadiazole derivative (1) 5-methylthio-2-mercapto-1,3,4-thiadiazole (2) 5-ethylthio-2-mercapto -1,3,4-thiadiazole (3) 5- (2-di Methylaminoethylthio) -2-mercapto-1,3,4-thiadiazole (4) 5- (2-carboxypropylthio) -2-mercapto-1,3,4-thiadiazole (5) 2-phenoxycarbonylmethylthio- 5-mercapto-1,3,4-thiadiazole 7 mercaptobenzthiazole derivative (1) 2-mercaptobenzthiazole (2) 5-nitro-2-mercaptobenzthiazole (3) 5-carboxy-2-mercaptobenzthiazole (4) ) 5-Sulfo-2-mercaptobenzthiazole 8 mercaptobenzoxazole derivative (1) 2-mercaptobenzoxazole (2) 5-nitro-2-mercaptobenzoxazole (3) 5-carboxy-2-mercaptobenzoxazole (4) 5-sulfo-2-mercaptobenzoxazo 9 benzotriazole derivative (1) 5,6-dimethylbenzotrial (2) 5-butylbenzotriazole (3) 5-methylbenzotriazole (4) 5-chlorobenzotriazole (5) 5-bromobenzotriazole (6) ) 5,6-Dichlorobenzotriazole (7) 4,6-Dichlorobenzotriazole (8) 5-Nitrobenzotriazole (9) 4-Nitro-6-chloro-benzotriazole (10) 4,5,6-Trichlorobenzo Triazole (11) 5-Carboxybenzotriazole (12) 5-Sulfobenzotriazole Na salt (13) 5-Methoxycarbonylbenzotriazole (14) 5-Aminobenzotriazole (15) 5-Butoxybenzotriazole (16) 5-Ureido Benzotriazole (17) Benzotriazole (18) 5-fe Xycarbonyl benzotriazole (19) 5- (2,3-dichloropropyloxycarbonyl) benzotriazole 10 Benzimidazole derivative (1) Benzimidazole (2) 5-chlorobenzimidazole (3) 5-nitrobenzimidazole (4) 5 -N-Butylbenzimidazole (5) 5-methylbenzimidazole (6) 4-chlorobenzimidazole (7) 5,6-dimethylbenzimidazole (8) 5-nitro-2- (trifluoromethyl) benzimidazole 11 indazole Derivatives (1) 5-nitroindazole (2) 6-nitroindazole (3) 5-aminoindazole (4) 6-aminoindazole (5) indazole (6) 3-nitroindazole (7) 5-nitro-3-chloro Indazole (8) 3-Chloro -5-nitroindazole (9) 3-carboxy-5-nitroindazole 12 tetrazole derivative (1) 5- (4-nitrophenyl) tetrazole (2) 5-phenyltetrazole (3) 5- (3-carboxyphenyl)- Tetrazole 13 tetrazaindene derivative (1) 4-hydroxy-6-methyl-5-nitro-1,3,
3a, 7-Tetraazaindene (2) 4-mercapto-6-methyl-5-nitro-1,3,3
3a, 7-Tetraazaindene 14 mercaptoaryl derivative (1) 4-nitrothiophenol (2) thiophenol (3) 2-carboxythiophenol Further, general formula (R-1), (R-2), (R- In 3), R ₁ or Time _t PUG is a ballast group or a general formula (R-1), (R-2), (R-3) commonly used in a non-moving photographic additive such as a coupler. A group which promotes the adsorption of the compound represented by the formula () 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 -Oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione,
Cyclic thioamide groups such as thiotriazine and 1,3-imidazoline-2-thione, linear thioamide groups, aliphatic mercapto groups, aromatic mercapto groups, and heterocyclic mercapto groups (the carbon atom to which the -SH group is bonded In the case of a nitrogen atom, it is synonymous with a cyclic thioamide group having a tautomeric relationship therewith, and specific examples of this group are the same as those listed above.), A group having a disulfide bond, benzotriazole, Triazole, tetrazole, 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.
4,684,604, Japanese Patent Application No. 63-98,803, U.S. Pat. No. 3,37
9,529, 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 is a suitable water-miscible organic solvent such as alcohols (metamer, 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.

Further, by a well-known emulsification dispersion method, oil such as dibutyl phthalate, tricresyl phosphate, glycerin triacetate or diethyl phthalate is dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. It is also possible to create and use things. 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 general formula (R-1), (R-2) or (R-
When the compound represented by 3) is incorporated into the photographic emulsion layer or the hydrophilic colloid layer, the compound of the present invention is dissolved in water or a water-miscible organic solvent (if necessary, alkali hydroxide or tertiary It may be added with an amine to form a salt and dissolved), or added to a hydrophilic colloid solution (eg, silver halide emulsion, gelatin aqueous solution, etc.) (at this time, if necessary, an acid or alkali is added to adjust the pH). The compound of the present invention may be used alone or in combination of two or more kinds. The addition amount of the compound of the present invention is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol per mol of silver halide, and halogen to be combined An appropriate value can be selected according to the properties of the silver halide emulsion.

The general formula (I) and the general formulas (R-1), (R
When the compound represented by -2) or (R-3) is used in combination with a negative emulsion, a negative image having 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 formula (I) or (R-1), (R-2) or (R-3) of the present invention is used in combination with a negative emulsion to form a negative image having high contrast. It is preferable to use it.

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 tetrahedron, a crystal having an irregular crystal such as a sphere or a plate, or a complex form of these crystals. May be provided.

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.

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.

It is preferable to use an iridium salt or a rhodium salt before the physical ripening step in the production step of the silver halide emulsion, particularly during grain formation.

In the present invention, the silver halide emulsion layer preferably contains two kinds of monodisperse emulsions having different average grain sizes.
ax) It is preferable in terms of increase, the small size monodisperse particles are preferably chemically 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.

The average grain size of the small-sized monodispersed grains is 90% or less, preferably 80% or less of the average size of the large-sized silver halide monodispersed grains. The average grain size of the silver halide emulsion grains is preferably from 0.02 μm to 1.0 μm, more preferably from 0.1 μm to 0.5 μm, and the average grain size of the large size and small size monodispersed grains is included in this range. preferable.

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. Along with 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.
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.

Among these, preferred are benzotriazoles (eg 5-methylbenzotriazole) and nitroindazoles (eg 5-nitroindazole).
It is. 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.

These accelerators have an optimal addition amount that varies depending on the type of the compound, but 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 limited 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.

As the organic desensitizer, those represented by the general formulas (III) to (V) described in JP-A-63-141608 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
It is preferable that x10 ^-5 mol / m ^{2 be} 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 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 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 added to the coating solution after being dissolved in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof].

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. Patents 3,705,805, 3,707,375, 4,045,229,
No. 3,700,455, No. 3,499,762, West German patent application publication 1,54
It is described in No. 7,863.

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.

In the photographic light-sensitive material of the present invention, a matting agent such as silica, magnesium oxide or polymethylmethacrylate may be contained in the photographic emulsion layer or the hydrophilic colloid layer for the purpose of preventing adhesion.

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 ultrahigh 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 high acrylic developer having a pH value close to pH 13 described in U.S. Pat. Instead, a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains sulfite ions as a preservative in an amount of 0.15 mol / l or more, and has a pH of 10.5 to
With a developer having a pH of 12.3, especially pH 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 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-pyrazolidone are preferable. In some cases, a combination of types or a combination of dihydroxybenzenes and p-aminophenols is used. It is preferable that the developing agent is generally used in an amount of 0.05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols is used, the former is 0.05 mol / l to 0.5 mol / l and the latter is 0.06 mol / l.
It is preferably used in an amount of less than mol / l.

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 / l, particularly preferably at least 0.5 mol / l.

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.

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 at 40 ° C, as shown in Table 1,
The redox compound of the present invention and the compound of general formula (I) are added, and further 5-methylbenztriazole, 4-hydroxy-1,3,3a, 7-tetrazaindene, the following compounds (a) and (b) And 30 wt% of polyethyl acrylate to gelatin and the following compound (c) as a gelatin hardening agent were added, and silver was formed on a polyethylene terephthalate film (150 μ) having an undercoat layer (0.5 μ) made of vinylidene chloride copolymer. The amount of coating 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) [1] Halftone dot quality These samples were subjected to an optical wedge and a contact screen (Fujifilm, 150L) using tungsten light of 3200 ° K.
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 to give a halftone = 95% halftone dot area ratio △ log E (log E 95%)-Exposure to give a 5% halftone dot area ratio (log E 5%) Was evaluated on a 5-point scale. In the five-point evaluation, "5" indicates the best quality and "1" indicates the worst quality.
"5" and "4" are practically usable as the halftone dot masters for plate making, "3" is a practically usable limit level, "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 sample of the present invention has a remarkably wide halftone gradation and an improved halftone dot quality as compared with the comparative sample.

In particular, the sample of the present invention had a smooth halftone dot shape.

[2] Line drawing quality SPC-3 for plate-making camera uses originals with Mincho and Gothic characters of various grades created by printing with a phototypesetting machine.
Photographs were taken of these samples using 51 (manufactured by Dainippon Screen Co., Ltd.).

The 40μ linewidth Mincho characters of the manuscript are 40
The exposure time was adjusted so that it was reproduced as μ.

At this time, the reproducibility of Gothic characters and the optical density (Dmax) of the background were evaluated.

(1) Reproducibility of Gothic characters Visually evaluated in 5 levels. In the five-point evaluation, "5" indicates the best quality and "1" indicates the worst quality. "5" and "4" are practically usable, "3" is a practically usable limit level, and "2" and "1" are impractical qualities.

 The results are shown in Table 1.

(2) Background Optical Density (Dmax) The degree of blackening on these samples in the part corresponding to the white background part of the original was measured by a Macbeth optical densitometer. The higher Dmax is, the less noise there is as line drawing information, which is preferable.

 The results are shown in Table 1.

The sample of the present invention has good line drawing reproducibility, and
Gave a high Dmax.

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
Was filled with the developing solution-1 of Example-1, and the following three conditions were used.
Developed at 30 ° C for 30 seconds, fixed, washed with water and dried.

[A] Immediately after the temperature of the developing solution 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 filling the developing solution into the automatic processor, the Fujifilm GRANDEX GA-100 film was exposed to a size of 50.8 cm x 61.0 cm so that 50% of the area was developed. 200 per day
The sheet is processed, and a developing process is performed with the liquid repeated for 5 days. Replenish 100 cc of developer-I per processed sheet.

Table 2 shows the obtained photographic properties. 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 3, the use of the compound of the present invention unexpectedly improved the processing running stability.

Example 3 5.0 × 10 5 per mol of silver in an aqueous gelatin solution kept at 50 ° C.
After simultaneously mixing an aqueous solution of silver nitrate and an aqueous solution of sodium chloride in the presence of ^-6 mol of (NH ₄ ) ₃ RhCl ₆ , gelatin is added after removing soluble salts by a method well known in the art, and then chemically mixed. 2-methyl-4-
Hydroxy-1,3,3a, 7-tetraazaindene was added. This emulsion was a cubic monodispersed emulsion having an average grain size of 0.15 μm.

As shown in Table 3, the redox compound of the present invention and the compound of the general formula (I) were added to this emulsion, and the polyethyl acrylate latex was added to the solid content of 30 wt% of gelatin.
1,3-vinylsulfonyl-2- as a hardening agent
Add propanol and 3.8 g / m ² on polyester support
Of Ag. Gelatin was 1.8 g / m ² . On this, gelatin 1.5 g / m ² as a protective layer and polymethyl methacrylate particles (average particle size 2.
5μ) 0.3 g / m ² , and the following surfactant as a coating aid,
A protective layer containing a stabilizer and a UV absorber was applied and dried.

Stabilizer thioctic acid 2.1 mg / m ² The sample was exposed through a document as shown in FIG. 1 through a light source printer p-607 manufactured by Dainippon Screen Co., Ltd., developed at 38.degree. C. for 20 seconds, fixed, washed with water, dried, and then the quality of the printed characters was improved. 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 results are shown in Table 3. The sample of the present invention has excellent character image quality.

Example-4 The sample of Example-3 was subjected to post-exposure plate-making automatic developing machine FG660F type (manufactured by Fuji Photo Film Co., Ltd.) in the same manner as in Example-2.
Was filled with the developing solution of Example 1 at 34 ° C. under the following three conditions.
It was developed for 30 seconds, fixed, washed with water and dried.

[A] Immediately after the temperature of the developing solution 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 filling the developing solution into the automatic developing machine, the Fujifilm GRANDEX VU-100 film was exposed to a size of 50.8 cm x 61.0 cm so that 50% of the area was developed. 200 per day
The sheet is processed, and a developing process is performed with the liquid repeated for 5 days. Replenish 100 cc of developer-I per processed sheet.

Table 2 shows the obtained photographic properties. 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 3, the use of the compound of the present invention unexpectedly improved the processing running stability.

[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)

Claims (2)

(57) [Claims] 1. A silver halide photographic emulsion layer having at least one photographic emulsion layer, and said photographic emulsion layer or at least one other hydrophilic colloid layer being oxidized with a compound represented by the following general formula (I). A silver halide photographic light-sensitive material comprising a redox compound capable of releasing a development inhibitor, each of which contains at least one compound having a hydrazine group as a redox group. General formula (I) In the general formula (I), R ¹ and R ² are both hydrogen atoms,
Alternatively, one is a hydrogen atom and the other is a sulfonyl group or an acyl group. R ¹⁰ is an alkyl group, aralkyl group, alkoxy group, arylamino group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group,
Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group,
Sulfo group, phosphoric acid amide group, carboxyl group or L
_l represents an X group. k represents 0, 1 or 2. R ¹¹ represents a group having the same meaning as R ³ below or an L ₁ X group. Y ¹ is -CONH-, -SO ₂ NH-, (Y ² is -O-, -NH- or Represents R ³ represents a group selected from the group consisting of an aliphatic group, an aromatic group and a heterocyclic group). R ⁴ represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an oxycarbonyl group and a carbamoyl group. G is a carbonyl group, a sulfonyl group, a sulfinyl group, an iminomethylene group and Represents a divalent group selected from the group consisting of: However, in the above general formula (I) At least one of the portion and R ⁴ has an adsorption promoting group on the silver halide grain represented by L ₁ X. Where X
Is a group containing a cyclic thioamide group, a group containing a mercapto group,
It represents a group selected from the group consisting of a group containing a disulfide bond and a 5- to 6-membered nitrogen-containing heterocyclic group, L represents a divalent linking group, and l represents an integer of 0 to 1. 2. A redox compound represented by the following general formula (R-
1), (R-2) and (R-3), which are at least one compound selected from the compounds represented by the formula (1). material. 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
Is -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. PU
G represents a development inhibitor.