JPH03294845A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain hard-contast images by using a developer having high stability by incorporating a redox compd. which can release a development inhibitor when oxidized and a specific compd. into at least one layer of silver halide emulsion layers and other hydrophilic colloidal layers. CONSTITUTION:The redox compd. which can release the development inhibitor when oxidized and the compd. expressed by formula I are incorporated into at least one layer of the silver halide emulsion layers and the other hydrophilic colloidal layers. In the formula I, Z1 and Z2 respectively densote the nonmetal atom group necessary for perfecting a benzooxazole nucleus, benzothiazole nuclees, benzocerenazole nucleus, naphthooxazole nucleus, naphthothiazole nucleus, thiazole nucleus, thiazoline nucleus, etc. R1 and R2 respectively denote an alkyl group or aralkyl group; X denotes a charge balance paired ion; n denotes 0 or 1. The hard-contrast images are formed by using the developer having the high stability in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material and a method for forming an ultra-high contrast negative image using the same, and in particular to a silver halide photograph used in a photolithography process. The present invention relates to ultra-high contrast negative type photographic materials suitable for photosensitive materials.

(Prior Art) In the field of photoengraving, in order to deal with the diversity and complexity of printed matter, there are demands for photosensitive materials with good original reproducibility, stable processing solutions, and easy replenishment.

Particularly in the line drawing process, manuscripts are created by pasting typesetting characters, handwritten characters, illustrations, halftone photographs, etc. Therefore, a document contains images of different densities and line widths, and there is a strong desire for a plate-making camera, a photosensitive material, or an image forming method that can finish these documents with good reproduction. On the other hand, enlarging (stretching) or reducing (shrinking) halftone photographs is widely used in plate making for catalogs and large posters. The point will be photographed. When reduced, the number of lines/ink is larger than that of the original, resulting in a photograph of a thinner point. Therefore, in order to maintain halftone reproducibility, an image forming method having a wider latitude is required.

A halogen lamp or a xenon lamp is used as a light source for a plate-making camera. In order to obtain sensitivity to these light sources, photographic materials are usually orthosensitized. However, it has been discovered that ortho-sensitized photographic materials are more strongly affected by the chromatic aberration of lenses, and as a result, image quality tends to deteriorate. Moreover, this deterioration is more noticeable for xenon lamp light sources.

As a system to meet the demands for a wide latitude, we developed a lithium-type silver halide photosensitive material made of silver chlorobromide (with a silver chloride content of at least 50% or more) with an extremely low effective concentration of sulfite ions (usually 0.1%). A method is known in which a line or halftone image with high contrast and high blackening density, in which image areas and non-image areas are clearly distinguished, is obtained by processing with a hydroquinone developer (mol/1 or less). However, with this method, the development is extremely unstable against air oxidation due to the low sulfite concentration in the developer.
Currently, various efforts and innovations have been made to keep the temperature of the liquid stable, and the processing speed is extremely slow, reducing work efficiency.

For this reason, the above development method (lith development system)
There is a need for an image forming system that eliminates the instability of image formation caused by the process, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics, and one example of this is U.S. Pat. No. 4,168,977, No. 4
．． 221. No. 857, No. 4,224,401, No. 4,243゜739, No. 4,272,606, No. 4
, No. 311.781, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound has been added is treated with a sulfite preservative of 0.15 mol/1 at pH 11.0 to 12.3. A system has been proposed for forming ultra-high contrast negative images with γ of over 10 by processing with a developer containing the above components and having good storage stability. This new image forming system has the feature that it can also use silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chlorobromide, which has a high silver chloride content. There is.

The above image system has sharp halftone dot quality, processing stability,
Although it shows excellent performance in terms of speed and original reproducibility, a system with further improved original reproducibility is desired in order to deal with the variety of printed matter in recent years.

JP-A-61-213847, JP-A No. 64-72140 and US Pat. No. 4,684,604 disclose photosensitive materials containing redox compounds that release photographically useful groups upon oxidation.
On the other hand, examples using silver chlorobromide include JP-A Nos. 60-83028, 60-112034, 62-235947,
No. 63-103232 discloses an attempt to widen the gradation reproduction range. However, in ultra-high contrast processing systems using hydrazine derivatives, these redox compounds have the disadvantage of inhibiting high contrast, and their properties cannot be utilized.

There wasn't.

(Objectives of the Invention) Therefore, the first object of the present invention is to provide a photosensitive material for plate making that can produce high-contrast images using a highly stable developer.

A second object of the present invention is to provide a silver halide photographic light-sensitive material containing a hydrazine compound, which can provide high-quality halftone dots and has a wide halftone gradation.

Thirdly, it is an object of the present invention to provide a silver halide photographic light-sensitive material containing a hydrazine compound, which is free from black spots.

(Structure of the Invention) These objects of the present invention are to provide a silver halide photographic photosensitive material having at least one silver halide emulsion layer containing silver halide and a hydrazine derivative having a silver chloride content of at least 50 mol % on a support. In the material, at least one layer of the silver halide emulsion layer and other hydrophilic colloid layers contains a redox compound capable of releasing a development inhibitor upon oxidation and a compound represented by the following general formula (I). This was achieved using a silver halide photographic material characterized by the following.

General formula (I) Z and Z are each a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a selenazole nucleus, Represents a group of nonmetallic atoms necessary to complete a selenazoline nucleus, pyridine nucleus, benzimidazole nucleus, or quinoline nucleus.

R1 and R8 each represent an alkyl group or an aralkyl group. X is a charge balance counterion and n is O or l
represents.

The compound represented by the general formula (I) having substantially no absorption maximum in the visible region will be explained.

General formula (I) Z, and 2. are benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, thiazole nucleus, thiazoline nucleus, oxazole nucleus, selenazole nucleus, selenazoline nucleus, pyridine nucleus, benzimidazole nucleus, or Represents a group of nonmetallic atoms necessary to complete the quinoline nucleus.

R1 and R2 each represent an alkyl group or an aralkyl group. X is a charge balance counterion and n is O or 1
represents.

Here, when general formula (I) is a radical, preferably 2. ．． 2. The atomic group represented by or R1, R
2 from which one hydrogen atom has been removed, and particularly preferred is one from which one hydrogen atom has been removed from R, R2.

Furthermore, in the general formula (I), in those having oxidation as a substituent (for example, R1, R9 are alkyl groups or aralkyl groups having an acid group), the general formula (I) itself is
) can be a compound represented by

In general formula (I), the heterocycle formed by Zl and Z is preferably a benzoxazole nucleus, a benzothiazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a thiazole nucleus, or an oxazole nucleus, more preferably a benzoxazole nucleus, An oxazole nucleus, a benzothiazole nucleus, or a naphthoxazole nucleus, most preferably a benzoxazole nucleus or a naphthoxazole nucleus. In the general formula (I), the heterocycle formed by Z or Z2 may be substituted with at least one substituent, and examples of the substituent include a halogen atom (for example, fluorine, chlorine, bromine, iodine), Nitro group, alkyl group (preferably one with 1 to 4 carbon atoms, e.g. methyl group, ethyl group, trifluoromethyl group, benzyl group, phenethyl group), aryl group (e.g. phenyl group), alkoxy group (preferably one with carbon number 1 to 4, such as methoxy group, ethoxy group, propoxy group, butoxy group), carboxyl group, alkoxycarbonyl group (preferably one having 2 to 5 carbon atoms,
Examples include ethoxycarbonyl group), hydroxy group, and cyano group.

Regarding Zl and Z2 in general formula (I), examples of the benzothiazole nucleus include benzothiazole, 5-chlorobenzothiazole, 5-nitrobenzothiazole, 5-methylbenzothiazole, 6-bromobenzothiazole, 5
-Iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-carboxybenzothiazole, 5
Examples of the naphthothiazole nucleus include naphtho[1
, 2-d) Thiazole, NaphthoC1,2-d) Thiazole, Naphtho[2゜3-d]thiazole, 5-methoxynaphtho[1゜2-d]thiazole, 5-methoxynaphtho[
2゜3-d]thiazole, etc., and examples of the benzoselenazole nucleus include benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole,
5-hydroxybenzoselenazole, 5-chloro-6-
methylbenzoselenazole, etc.; examples of the naphthoselenazole nucleus include naphtho[1,2-dl selenazole, naphtho[2゜1-d]selenazole, etc.; examples of the thiazole nucleus include thiazole nucleus, 4-methylthiazole, etc. Examples of the thiazoline nucleus include a thiazoline nucleus, a 4-methylthiazoline nucleus, and the like.

Regarding 21 and Z2 in general formula (1), examples of the benzoxazole nucleus include benzoxazole nucleus, 5
-chlorobenzoxazole nucleus, 5-methylbenzoxazole nucleus, 5-bromobenzoxazole nucleus, 5-fluorobenzoxazole nucleus, 5-phenylbenzoxazole nucleus, 5-methoxybenzoxazole nucleus, 5-
Ethoxybenzoxazole nucleus, 5-trifluoromethylbenzoxazole nucleus, 5-hydroxybenzoxazole nucleus, 5-carboxybenzoxazole nucleus, 6-
Examples of the naphthoxazole nucleus include naphtho(2, 1-d) Oxazole nucleus, naphtho(1,2-d) oxazole nucleus, naphtho[2,3d]
Examples include oxazole nucleus, 5-methoxynaphtho[1°2-d]oxazole nucleus, and the like.

Furthermore, regarding Z and Z2, examples of the oxazole nucleus include oxazole nucleus, 4-methyloxazole nucleus, 4-
Phenyloxazole nucleus, 4-methoxyoxazole nucleus, 4,5-dimethyloxazole nucleus, 5-phenyloxazole nucleus or 4-methoxyoxazole nucleus, etc., and examples of pyridine nucleus include 2-pyridine nucleus, 4-pyridine nucleus, 5-methyl -2-pyridine nucleus, 3-methyl-4-pyridine nucleus, etc., and quinoline nucleus such as 2-quinoline nucleus, 4-quinoline nucleus, 3-methyl-2-quinoline nucleus, 5-ethyl-2-quinoline nucleus, 8-fluoro-2-
Examples include quinoline nucleus, 6-medoxy-2-quinoline nucleus, 8-chloro-4-quinoline nucleus, and 8-methyl-4-quinoline nucleus.

In the general formula (I), the alkyl groups represented by R and R2 include unsubstituted and substituted alkyl groups, and the unsubstituted alkyl group preferably has 18 or less carbon atoms, particularly 8 or less carbon atoms, such as a methyl group. , ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octadecyl group, etc. In addition, as substituted alkyl groups,
The alkyl moiety preferably has 6 or less carbon atoms, particularly preferably 4 or less carbon atoms. They may be coupled via

For example, 2-sulfoethyl group, 3-sulfobrovir group, 3
-Sulfobutyl group, 4-sulfobutyl group, 2-(3-sulfopropoxy)ethyl group, 2-C2-(3-sulfopropoxy)ethoxy]ethyl group, 2-hydroxy-3
-sulfopropyl group, p-sulfophenethyl group, p-sulfophenylpropyl group, etc.) an alkyl group substituted with a carboxy group (the carboxy group may be bonded via an alkoxy group, an aryl group, etc.);

For example, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, etc.), hydroxyalkyl group (e.g. 2-hydroxyethyl group, 3-hydroxypropyl group, etc.), acyloxy Alkyl groups (e.g., 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl groups (e.g., 2-methoxyethyl group, 3-methoxypropyl group, etc.), alkoxycarbonylalkyl groups (e.g., 2-methoxycarbonyl group, etc.) ethyl group, 3-methoxycarbonylpropyl group, 4-ethoxycarbonylbutyl group, etc.), vinyl group-substituted alkyl group (e.g. allyl group), cyanoalkyl group (e.g. 2-cyanoethyl group, etc.), carbamoyl alkyl group (e.g. 2-cyanoethyl group, etc.) carbamoylethyl group), aryloxyalkyl group (e.g. 2-
phenoxyethyl group, 3-phenoxypropyl group, etc.)
, an aralkyl group (eg, 2-phenethyl group, 3-phenylpropyl group, etc.), or an aryloxyalkyl group (eg, 2-phenoxyethyl group, 3-phenoxypropyl group, etc.).

As the substituents represented by R, R, it is particularly preferable that at least one of them is an alkyl group having a sulfo group or a carboxyl group.

Charge balance counter ion , ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion, etc. In this case n
is 1.

If the heterocyclic quaternary ammonium salt further contains an anionic substituent such as a sulfoalkyl substituent, the salt can be in the form of a betaine, in which case no counterion is required and n is 0. . When the heterocyclic quaternary ammonium salt has two anionic substituents, e.g. two sulfoalkyl groups, X4 is an anionic counterion, e.g. an alkali metal ion (sodium ion, potassium ion, etc.) and ammonium salts (triethylammonium, etc.).

Here, the term "compound that does not substantially have an absorption maximum in the visible light region" refers to a compound that has a color tone that is below a level that does not cause any practical problems in residual color on photographic light-sensitive materials. It is a compound whose residual color is below a level that poses no practical problem.

Preferably, the above compound has an absorption maximum in methanol of 460 nm or less, more preferably 430 nm or less.

Specific examples of the compound represented by general formula (I) are shown below.

However, the present invention is not limited to the following compounds.

-1 -2 -3 (CH2)s (CH2)sS03)1
-N(C2Ha)3 5Ose-4 -7- -8 -6- ■-11 1-16 ■-17 ■-18 ■-13 ■-14 2H5 (CH2).

“Son” -15 ose -19 ■-20 (CH2)3 (CH2).

5O3H-N(CzHs)3 S03θ ■ ■ CO□H O3e l-22 ■-25 Js ■-23 ■-24 C,R5 (CHz)s 03 ■-26 2H5 , bu3Na so, "' General formula of the present invention The content of the compound represented by (I) is determined by the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, and the type of antifogging compound. It is desirable to select the optimum amount depending on the amount of silver halide, etc., and testing methods for the selection are well known to those skilled in the art.
-" mol, especially in the range of 10-" to 5X10-" mol.

The redox compound of the present invention that can release a development inhibitor when oxidized will be explained.

The redox group of the redox compound is preferably hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones, and more preferably hydrazines.

The hydrazines used as the redox compound capable of releasing a development inhibitor upon oxidation of the present invention are preferably the following general formula (II-1), general formula (■-2),
It is represented by general formula (If-3). General formula (II-1)
Particularly preferred are compounds represented by:

General formula (II-1) Rs-N-N-G+-(Time), -PUGI A
t General formula (II-2) General formula (II-3) In these formulas, R1 is an aliphatic group or an aromatic group -〇- group, -C- group, S〇- group, -5O2- group 11 or -P- group. G is just a bond, G, -
R.

-O--S- or -N-, R4 is 2 Represents a hydrogen atom or R3.

A1 and A2 represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and may be substituted. In general formula (II-1), AA! At least one of them is a hydrogen atom. A is synonymous with A1 or -CHz
CH+T 1me)l PUGA.

represents.

A4 represents a nitro group, a cyan group, a carboxyl group, a sulfo group or -G1 G2 Rs.

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

General formulas (II-1), (II-2), and (IT-3) will be explained in more detail.

In general formulas (■ to I), (II-2), and (II-3), the aliphatic group represented by R1 preferably has 1 to 3 carbon atoms.
In particular, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.

This alkyl group may have a substituent.

The aromatic group represented by RI in general formulas (II-1), (II-2), and (II-3) 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.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring, an isoquinoline ring, etc. Among these, those containing a benzene ring are preferred.

Particularly preferred as R8 is an aryl group.

The aryl group or unsaturated heterocyclic group of R3 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 group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group,
Acyl group, alkoxycarbonyl group, acyloxy group,
Examples include carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, etc. Preferred substituents include linear, branched or cyclic alkyl group (preferably one having 1 to 20 carbon atoms), aralkyl group (preferably has 7 to 30 carbon atoms), alkoxy group (preferably has 1 to 30 carbon atoms), substituted amino group (preferably has 1 to 30 carbon atoms)
~30 alkyl group substituted), acylamino group (preferably having 2 to 40 carbon atoms), sulfonamide group (preferably having 1 to 40 carbon atoms)
, a ureido group (preferably one having 1 to 40 carbon atoms,
Examples include phosphoric acid amide groups (preferably those having 1 to 40 carbon atoms).

General formulas (II-1), (If-2), (II-3) and 0
011
1 is preferably a -C- group or a -SO,- group, with a -C group being most preferred.

AI and A are preferably hydrogen atoms;

is a hydrogen atom, -CH2-CH(-Time-)-
, PUGA4 are preferred.

In the general formulas (■ to 1), (II-2), and (II-3), Time represents a divalent linking group and may have a timing adjustment function.

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

As the divalent linking group represented by Time, for example, U.S. Pat.
No. 135), etc., which releases PUG through an intramolecular ring-opening reaction of p-nitrophenoxy derivatives, and US Pat. No. 4. 310. No. 612 (Unexamined Japanese Patent Publication No. 55-53, 33
U.S. Pat. No. 4,330,617 and U.S. Pat. No. 4,446,216, which release PUG through an intramolecular ring-closing reaction after ring cleavage as described in U.S. Pat.
No. 4,483,919, JP-A-59-121.3
Those that release PU and G along with the production of acid anhydride through the intramolecular ring-closing reaction of the carboxyl group of the succinic acid monoester or its analog described in No. 28, etc.; U.S. Patent No. 4
, No. 409, 323, No. 4.421.845, Research Disclosure Magazine Nα21, 228 (198
(December 1997), U.S. Patent No. 4,416,977 (Japanese Unexamined Patent Publication No. 135.944/1982), Japanese Unexamined Patent Publication No. 209/7/1983
No. 36, No. 58-209,738, etc., which generates quinomonomethane or its analogs by electron transfer via a double bond conjugated with an aryloxy group or a heterocyclic oxy group and releases PUG. ; U.S. Patent No. 4,4
20.554 (Japanese Patent Publication No. 57-136,640), JP-A No. 57-135゜945, JP-A No. 57-188,035
No. 58-98.728 and No. 58-209,7
A nitrogen-containing heterocycle which releases PUG from the γ-position of the enamine by electron transfer of the moiety having an enamine structure in the nitrogen-containing heterocycle described in No. 37, etc.; P is formed by an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with a nitrogen atom.
Those that release UG; U.S. Patent No. 4.146.396 (Japanese Patent Application Laid-Open No. 52-90932), JP-A-59-93-4
No. 42, JP-A-59-75475, JP-A-60-24
9148, JP-A-60-249149, etc., which release PUG with the production of aldehydes; JP-A-51-146,828, JP-A-57-179.842, JP-A-59-104, 641, which releases PUG with decarboxylation of carboxyl groups, -0-COOC
R, Rb-PUG (R,, R, represents a -valent group.)
has the structure and releases PUG with decarboxylation and subsequent generation of aldehydes; JP-A-60-7-429
which releases PUG with formation of isocyanates as described in US Pat. No. 4,438.1! ] P by the coupling reaction with the oxidized product of the color developer described in No. 3 etc.
We can list things that emit UG.

For specific examples of these divalent linking groups represented by Time, see JP-A No. 61-236,549 and Japanese Patent Application No. 63-Sho.
It is also described in detail in No. 98,803.

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

The development inhibitor represented by PUG or (T im e ++ PU G is a known development inhibitor having a heteroatom and bonded via a heteroatom, such as those described by C.E.C. Mies (C, E.

K., Mees) and Chi. H. James (T.
,H.

James) [The Theory of the Photographic Process]
he Photo-graphic Processe
s) J 3rd edition, 1966 Macmillan (IJa(mill)
an) published by Sha, pages 344 to 346.

The development inhibitor represented by PUG may be substituted. Examples of substituents include those listed as substituents for R3, and these groups may be further substituted.

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

Also, general formulas (I[-1), (II-2), (I[-3)
In , R1 or +Time-)-, PUG contains a ballast group commonly used in immobile photographic additives such as couplers, general formulas (II-1), (II-2
) A group that promotes adsorption of the compound represented by (II-3) to silver halide may be incorporated.

The ballast group has general formulas (II-1), (II-2), (I
An organic group that provides a sufficient molecular weight to substantially prevent the compound represented by I-3 from diffusing into other layers or processing liquids, and includes alkyl groups, aryl groups, heterocyclic groups, ether groups, and thioethers. group, an amide group, a ureido group, a urethane group, a sulfonamide group, etc. The ballast group is preferably a ballast group having a substituted benzene ring, particularly a ballast group having a benzene ring substituted with a branched alkyl group.

Specifically, the adsorption promoting group to silver halide is 4-
Thiazoline-2-thione, 4-imidacyline-2-thione, 2-thiohydantoin, rhodanine, thiobarbital acid, tetrazoline-5-thione, 1,2.4-) liazoline-3-thione, 1. 3. 4-oxazoline-2-thione, benzimidacilline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-
Thione, thiotriazine, 1,3-imidacyline-2-
Cyclic thioamide group such as thione, chain thioamide group,
Aliphatic mercapto group, aromatic mercapto group, heterocyclic mercapto group (if the carbon atom to which the -3H group is bonded is a nitrogen atom, it has the same meaning as a cyclic thioamide group that has a tautomeric relationship with this group, Specific examples of groups are the same as those listed above), groups having a disulfide bond, benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, thiazoline, benzoxazole, oxazole, oxazoline , thiadiazole, oxathiazole, triazine, azaindene, etc., consisting of a combination of nitrogen, oxygen, sulfur and carbon.
Examples thereof include a nitrogen-containing heterocyclic group having a member, and a quaternary heterocyclic salt such as benzimidazolinium.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for R1.

Specific examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

I-1 -5 1-6 -3 -7 ll-9 ■ ■ 2 ■ 7 ■ 9 ■-20 ■ 4 ■ 5 -2 1 ■ 2 ■ 3 NO7 NO! ■ 24 ■-25 ■-29 ■ 1 NO9 ■-26 Hs ■-27 ■-28 ■-32 ■-33 SU, Na ■ 34 CaH+s ■-35 ■-36 The redox compounds used in the present invention include the above. In addition to the
No. 2-260,153, Japanese Patent Application No. 1102.393, No. 1-102.394, No. 1-102,395, No. 1
, 114,455 can be used.

The method for synthesizing the redox compound used in the present invention is, for example, JP-A-61-213,847, JP-A No. 62260.153.
No. 4, U.S. Pat. 684. No. 604, patent application 1986
-98,803, U.S. Patent No. 3,379.529,
No. 3,620,746, No. 4,377.634, No. 4.332.878, JP-A-49-129,536, No. 56-153,336, No. 56-153,342
It is written in the number etc.

The redox compound of the present invention is preferably 1X10-' to 5X10-' mol per mole of silver halide, more preferably 1
It is used within the molar range of Xl0-' to lXl0-''.

The redox compound of the present invention can be used in a suitable water-miscible organic solvent, such as alcohols (methanol, ethanol, propatool, fluorinated alcohols), ketones (acetone, methyl ethyl ketone), dimethyl formamide, dimethyl sulfoxide, methyl cellosolve, etc. It can be used by dissolving it in

In addition, by the well-known emulsification and dispersion method, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate, or diethyl phthalate can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and then mechanically emulsified and dispersed. You can also create and use things.

Alternatively, by a method known as solid dispersion method,
The powder of the redox compound can also be dispersed in water using a ball mill, a colloid mill, or an ultrasonic wave.

A layer containing the redox compound of the present invention is provided above or below a photosensitive emulsion layer containing a hydrazine nucleating agent. The layer containing the redox compound of the present invention may further contain photosensitive or non-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 the hydrazine nucleating agent.

The hydrazine derivative used in the present invention has the following general formula (
Preference is given to compounds represented by II[).

stomach.

General formula (III) R, -N-N-V-R.

I Bz In the formula, R5 represents an aliphatic group or an aromatic group, R6 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and ■ represents a 10- group, -SO.

7 represents a carbonyl group or iminomethylene group, B1, B
Both 2 represent a hydrogen atom, or one of them is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (■), the aliphatic group represented by R6 preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. This alkyl group may have a substituent.

In the general formula (II[), the aromatic group represented by R is a monocyclic or bicyclic ring group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be fused with an aryl group.

Preferred as R6 is an aryl group, particularly preferably one containing a benzene ring.

The aliphatic group or aromatic group of R6 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, a ureido group, Urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
Alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group, carboxyl group, phosphoric acid amide group, diacylamino group, imide R5 Preferred substituents are alkyl groups (preferably carbon atoms
~20 carbon atoms), aralkyl groups (preferably 7~20 carbon atoms),
30), alkoxy group (preferably 1 to 2 carbon atoms)
0), substituted amino groups (preferably 1 to 20 carbon atoms), substituted amino groups (preferably 1-20 carbon atoms)
(an amino group substituted with an alkyl group), an acylamino group (preferably one having 2 to 30 carbon atoms), a sulfonamide group (preferably one having 1 to 30 carbon atoms), a ureido group (preferably one having 1 carbon number) 30), a phosphoric acid amide group (preferably one having 1 to 30 carbon atoms), and the like.

The alkyl group represented by R6 in general formula (III) 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, one containing a benzene ring). .

When 1 (2) is a -C- group, preferred among the groups represented by R6 are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-
(methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxybenzyl group, etc.), aryl group (e.g., phenyl group, 3,5-dichlorophenyl group, 0-methanesulfonamidophenyl group, 4 -methanesulfonylphenyl group, 2
-hydroxymethylphenyl group, etc.), and a hydrogen atom is particularly preferred.

R6 may be substituted, and as the substituent, the substituents listed for R6 can be applied.

1 V in general formula (III) is most preferably a -C- group.

Also, R6 splits the VRs part from the remaining molecules,
-VR, may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the moiety; examples thereof include those described in JP-A No. 63-29751, etc. It will be done.

Hydrogen atoms are most preferred as B1 and B2.

R6 or R@ in the general formula (III) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

Examples of the polymer include those described in JP-A-1-100530.

R5 or R6 in general formula (III) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea group,
U.S. Pat. No. 4,385.108, U.S. Pat.
No. 59,347, JP-A No. 59-195,233, No. 5
9-200゜231, 59-201.045, 59-201.046, 59-201.047,
No. 59-201,048, No. 59-201,049, JP-A-61-170,733, No. 61-270,7
No. 44, No. 62-948, Patent Application No. 62-67.508
No. 62-67.501 and No. 62-67.510.

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

ll-1 -2 I[I-3 ll-5 ■-1 ■-12 -8 ll-13 ■-14 ■-10 IJ ShiaH ■-15 ■-16 I4 -N ■-22 ■-23 ■- 24 ■-18 ll-19 ■ 0 ■-25 ■-26 Song In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCH DISCLOSURE
Item23516 (November 1983 issue, P, 34
6) and the documents cited therein, as well as U.S. Pat.
No. 80.207, No. 4,269,929, No. 4.27
No. 6.364, No. 4,278,748, No. 4,385
, No. 108, No. 4,459,347, No. 4,560,
No. 638, No. 4.478.928, British Patent No. 2,01
1,391B, JP-A-60-179734, JP-A No. 62-
No. 270,948, No. 63-29,751, No. 61-
170゜733, 61-270.74.4, 6
No. 2-948, EP 217,310, or US 4
゜686.167, JP 62-178,246,
No. 63-32,538, No. 63-104゜047,
No. 63-121,838, No. 63-129.337, No. 63-223,744, No. 63-234,244
No. 63-234,245, No. 63-234,24
No. 6, No. 63-294.552, No. 63-306, 4
No. 38, JP-A No. 1-100,530, 1. 105
．． No. 941, No. 1-105,943, Japanese Unexamined Patent Publication No. 1983-
No. 1O,233, Japanese Patent Application Publication No. 1-90,439, Patent Application No. 1989
No. 3-105,682, No. 63-114,118, No. 63-110.051, No. 63-114.119,
No. 63-116,239, No. 63-147,339, No. 63-179,760, No. 63-229,163
No., Japanese Patent Application No. 1-18.377, No. 1-18.378, No. 1-18.379, No. 1-15,755, No. 1
-16.814, 1-40,792, 1-42
．． No. 615, No. 1-42, 616, No. 1-123.6
93 and No. 1-126.284 can be used.

The amount of the hydrazine derivative added in the present invention ranges from lXl0-@mol to 5XIO per mole of silver halide.
-' mol is preferable, and the addition amount is particularly preferably in the range of 1X10-' mol to 2X10-'' mol.

The silver halide emulsion used in the present invention may be any one of silver chloride, silver chlorobromide, silver iodochloride, and silver iodochlorobromide, but at least 50 mol % of the emulsion is composed of silver chloride. Among these, those containing a small amount (70 mol% of silver chloride) are preferable.The silver iodide content is 3 mol% or less, more preferably 0.
．． It is 5 mol% or less.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less.
It is preferably 5μ or less. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse herein means that at least 95% of the particles by weight or number of particles is composed of particles having a size within ±40% of the average particle size.

Silver halide grains in photographic emulsions may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
ular) crystals, or a composite form of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

Two or more silver halide emulsions formed separately may be used in combination.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a water-soluble dye as a filter dye or for various purposes such as preventing irradiation. Filter dyes include dyes for further lowering photographic sensitivity, preferably ultraviolet absorbers that have a spectral absorption maximum in the intrinsic sensitivity range of silver halide, and dyes that are safe against safelight light when handled as bright-room sensitive materials. In order to increase the wavelength, dyes having substantial light absorption mainly in the 350 nm to 600 nm region are used.

These dyes are added to the emulsion layer depending on the purpose, or they are added together with a mordant to the upper part of the silver halide emulsion layer, that is, to the non-light-sensitive hydrophilic colloid layer which is further away from the silver halide emulsion layer with respect to the support. It is preferable to use it by fixing it.

Although it varies depending on the molar extinction coefficient of the dye, it is usually 10-! g
/ rrr to 1 g/rrr. Preferably it is 50 to 500 ■/durability.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169, and some are listed below.

SO,K SO, to OsK O2K 0sNa SO,Na The above dye is dissolved in a suitable solvent [e.g., water, alcohol (e.g. methanol, ethanol, propatool, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof]. It is added to the coating solution for a non-photosensitive hydrophilic colloid layer of the present invention.

Two or more of these dyes can also be used in combination.

The dyes of the invention are used in amounts necessary to enable bright room handling.

The specific amount of dye used is generally 10-”g/rrr~
Preferred amounts can be found in the range of Ig/I, especially from 10-'g/rrr to 0.5 g/I.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted (1,3,3a,7) tetrazaindenes); A number of compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.), pentaazaindenes, etc.; Among these, preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be included in the treatment liquid.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, active vinyl compounds (1,3゜5-triacryloyl-hexahydro-S-triazine, ■,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-8 -triazine, etc.), mucohalogen acids, etc. can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

Additionally, a polymer latex such as polyalkyl acrylate may be included for dimensional stability.

Development accelerators or nucleating and infectious development accelerators suitable for use in the present invention include JP-A-53-77616 and JP-A-53-77616;
4-37732, 53-137゜133, 60-1
In addition to the compounds disclosed in US Pat. No. 40,340, No. 60-14959, etc., various compounds containing N or S atoms are effective.

Next, specific examples are listed.

, S-S, CH2CH \CH2' CHtCHzCHtCHzCOOH C1e CH2C82N(C2H5)2 N (C2Hs) 2NCH2CHCH20HH n-CtHoN(CtHtOH)t The optimum addition amount of these accelerators varies depending on the type of compound, but 1.0XIO- '〜 0.5g/rrr.

Preferably, it is used in a range of 5.0×10 −” to 0.1 g/po.

In order to obtain ultra-high contrast photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or U.S. Pat.
It is not necessary to use a highly alkaline developer with a pH close to 13 as described in No. 9,975, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains 0.15 mol/1 or more of sulfite ion as a preservative, and has a pH of
By using a developer having a pH of 10.5 to 12.3, particularly 11.0 to 12.0, a sufficiently high contrast negative image can be obtained.

There are no particular limitations on the developing agent that can be used in the method of the present invention, such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone, 4゜4-dimethyl-1-phenyl- 3-pyrazolidone), aminophenols (e.g. N
-methyl-p-aminophenol) can be used alone or in combination.

In particular, the silver halide photosensitive material of the present invention contains dihydroxybenzenes as a main developing agent and 3-3 as an auxiliary developing agent.
Suitable for processing with developers containing pyrazolidones or aminophenols. Preferably, in this developer, dihydroxybenzenes are used in an amount of 0.05 to 0.5 mol/j2.3-pyrazolidones or aminophenols in a range of 0.06 mol/1 or less.

Further, as described in US Pat. No. 4,269,929, the development speed can be increased and the development time can be shortened by adding amines to the developer.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). Can be done.

In addition, if necessary, water softeners, solubilizers, color toning agents, development accelerators, surfactants (preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, silver stains on the film, etc. Inhibitors such as silver 2-mercaptobenzimidazole sulfonate may also be included.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.

The processing temperature in the method of the invention is usually from 18°C to 50°C.
Selected between ℃.

Although it is preferable to use an automatic processor for photographic processing, the method of the present invention allows the total processing time from the time the photosensitive material is placed in the automatic processor to the time it comes out to be 90 to 120 seconds. , sufficiently ultra-high contrast negative gradation photographic characteristics can be obtained.

In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
Compounds described in No. 4,347 can be used. Patent application 1986-109 as a solubilizing agent added to the developer.
Compounds described in No. 743 can be used. Furthermore, as a pH buffering agent for use in developing solutions, JP-A-60-93,4
Compounds described in No. 33 or Japanese Patent Application No. 61-28708
Compounds described in can be used.

The present invention will be described in detail below with reference to Examples.

(Example) Emulsions [A) and CB) were prepared as shown below.

[Emulsion A]

4X10 per mole of silver in an aqueous gelatin solution kept at 50°C.
- In the presence of mol of potassium iridium(III) hexachloride and ammonia, an aqueous solution of silver nitrate and an aqueous solution of potassium iodide and potassium bromide were simultaneously added for 60 minutes, and the pA
By keeping g at 7.8, the average particle size is 0.28
A cubic monodisperse emulsion with an average silver iodide content of 0.3 mol % was prepared. This emulsion was desalted by the flocculation method, after which 40 g of inert gelatin was added per mole of silver, and 10-3 moles of Kl per mole of silver were added.
The mixture was added to the solution, allowed to stand for 15 minutes, and then cooled down.

[Emulsion B]

4X10 per mole of silver in an aqueous gelatin solution kept at 45°C.
−'Mole of potassium iridium(III) chloride, 2XIO”
In the presence of molar ammonium hexachloride rhodium (Illr) and ammonia, an average particle size of 0 was obtained by simultaneously adding an aqueous solution of silver nitrate and an aqueous solution of sodium chloride and potassium bromide for 60 minutes while maintaining the pAg at 7.8. A cubic monodisperse emulsion with a particle diameter of .28μ and an average silver chloride content of 70 mol% was prepared. In the same manner as Emulsion A, after desalting and adding inert gelatin, the mixture was kept at 60°C and chemically ripened by adding 8 quartz of chloroauric acid and 5 quartz of sodium thiosulfate. To this emulsion was further added 10-' mol of Kl solution per 1 mol of silver.
After allowing the mixture to stand for several minutes, the temperature was lowered.

These emulsions were divided into 1X10-' moles of 5,5'-dichloro-9-ethyl-5,5'-dichloro-9-ethyl-per mole of silver as a sensitizing dye.
3,3'-bis(3-sulfopropyl)oxacarbocyanine (sensitizing dye 1), and 5-[3-(4-sulfobutyl)-5-chloro-2-oxazolidylidene]
-1-hydroxyethyl-3-(2-pyridyl)-2-
Thiohydantoin (sensitizing dye 2) and the general formula of the present invention (
Compounds I) and (IF) were added as in Table 1.

In addition, the following hydrazine derivatives were added, and further 5-methylbenztriazole, 4-hydroxy-
1,3,3a,7-chitrazaindene, hydroquinone 200/a, the following compounds (a), (b), (c), 30 wt% polyethyl acrylate based on gelatin, and the following compound (d) as a gelatin hardening agent. Add
Polyethylene terephthalate film (150μ) with an undercoat layer (0.5μ) consisting of vinylidene chloride copolymer
) so that the amount of silver was 3.4 g/rrf.

15.0■/d CI (Coating of protective layer) Gelatin 1. 5g/rrr,
Polymethyl methacrylate particles (average particle size 2.5μ)
0. 3 g/n (applied using the following surfactants).

(CI(2CH÷,.(-CH,C÷,.

Cool(C00C2H400C -(-C-CH,-)- Ha 200■/d (d) HC)it = CH302CHtCHCI(!5OIC
2 for H=CH2 gelatin. (1wt% CH, C00C, H,.

CHCOOC,H,,31rng/d S Os Na C,F,7SO2NCH,C00K CsHr 2. 5./A These samples were exposed to 3200° tungsten light through an optical wedge and a contact screen (Fuji Film, 150L chain dot type), then developed with the following developer at 34°C for 30 seconds, fixed, washed with water, and dried. did.

Table 2 shows the photographic properties and black porosity measurement results of the obtained sample. The halftone gradation is expressed by the following formula.

*Exposure amount that gives halftone area ratio of -95% (1og
Exposure amount (fog) giving a halftone area ratio of -5%
E5%) The halftone dot quality was visually evaluated on a five-level scale. The 5-level evaluation is
"5" indicates the best quality, and "1" indicates the worst quality. As a halftone original for plate making, "5" and r4J are practical, and "
3 is the practical limit level, and 2 and 1 are impractical quality levels. The one between "4" and "3" is r3. It was set to 5J.

Kurobot was evaluated on a five-point scale based on microscopic observation.
5 represents the best quality and 1 represents the worst quality. "5
” or “4” is practical, “3” is poor or barely practical, and “2j or “1” is impractical. The one between "4" and "3" was evaluated as r3.5J.

The samples of the present invention maintain high contrast and have wide halftones. The quality of the halftone dots is as follows: Sample 1. IL21.31 lacks smoothness, and samples 2 to 10 and 22 to 30 have low optical density.
In contrast, the sample of the present invention has a high optical density and a smooth shape. Furthermore, black spots were improved compared to Samples 12-14 and 32-34.

table.

2 table.

Claims (4)

[Claims] (1) silver chloride content on the support of at least 50 mol %;
In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing silver halide and a hydrazine derivative, the silver halide emulsion layer and at least one other hydrophilic colloid layer are oxidized. A silver halide photographic material comprising a redox compound capable of releasing a development inhibitor and a compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Z_1 and Z_2 are respectively benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus,
Represents a group of nonmetallic atoms necessary to complete a thiazole nucleus, thiazoline nucleus, oxazole nucleus, selenazole nucleus, selenazoline nucleus, pyridine nucleus, benzimidazole nucleus, or quinoline nucleus. R_1 and R_2 each represent an alkyl group or an aralkyl group. X is a charge balance counterion, and n represents 0 or 1. (2) Claim No. (1) characterized in that the redox compound has hydroquinones, catechols, naphthohydroquinones, aminophenols, pyrazolidones, hydrazines, hydroxylamines, and reductones as redox groups. The silver halide photographic material described in Section 1. (3) Claim (1) characterized in that the redox compound has a hydrazine as a redox group.
The silver halide photographic material described in Section 1. (4) The redox compound has the following general formula (II-1), (I
The silver halide photographic material according to claim (1), characterized in that it is represented by I-2) or (II-3). General formula (II-1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II-2) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II-3) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In these formulas, R_3 represents an aliphatic group or an aromatic group. G_1 has ▲mathematical formulas, chemical formulas, tables, etc.▼group, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. There are tables, etc. ▼ Represents a group. G
_2 represents a simple bond, -O-, -S-, or ▲a numerical formula, chemical formula, table, etc.▼, and R_4 represents a hydrogen atom or R_3. A_1 and A_2 represent a hydrogen atom, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group, and may be substituted. In general formula (II-1), at least one of A_1 and A_2 is a hydrogen atom. A_3 has the same meaning as A_1 or represents ▲There are mathematical formulas, chemical formulas, tables, etc.▼. A_4 represents a nitro group, a cyano group, a carboxyl group, a sulfo group or -G_1-G_2-R_3. Time represents a divalent linking group, and t represents 0 or 1. PUG stands for development inhibitor.