JP2683743B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material capable of stably giving a photographic image with high contrast.

[Background of the Invention]

Generally, a high-contrast photographic image is used to form a photographic image in which characters or halftones are decomposed in the photolithography process, and a fine line image is formed in the ultraprecision photolithography process. It is known that a certain kind of silver halide photographic light-sensitive material can form a photographic image with extremely high contrast.

Conventionally, for example, a light-sensitive material made of a silver chlorobromide emulsion having an average grain size of 0.2 μm, a narrow grain distribution, a uniform grain shape, and a high silver chloride content (at least 50 mol% or more) is used as a sulfite ion. There is known a technique of obtaining an image having high contrast, high sharpness and high resolution, for example, a halftone dot image or a fine line image, by processing with an alkaline hydroquinone developing solution having a low concentration.

This type of silver halide photosensitive material is known as a lith type photosensitive material.

The photoengraving process includes a step of converting a continuous tone original into a halftone image, that is, a step of converting a continuous tone density change of the original into a set of halftone dots having an area proportional to the density. I have.

For this purpose, the lithographic light-sensitive material is used to photograph a document through an intersecting screen or a contact screen, and then develop it to form a halftone image.

For this purpose, a silver halide photographic light-sensitive material containing fine grains and a silver halide emulsion in which the grain size and the grain shape are uniform is used.Even when this type of silver halide photographic light-sensitive material is used, When processed with a general black-and-white developer, the halftone quality and the like are inferior to those when developed with a lith-type developer. Therefore, the concentration of sulfite ion is extremely low, and the developing agent is processed by a developing solution called lith type developing solution which is a hydroquinone single agent. However, since the squirrel-type developer is susceptible to autoxidation, its stability is extremely poor.Therefore, a control method for keeping the development quality constant during continuous use is required as much as possible. Great efforts have been made to improve sex.

As an improved technique, in order to maintain the stability of the lith-type developer, a replenisher for compensating for deterioration of activity due to development processing (processing fatigue replenishment) and a replenisher for compensating for oxidative deterioration due to aging ( The so-called two-liquid separation replenishment method, in which replenishment with time-dependent fatigue) is performed using different replenishers, is generally widely used in automatic developing machines for photolithography. However, the above method has a drawback in that it is necessary to appropriately control the replenishment balance of the two liquids, and the apparatus and the operation are complicated.

On the other hand, a technique for obtaining a high-contrast image by processing with a developer having a high sulfite ion concentration is known.

The above technique involves incorporating a hydrazine compound into a silver halide photographic light-sensitive material.

According to this technique, the concentration of sulfite ion can be kept high in the developing solution, and stable processing can be performed with the preservability being enhanced.

However, the developer used for the silver halide photographic light-sensitive material containing a hydrazine compound is liable to cause fog because it is necessary to have a relatively high pH value in order to obtain a high contrast. Various organic inhibitors must be included in high concentrations, which results in
It has the drawback of sacrificing sensitivity. Therefore, a silver halide photographic light-sensitive material capable of obtaining a high-contrast image and having low fog and high sensitivity is strongly desired.

[Object of the invention]

The present invention, in a silver halide photographic light-sensitive material containing a hydrazine compound, a highly sensitive and high-contrast image can be obtained, and even when applied to a plate-making light-sensitive material, it does not depend on the size of the halftone dot area and has a high quality. It is an object of the present invention to provide a silver halide photographic light-sensitive material capable of obtaining the following halftone dots.

[Configuration of the invention]

The object of the present invention has been achieved by a silver halide photographic light-sensitive material containing a combination of a compound represented by the following general formula [I] and a hydrazine compound.

General formula [I] In the formula, Z represents an atomic group necessary for completing an oxazole nucleus, a benzoxazole nucleus or a naphthoxazole nucleus.

R ¹ represents an unsubstituted or substituted alkyl group.

R ² is ^{-R 4 -S-R 5, -R} 4 -SO 2 -R 5 or Wherein R ⁴ represents an alkylene group, and R ⁵ and R ⁶
And R ⁷ represents a hydroxyalkyl group, a cyanoalkyl group, an alkoxyalkyl group, a carboxyalkyl group, a carbamoylalkyl group, a sulfamoylalkyl group, an alkylsulfonylaminoalkyl group, an alkylsulfonylalkyl group, or an alkoxycarbonylalkyl group, R ⁶ and R ⁷ may form a ring.

R ³ represents a group capable of being substituted, n represents an integer of 0-4.

 Hereinafter, the present invention will be described.

First, the compound represented by the general formula [I] will be described in detail.

In the general formula [I], Z represents an atomic group necessary for completing an oxazole nucleus, a benzoxazole nucleus or a naphthoxazole nucleus, and these nuclei may have a substituent on a carbon atom. The invention also includes such. Specific examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group), carbon Alkoxy group having 1 to 4 (eg methoxy group, ethoxy group, propoxy group, butoxy group), hydroxy group, alkoxycarbonyl group having 2 to 6 carbon atoms (eg methoxycarbonyl group, ethoxycarbonyl group, etc.), 2 to 2 carbon atoms 5, alkylcarbonyloxy group (eg, acetyloxy group, propionyloxy group, etc.), phenyl group, hydroxyphenyl group and the like.

Specific examples of these nuclei include oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, and 4-phenyloxazole as oxazole nuclei; benzoxazole, 5-chlorobenzoxazole as benzoxazole nuclei; 5-
Bromobenzoxazole, 5-methylbenzoxazole, 5-ethylbenzoxazole, 5-methoxybenzoxazole, 5-hydroxybenzoxazole, 5-ethoxycarbonylbenzoxazole, 5-
Acetyloxybenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 6-
Methoxybenzoxazole, 5,6-dimethylbenzoxazole, 6-chloro-5-methylbenzoxazole, and the like, naphtho [1,2-
d] oxazole, naphtho [2,1-d] oxazole,
A core such as naphtho [2,3-d] oxazole can be mentioned.

R ¹ represents an unsubstituted or substituted alkyl group. Examples of the substituent include a hydroxy group, a sulfone group, a sulphate group, a carbonyl group, a halogen atom (for example, a fluorine atom,
Chlorine atom), an unsubstituted or substituted alkoxy group having 1 to 4 carbon atoms (the alkoxy group may be further substituted with a sulfo group or a hydroxy group), an alkoxycarbonyl group having 2 to 5 carbon atoms, and 1 to 4 carbon atoms. , An alkylsulfonyl group, a sulfamoyl group, an unsubstituted or substituted carbamoyl group (including a substituted carbamoyl group substituted with an alkyl group having 1 to 4 carbon atoms), a substituted phenyl group (examples of the substituent are a sulfo group, a carboxy group , Hydroxy group, etc.), vinyl group,
And the like.

Specific examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group. Examples of the substituted alkyl group include 2-hydroxyethyl group and 3-hydroxypropyl group as hydroxyalkyl, and 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group and 2 as sulfoalkyl group.
-Hydroxy-3-sulfopropyl group, 2-chloro-3
-Sulfopropyl group, etc., as carboxyalkyl group such as carboxymethyl group, carboxyethyl group, carboxypropyl group, 2,2,2-trifluoroethyl group, 2-
(3-Sulfopropyloxy) ethyl group, 2- (2-hydroxyethoxy) ethyl group, ethoxycarbonylethyl group, methylsulfonylethyl group, 2-sulfamoylethyl group as sulfamoylalkyl group, 2-carbamoylethyl group , 2-N, N-dimethylcarbamoylethyl group, etc., phenethyl group, p-carboxyphenethyl group, p-sulfophenethyl group as sulfoaralkyl group, o-sulfophenethyl group, etc., p-hydroxyphenethyl group, allyl group, phenoxyethyl group Groups and the like.

R ² is ^{-R 4 -S-R 5, -R} 4 -SO 2 -R 5 or Is a group represented by R ⁴ represents an alkylene group, but a lower alkyl group such as methylene, ethylene, trimethylene, tetramethylene and propylene is preferable. R ⁵ , R ⁶
Examples of the hydroxyalkyl group represented by R ⁷ include 2-hydroxyethyl group, 3-hydroxypropyl group and 2-hydroxypropyl group, and examples of the cyanoalkyl group include 2-cyanoethyl group and 3-cyanoethyl group. , A cyanomethyl group and the like, an alkoxyalkyl group such as a methoxyethyl group and an ethoxyethyl group, a carboxyalkyl group such as a carboxymethyl group and a carboxyethyl group, and a carbamoylalkyl group such as Examples thereof include carbamoylmethyl group, 2-carbamoylethyl group, N-hydroxyethylcarbamoyl group, N, N-dimethylcarbamoylmethyl group, morpholinocarbamoylmethyl group, piperidinocarbamoylmethyl group, and the like, and sulfamoylalkyl group. Example, if a sulfamoylamino methyl group,
Examples thereof include 2-sulfamoylethyl group and N-hydroxyethylsulfamoylethyl group, and examples of the alkylsulfonylaminoalkyl group include methanesulfonamidoethyl group, ethanesulfonamidoethyl group, and the like, and alkylsulfonylalkyl group. Examples thereof include a methanesulfonylethyl group and an ethanesulfonylethyl group, and examples of the alkoxycarbonylalkyl group include a methoxycarbonylmethyl group and a methoxycarbonylethyl group.

When R ⁶ and R ⁷ form a ring, they can form a hetero ring, and examples of the hetero ring group formed at this time include a morpholino group, a piperazino group, a piperidino group and the like.

R ³ is a group capable of substituting for a pyridine ring, for example, an alkyl group (eg, methyl group, ethyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, etc.), a halogen atom (eg, chlorine atom, bromine atom, fluorine atom). Etc.), carboxy group, hydroxy group, sulfo group and the like.

The compound represented by the above-mentioned general formula [I] can function as a spectral sensitizing dye, and it is particularly preferable that Z represents an atomic group necessary for completing a benzoxazole nucleus, ¹ represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms substituted with a sulfo group, a carboxyl group, and / or a hydroxyl group,
Specifically, sulfoethyl group, 3-sulfopropyl group, 3
-Sulfobutyl group, 4-sulfobutyl group, carboxymethyl group, carboxyethyl group, hydroxyethyl group, 3
-Sulfo-2-hydroxypropyl group and the like.

Next, typical examples of the compound represented by the above general formula [I] used in the present invention will be given, but it goes without saying that the compounds usable in the present invention are not limited to these.

The compounds represented by the above-mentioned general formula [I] used in the present invention include those disclosed in JP-B-46-549, 46-18105, and 46-105.
18106, 46-18108, 47-4085, 58-52574
U.S. Pat.Nos. 2,839,403, 3,384,486, 3,625,69
It can be synthesized according to the method for synthesizing dimethine merocyanine described in No. 8, No. 3,480,439, No. 3,567,458 and the like.

Next, a specific synthesis example of the exemplified compound (1) will be shown. Other compounds represented by the above general formula [I] can also be synthesized according to the following synthesis method.

Synthesis Example: Synthesis of Exemplified Compound (1) 1- (2-morpholinoethyl) -from N-morpholinoethylglycine ethyl ester and ethyl-2-pyridyldithiocarbamate according to the method described in JP-A-61-118743. 3- (2-Pyridyl) -2-thiohydantoin was synthesized. 3.1 g of this thiohydantoin compound and 2-
3.4 g of [2- (2-anilinovinyl) -3-benzoxazolio] ethanesulfonate is stirred in 30 ml of morpholine at room temperature. 300 ml of ether was added to the reaction solution, and the supernatant was removed by decantation after stirring. To the residue is added 50 ml of methanol to dissolve, 2 g of potassium acetate is added, and the mixture is stirred and cooled. The precipitated crystals were collected by filtration and recrystallized from water-containing methanol to obtain 2.0 g of a reddish purple Exemplified Compound (1).
The maximum absorption wavelength of the obtained compound in methanol solvent is
It was 483 nm.

In the present invention, the compound represented by the general formula [I] may be contained in the light-sensitive material, but it is preferably contained in the silver halide emulsion layer, in which case it is contained in the silver halide emulsion. It is generally suitable and preferable to add 10 ^-6 to 10 ^-1 mol per mol of silver, more preferably 10 ^-4 to 10 ^-1 mol.
^{-It is} recommended to add ² mol. When adding these, they can be dissolved in alcohols such as methanol and ethanol, ethers, ketones, glycols such as ethylene glycol and diethylene glycol, and then added to the emulsion.

The light-sensitive material of the present invention contains a hydrazine compound.
Examples of the hydrazine compound preferably used in the present invention include compounds represented by the following general formula [II] or general formula [III].

General formula [II] R ¹¹ NHNHCHO General formula [III] R ¹¹ NHNHCOR ^{12 In the} formula, R ¹¹ and R ¹² each represent an optionally substituted aryl group, a heterocyclic group or an optionally substituted alkyl group.

The aryl group represented by R ¹¹ and R ¹² includes a benzene ring or a naphthalene ring, and this ring may be substituted with various substituents, and a preferable substituent is a linear or branched alkyl group (preferably Are those having 1 to 20 carbon atoms, such as methyl group, ethyl group, isopropyl group, n-dodecyl group, etc.),
Alkoxy group (preferably having 1 to 20 carbon atoms, such as methoxy group, ethoxy group, etc.), aliphatic acylamino group (preferably having alkyl group having 2 to 21 carbon atoms, such as acetylamino group, heptylamino group, etc. ), An aromatic acylamino group, and the like. In addition to these, a substituted or unsubstituted aromatic ring as described above is -CONH-, -S.
-, - O -, - SO 2 NH -, - NHCONH -, - including those attached with a linking group such as CH ₂ CHN-. Similarly, the heterocyclic group may include a pyridine ring, a quinoline ring, a furan ring, and a thiophene ring. Moreover, these rings can have the same substituents as when substituting for an aryl group.

The hydrazine compound can be synthesized with reference to the description in US Pat. No. 4,269,929.

The hydrazine compound can be contained in any photographic constituent layer, preferably in the emulsion layer or in the hydrophilic colloid layer adjacent to the emulsion layer, and further in another hydrophilic colloid layer, but more preferably It is preferably contained in the emulsion layer or in a layer adjacent to the emulsion layer.

The hydrazine compound can be added after being dissolved in alcohols such as methanol and ethanol, glycols such as ethylene glycol and diethylene glycol, ethers and ketones, and the addition amount thereof is generally preferably silver halide. It is 10 ^-6 to 10 ^-1 per mol, and more preferably 10 ^-4 to 10 ^-2 .

Examples of particularly preferable hydrazine compounds are as follows.

(H-1) 1-formyl-2-phenylhydrazine (H-2) 1-formyl-2- (4-methoxyphenyl) hydrazine (H-3) 1-formyl-2- (2-pyridyl) hydrazine (H -4) 1-formyl-2- (2-furanyl) hydrazine (H-5) 1-formyl-2- (2-thiophenyl) hydrazine (H-6) 1-formyl-2- (4-acetamidophenyl) hydrazine (H-7) 1-formyl-2- (4-butylamidophenyl) hydrazine (H-8) 1-formyl-2- (4-phenylacetamidophenyl) hydrazine (H-9) 1-formyl-2- ( 4-dimethylaminophenyl)
Hydrazine (H-10) 1-formyl-2- (4-acetamido-2-methyl-phenyl) hydrazine (H-11) 1-formyl-2- [4- (3-phenyl-thioureido) phenyl] hydrazine (H -12) 1-formyl-2- [4- (3-ethyl-thioureido) phenyl] hydrazine (H-13) 1-formyl-2- {4- [4- (3-phenylthioureido) phenyl] carbamyl Phenyl} hydrazine (H-14) 1-formyl-2- {4- [3- (4,5-dimethylthiazol-2-yl) thioureylene] phenyl} hydrazine (H-15) 1-formyl-2- [4 -(Phenylthiocarbamyl) phenyl] hydrazine (H-16) 1-formyl-2- [4- (N-methylbenzothiazol-2-yl) thioureylenephenyl] hydrazide (H-17) 1-formyl-2-{[4- (1,3-dimethylbenzimidazol-2-yl) thioureylene] phenyl}
Hydrazine (H-18) 1-formyl-2-{[4- (5-methyl-2-thio-imidazol-3-yl) phenyl]} hydrazine (H-19) 1-formyl-2- {4- ( 3-n-butylureido) phenyl} hydrazine (H-20) 1-formyl-2- {4- [3- (p-chlorophenyl) ureido] phenyl} hydrazine (H-21) 1-formyl-2- (4 -{3- [p- (2-mercapto-tetrazol-3-yl) phenyl] thioureylene} phenyl) hydrazine (H-22) 1-formyl-2- {4- [ω- (N-sulfopropylbenzothiazole- 2-yl) propylamino] phenyl} hydrazine (H-23) 1-formyl-2- (4- {3- (p- (phenylsulfoaminophenyl] -ureylene} phenyl) hydrazine (H 24) 1-formyl-2- [4- (2,4-di-tert-pentylphenoxymethylamido) phenyl] hydrazine (H-25) 1-formyl-2- {4- [3- (p-ethylphenyl) ) Ureido] phenyl} hydrazine (H-26) 1-formyl-2- {4- [3- (2-methoxyphenyl) ureido] phenyl} hydrazine (H-27) 1-formyl-2- [4- (3 -Ethylureido) phenyl] hydrazine (H-28) 1-formyl-2- [4- (3-propylureido)
Phenyl] hydrazine (H-29) 1-formyl-2- {4- [3- (p-methoxyphenyl) ureido] phenyl} hydrazine (H-30) 1-formyl-2- {4- [3- (p -Methoxyphenyl) ureido] -2-methoxyphenyl} hydrazine (H-31) 1-formyl-2- {3- [3- (p-chlorophenyl) ureido] phenyl} hydrazine (H-32) 1-formyl-2 -[4- (3-n-Butylureido) phenyl] hydrazine (H-33) 1-formyl-2- [4- (3-dodecylureido)
Phenyl] hydrazine (H-34) 1-formyl-2- [4- (3-octadecylureido) phenyl] hydrazine (H-35) 1-formyl-2- {4- [3- (hexanoyl) ureido] phenyl} Hydrazine (H-36) 1-formyl-2- {4- [3- (benzyl) ureido] phenyl} hydrazine (H-37) 1-formyl-2- {4- [3- (pyridin-2-yl) Ureido] phenyl} hydrazine (H-38) 1-formyl-2- {4- [3- (thiophenyl-2
-Yl) ureido] phenyl} hydrazine (H-39) 1-formyl-2- {4- [3- (4-methylthiazol-2-yl) ureido] phenyl} hydrazine (H-40) 1-formyl-2 -{4- [3- (5-Nitrophenyl) ureido] phenyl} hydrazine (H-41) 1-n-hexylacetylamino-4- (2-acetylhydrazino) benzene (H-42) 1- (p -Chlorobenzoyl) -2-phenylhydrazine (H-43) 1- (p-cyanobenzoyl) -2-phenylhydrazine (H-44) 1- (p-carboxybenzoyl) -2-phenylhydrazine (H-45) 1- (3,5-dichlorobenzoyl) -2-phenylhydrazine (H-46) 1- (2-formylhydrazino) -4- (N-dimethylamino) benzene (H-47) 1- ( -Formylhydrazino) -4- (2-formyhydrazino) benzylbenzene The silver halide emulsion layer used in the silver halide photographic light-sensitive material of the present invention (hereinafter sometimes simply referred to as a light-sensitive material) contains various silver halides. Can be used. Examples thereof include silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. The effect of the present invention is particularly remarkable for silver bromide and silver iodobromide, and is particularly effective for a high-sensitivity light-sensitive material containing little silver iodide (AgI 5 mol% or less).

The method for preparing the silver halide emulsion in the silver halide emulsion layer of the light-sensitive material of the present invention may be, for example, a silver halide emulsion suspended in a hydrophilic colloid by a known method, for example, a neutral method or an ammonia method. The single-jet method, the double-jet method, and other emulsion preparation methods described above are used.

The silver halide contained in the silver halide emulsion layer used in the light-sensitive material of the present invention has an average grain size of 0.1 to 1.0 μm.
m, particularly preferably 0.1 to 0.7 μm, and at least 75%, particularly preferably 80% or more of the total number of particles is 0.
It is preferable to include silver halide having a grain size of 7 to 1.3 times.

Further, as a silver halide emulsion in which polyvalent metal ions (for example, iridium, rhodium, etc.) are occluded, US Pat.
Emulsions according to 3,271,157, 3,447,927 and 3,531,291 can also be used. The silver halide emulsion is usually used. That is, it can be sensitized by sensitization by chemical sensitization using an ionic compound, a gold compound, (chloroaurate, gold trichloride, etc.).

For the silver halide emulsion layer or other hydrophilic colloid layer, polymer latex composed of homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. is used to improve dimensional stability of photographic materials and film physical properties. It may be contained in order to improve.

The silver halide emulsion used in the present invention can be imparted with color sensitivity in a desired photosensitive wavelength region by using a sensitizing dye. As the sensitizing dye, those commonly used such as methine dyes such as cyanine, heminanine, rhodacyanine, merocyanine, oxanol, and hemioxonol, and styryl dyes can be used, but at least the dye represented by the general formula [I] can be used. It is necessary to contain.

For the silver halide emulsion, those represented by the following general formula [IV] or (V) are useful as stabilizers or antifoggants, and these are preferably used.

General formula (IV) General formula [V] In the formula, R _a , R _b , R _c and R _d may be the same or different and each is a hydrogen atom, a halogen atom, a nitro group, an amino group, a cyano group, a hydroxyl group, a carboxyl group or an alkoxy group. Represents an acyl group or a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and R _b and R _c may be bonded to each other to form a 5- or 6-membered closed ring structure.

Specific examples of the compounds represented by the above general formulas [IV] and [V] include the following.

(S-1) 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (S-2) 4-Hydroxy-5-ethyl-6-methyl-1,3,3a, 7
-Tetrazaindene (S-3) 2-mercaptomethyl-4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (S-4) 2-carboxy-4-hydroxy-6-methyl- 1,3,
3a, 7-Tetrazaindene (S-5) 2,4-dihydroxy-6-methyl-1,3,3a, 7-tetrazaindene (S-6) 2-amino-5-carboxy-4-hydroxy- 1,3,
3a, 7-Tetrazaindene (S-7) 5-carboxy-4-hydroxy-1,3,3a, 7-tetrazaindene (S-8) 2-Methyl-4-hydroxy-6-methyl-1, 3,3a, 7
-Tetrazaindene (S-9) 4-hydroxy-5-cyano-1,3,3a, 7-tetrazaindene (S-10) 3-chloro-4-hydroxy-6-methyl-1,3,3a , 7
-Tetrazaindene (S-11) 2,4-dihydroxy-6-methyl-1,3,3a, 7-tetrazaindene (S-12) 1,2-bis (4-hydroxy-6-methyl-1) , 3,3a, 7
-Tetrazainden-2-yl) -1,2-hydroxyethane (S-13) 5-amino-7-hydroxy-2-p-methoxyphenyl-1,2,3,4,6-pentaazaindene The compound can be added during the physical ripening of silver halide and / or at the end thereof. The silver halide can be present in the process of growing and forming in a hydrophilic colloid layer such as gelatin. Further, it may be added immediately before chemical ripening, during chemical ripening and / or at the end, or may be added at the time of preparing the coating solution. As a general preferred addition method, at the end of chemical ripening, 10 ^-6 to
It can be added in the range of 10 ^-1 , more preferably 10 ^-4 to 10 ^-2 . When the above compound is added to the emulsion, it can be added after dissolution according to the method of adding the compound represented by the general formula [I].

Further, the light-sensitive material of the present invention has the following general formula [VI] or [VII] general formula [VI] general formula [VII] Ar-OH HO-Ar-OH as a fog inhibitor or stabilizer. Aromatic ring is substituted with an alkyl group (having 1 to 25 carbon atoms), a halogen atom, a hydroxy group, a hydroxyalkyl group (the alkyl group may be substituted with a hydroxy group or a halogen atom), an aldoxime group, etc. May be done. ], A remarkable fog suppression effect can be obtained.

 Specifically, the following compounds can be mentioned.

(1) Hydroquinone (2) Methylhydroquinone (3) Chlorohydroquinone (4) Hydroquinone monosulfonate (5) 2,5-Diethylhydroquinone (6) 1,4-Dihydroxynaphthalene (7) 2,3-Dihydroxynaphthalene (8) Gentisaldoxime (9) 2,5-dihydroxyacetophenone oxime (10) Gentisamide (11) N-methylgentisamide (12) N- (β-hydroxyethyl) gentisamide (13) N- (n-hexadecyl) gentisamide (14) salicylaldoxime (15) resorcylaldoxime (16) hydroquinone monobenzoate (17) hydroquinone aldoxime The above compounds are described in US Patent No. 2,675,314 and British Patent No. 62.
It can be synthesized with reference to the descriptions of 3,448 and JP-A No. 52-11029.

In addition, the fog-inhibiting agent which can be usually used in silver halide emulsions can be used in the silver halide photographic emulsion used in the present invention. Any of the hydrazine compounds, polyalkylene oxide compounds, antifoggants or stabilizers mentioned above are generally used per mol of silver halide.
Concentration of 10 ^-9 to 10 ^-1 mol / silver 1 mol, more preferably 5 ×
It can be used at a concentration of 10 ^{−4 to} 5 × 10 ⁻² mol / silver 1 mol.

To add these additives to the silver halide emulsion, known methods for preparing additives can be used. That is, it may be dissolved in alcohols such as methyl alcohol, ethyl alcohol and the like, ketones such as ethers (diethyl ether, dipropyl ether) acetone, dioxane, petroleum ether, or nonionic, anionic and cationic surfactants. It may be dispersed in a solvent having a boiling point and added.

The light-sensitive material of the present invention can contain a polyethylene oxide compound represented by the following general formula [VIII] as a development modifier in the silver halide emulsion and / or in the hydrophilic colloid layer adjacent to the emulsion layer.

In the general formula [VIII] _{HO (CH 2 CH 2 O)} n H [wherein, n represents an integer of 10 to 100. Further, the following general formula [IX] which is a block polymer of polyalkylene oxide [In the formula, b represents an integer of 10 to 50, a and c each represent an integer such that a + c is 5 to 50, and the polyoxyethylene group accounts for 10 to 70% by weight of the above block polymer. ] Alternatively, the compound represented by the following general formula [X] can be contained in the emulsion layer and / or in the hydrophilic colloid layer adjacent to the emulsion layer.

General formula [X] [In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms in the alkyl group portion, an arylcarbonyl group (for example, benzoyl, p-methylbenzoyl, etc.) and the like. In the formula, d represents an integer of 10 to 100. The polyalkylene oxide polymer as described above is useful for the purpose of the present invention.

These compounds include polyols such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene polymers, aliphatic alcohols, phenols,
It can be synthesized by condensing a fatty acid, ethylene oxide, propylene oxide and the like. The number of polyalkylene oxide chains in the molecule may be not one but a block copolymer divided into two or more places. At this time, it is generally necessary that the total degree of polymerization of the polyalkylene oxide be 10 or more, and 100 or less is preferable.

Next, specific examples of the polyalkylene oxide compound that can be used in the light-sensitive material of the present invention will be shown, but the invention is not limited thereto.

Specific examples of polyalkylene oxide compounds: (I-1) HO (CH ₂ CH ₂ O) _n [n-35] (I-2) nC ₄ H ₉ O (CH ₂ CH ₂ O) _n H [n = 20 ] (I-3) nC ₈ H ₁₇ O (CH ₂ CH ₂ O) _n H [n = 30] (I-4) nC ₁₂ H ₂₅ O (CH ₂ CH ₂ O) _n H [n = 30] The addition amount of the polyalkylene oxide compound used in the present invention is preferably 10 mg to 3 g per mol of silver halide, and the addition timing can be selected at any time during the process of producing a light-sensitive material. For example, it is preferably added after the completion of the second ripening.

The silver halide photographic emulsion that can be used in the present invention includes, for example, aldehydes (formaldehydes, glyoxal, glutaraldehydes,
Mucochloric acid, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compounds (1,3,5-triacroyl-hexahydro-s-triazine, bis (Vinylsulfonyl) methyl ether, etc.), active halide (2,4-dichloro-6-
(Hydroxy-s-triazine etc.) and the like can be used alone or in combination, and those usually used as thickeners, matting agents, coating aids and the like can be used. Also,
As the binder, a commonly used hydrophilic binder having a protective colloid property can be used.

When the present invention is applied to a color light-sensitive material, those usually used as couplers, ultraviolet absorbers, optical brighteners, image stabilizers, antioxidants, lubricants, sequestering agents, emulsifying dispersants, etc. Can be used.

In the light-sensitive material of the present invention, as a layer other than the silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer, an undercoat layer, an auxiliary layer, an anti-irradiation layer, a backing layer and the like are optionally provided. Often, the support used may be selected from baryta paper, polyethylene-coated paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc., depending on the intended use of the light-sensitive material.

The light-sensitive material of the present invention contains HO- (CH = CH) _n- OH as a developer.
Type, H ₂ N- (C = C) _n -NH ₂ type, a developer having a heterocycle, and other commonly used developers can be used.

Typical examples of HO- (CH = CH) _n -OH type developers include catechol, pyrogallol and its derivatives, and ascorbic acid, and hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, tolhydroquinone, methylhydroquinone, 2 , 3
-Dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone and the like.

Typical examples of HO- (CH = CH) _n -NH ₂ type developers are ortho and para aminophenols or aminopyrazolones, and 4-aminophenol, 2-amino-6-phenylphenol, 2-amino- 4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3,
4-diaminophenol, 3-methyl-4,6-diaminophenol, 2,4-diaminoresorcinol, 2,4,6-triaminophenol, N-methyl-p-aminophenol, N-β-hydroxyethyl-p -Aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol and the like can be mentioned.

Examples of the developer having a heterocycle include 1-phenyl-3-pyrazolidone (phenidone), 1-phenyl-4
-Amino-5-pyrazolone, 1- (p-aminophenyl) -3-amino-pyrazolin, 1-phenyl-2-methyl-4-amino-5-pyrazolone, 1-phenyl-4,
4'-dimethyl-3-pyrazolidone (dimesone), 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone (dimesone-s) and the like can be mentioned.

In addition, The James of TH Theory of the Photographic Process 4th Edition (The Theory of
the Photographic Process, Fourth Edition) No. 291-33
Page 4 and the Journal of the American Chemical Soc
Society, Vol. 73, page 3100 (1951), can be effectively used for processing the light-sensitive material of the present invention. These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination. A preferred combination is a combination of hydroquinone and phenidone or hydroquinone and dimezone, the hydroquinone generally being 5 g to 50 g / l,
Further, phenidone or dimezone is preferably used in the range of 0.05 g to 5 g / l.

Further, even if a sulfite such as sodium sulfite, potassium sulfite, or ammonium sulfite is used as a preservative in the developer used for the light-sensitive material of the present invention, the effect of the present invention is not impaired. The sulfite concentration is preferably 0.06 to 1 gram ion / l. Also, hydroxylamine and hydrazide compounds may be used as preservatives. Others: Adjusting pH and providing a buffer function by using caustic alkali, alkali carbonate or amine as used in general black and white developers, inorganic development inhibitors such as bromcali, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol , Benzyl alcohol, development accelerators such as polyalkylene oxides, sodium alkylaryl sulfonates, natural saponins, surfactants such as saccharides or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin and gluoxal, sulfuric acid The addition of an ionic strength modifier such as sodium is optional.
The pH value is generally preferably set to any value between 9 and 12,
From the viewpoint of homeostasis and photographic performance, it is more preferable to use in the range of pH 10-11.

The developer used in the light-sensitive material of the present invention may contain alkanolamine and glycols. Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine and the like, with preference given to triethanolamine. The preferred content of these alkanolamines is from 2 to 300 g per developer, especially per developer.
10 to 200 g is preferable.

Examples of glycols include ethylene glycol,
Examples thereof include diene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol and 2-methoxyethanol, and diethylene glycol is preferable. The amount of these glycols used is preferably 10 to 200 g per developer, and particularly preferably 20 to 100 g per developer.

The above alkanolamines and glycols may be used alone or in combination of two or more.

Processing of the light-sensitive material of the present invention with a developer can be performed under various conditions, but the development temperature is preferably 50 ° C. or lower,
In particular, the temperature is preferably around 40 ° C., and the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, a good result is often obtained. It is optional to employ processing steps other than development, such as washing with water, stabilization of stoppage, fixing, and, if necessary, steps of pre-curing and neutralization, and these steps can be omitted as appropriate. Furthermore, these processes may be so-called hand developing processes such as plate developing and frame developing, or may be mechanical developing such as roller developing and hanger developing.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. However, as a matter of course, the technical scope of the present invention is not limited to the following embodiments, and various embodiments can be applied.

Hereinafter, a high-sensitivity silver halide photographic light-sensitive material, that is, a so-called dark room type silver halide photographic light-sensitive material will be described as an embodiment of the present invention, but the present invention is not limited thereto.

Example 1 A silver chlorobromide emulsion containing 10 ^-7 mol of iridium / 1 mol of silver by the simultaneous mixing method (70 mol% of silver chloride per 1 mol of silver).
Was prepared. The average grain size was 0.08 μm. This emulsion was washed with water and desalted in a conventional manner, and then sensitized with sulfur in the presence of 5 × 10 ⁻⁷ mol / Ag1 mol of rhodium salt at 50 ° C. for 60 minutes to obtain a stabilizer after sensitization. 1.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3 g of hydroquinone, 2 g of phenidone,
Butylaminodiethanol (2 g) and resorcinaldoxime (2 g) were added per mol of silver.

Further, benzyladenine and 1-phenyl-5-mercaptotetrazole as fog-inhibiting agents were each 0.1 g per 1 mol of silver, and acrylic acid was used as a latex polymer.
Add 5 g of butyl acrylate polymer per mol of silver, 0.1 g of polyethylene glycol of ethylene oxide chain 30 (one of the terminal groups is dodecylbenzene) as a development modifier per mol of silver, and add sodium dodecylbenzenesulfonate as a coating aid. , Saponin, and a styrene-maleic acid copolymer as a thickener were added to prepare an emulsion. This emulsion was divided into 10 parts, and the general formula [I] shown in Table 1 or its comparative compound (below) and the compound represented by the general formula [II] as a hydrazine compound were added thereto to prepare an emulsion coating solution.

The compound represented by the general formula [I] is 3 × 10 ⁻⁴ mol / silver 1
3 × 10 ⁻³ mol / mol, the compound represented by the general formula [II]
1 mol of silver was added.

Then, a coating solution for emulsion protective film was prepared as follows. That is, 10 liters of pure water was added to 1 kg of gelatin and swelled at 40 ° C.
After heating to 30 g, a polymer of methyl metacurate (average particle size 0.27 μm) 30 g as a matting agent, sulfosuccinic acid alkyl ester 5 g as an activator, 1- (p-acetylamidophenyl) -5-mercaptotetrazole 1 g, poly 5 g of alkylene oxide and 5 g of lithium chloride salt were dispersed in gelatin and finished to 20 l to prepare a coating liquid for protective film.

Preparation of silver halide photographic light-sensitive material A combination of the emulsion coating solution and the coating solution for protective film prepared as follows on a 100 μm-thick polyethylene terephthalate support which has been subjected to subbing processing, and silver amount by simultaneous multi-layer coating by the slide hopper method. 1.5 g / m ^2, the sample so that the amount with gelatin of the emulsion layer is 0.8 g / m ^2, also the amount with gelatin of the protective layer is shown in application to table 1 to be 1.1 g / m ² No. 1 to N
Created o.10. At the time of multi-layer coating, four kinds of hardeners of formaldehyde, mucochloric acid, 1,3,5-triazine cyanuric acid and ethyleneimine were added inline to the protective coating solution to harden the film so that the swelling degree was 1.8. .

These samples were subjected to stepwise exposure with xenon light through a commercially available ordinary contact screen (gray negative 150 line), and then developed with the developer formulation shown below. The fixer used was the rapid fixer with the following formulation. The development conditions are 40 ° C for 10 seconds and 35 ° C for 10 seconds for fixing.
Seconds, washing at 30 ° C. for 10 seconds, and drying at 45 ° C. for 10 seconds.

The quality of each halftone dot area of 10%, 50% and 95% of the treated sample was evaluated by visual observation using a 100 times magnifying glass on a scale of 5 levels. As for the evaluation points, “1” is the lowest grade, and the grade is high in order, and the rank “5” indicates the best level.

Developer formulation Sodium sulfosalicylate 35g Ethylenediaminetetraacetic acid disodium salt 1g Sodium sulfite 120g Butylaminodiethanolamine 20g N-methyl-p-aminophenol (hemisulphate) 0.3g Sodium bromide 6.0g 5-Methylbenzotriazole 0.9g 2- Mercaptobenzimidazole-5-sulfonic acid 0.1g 1-Phenyl-5-mercaptotetrazole 0.1g Adjust to pH 11.5 with KOH.

<Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17g Sodium acetate / trihydrate 6.5g Boric acid 6g Sodium citrate / dihydrate 2g (Composition B) Pure water (ion) Exchange) 17 ml Sulfuric acid (50% W / W aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / W aqueous solution) 26.5 g When using the fixer, the above composition A and composition B in 500 ml of water are used. Were melted in this order and finished to 1 before use. The pH of this fixer was adjusted to 5 with acetic acid.

The following compound was used as a compound for comparison with the compound represented by the general formula [I].

a 1- (2-hydroxyethoxyethyl) -3-phenyl-5-[(3-sulfobutyl-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt b 1- (2-diethylaminoethyl)- 3-ethyl-
5-[(3-Sulfopropyl-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt c 1- (2-hydroxyethyl) -3-ethyl-5
[(3-Sulfoethyl-2-benzoxazolinidene)
Ethylidene] -2-thiohydantoin sodium salt As is clear from Table 1, in the light-sensitive material using the hydrazine compound, by using the compound represented by the general formula [I] of the present invention, high quality halftone dots can be obtained and at the same time high sensitivity can be obtained. I understand.

〔The invention's effect〕

Sensitivity and contrast are improved in a light-sensitive material containing a hydrazine compound, and when it is applied to a light-sensitive material requiring halftone dot quality, high-quality halftone dots are obtained by halftone dot formation regardless of the halftone dot area size. be able to.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising a compound represented by the following general formula [I] and a hydrazine compound in combination. General formula [I] In the formula, Z represents an atomic group necessary for completing an oxazole nucleus, a benzoxazole nucleus or a naphthoxazole nucleus. R ¹ represents an unsubstituted or substituted alkyl group. R ² is ^{-R 4 -S-R 5, -R} 4 -SO 2 -R 5 or Wherein R ⁴ represents an alkylene group, and R ⁵ and R ⁶
And R ⁷ represents a hydroxyalkyl group, a cyanoalkyl group, an alkoxyalkyl group, a carboxyalkyl group, a carbamoylalkyl group, a sulfamoylalkyl group, an alkylsulfonylaminoalkyl group, an alkylsulfonylalkyl group, or an alkoxycarbonylalkyl group, R ⁶ and R ⁷ may form a ring. R ³ represents a group capable of being substituted, n represents an integer of 0-4.