JPH03168736A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain images having a high sensitivity and high contrast and to obtain high-quality dots regardless of the sizes of dot areas by incorporating a specific compd. and hydrazine compd. into the above photosensitive material. CONSTITUTION:This photosensitive material contains the compd. expressed by formula and the hydrazine compd. In the formula I, R1 and R2 denote substd. and unsubstd. alkyl groups. The hydrazine compd. is exemplified by the compd. expressed by formula R1NHNHCHO or R1NHNHCOR2, where R1 and R2 respectively denote substd. or unsubstd. aryl groups or substd. or unsubstd. alkyl groups. The aryl groups expressed by R1 and R2 include a benzene ring or naphthalene ring which ring may be substd. with various substituents. The preferable substituents include straight and branched alkyl groups, etc. Thus, the sensitivity and contrast are improved and the high-quality dots are obtd. regardless of the sizes of the dot areas in the dot formation.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming method, and more particularly to a silver image forming method that stably provides high contrast photographic images.

(Prior Art) In general, in the photolithography process, characters or halftone-resolved photographic images are used, and in the ultra-precision photolithography process, fine line image forms or high-contrast photographic images are used. It is known that certain silver halide photographic materials for this purpose can form photographic images with extremely high contrast.

Conventionally, for example, photosensitive materials made of silver chlorobromide emulsions with an average grain size of 0.2 μm, a narrow grain distribution and uniform grain shape, and a high silver chloride content (at least 50 mol% or more) have been used. A method of obtaining images with high contrast, high sharpness, and high resolution, such as halftone dot images or fine line images, is being carried out by processing with an alkaline hydroquinone developer having a low sulfite ion intensity.

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

The photolithography process involves converting a continuous-tone original into a halftone image, that is, converting the continuous-tone density changes of the original into a set of halftone dots with an area proportional to the density. ing.

For this purpose, the above-mentioned lithium-type photosensitive material is used to photograph the original material through an intersection screen or contact screen, and then to form a halftone dot image by performing development processing.

For this purpose, a silver halide photographic material containing a silver halide emulsion with fine grains and a uniform grain size and shape is used, but even when this type of silver halide photographic material is used, When processed with a general black and white developer, the quality of halftone dots, etc. is inferior to that obtained with a Lith type developer. Therefore, the sulfite ion concentration is extremely low,
Processing is performed using a developer called a Lith type developer, which uses hydroquinone as a single agent. However, since Lith-type developers are susceptible to auto-oxidation and have extremely poor storage stability, there is a strong need for control methods to maintain constant development quality even during continuous use. Much effort has been made to improve sex.

As a method to improve this, in order to maintain the stability of the above-mentioned Lith type developer, there is a replenisher that compensates for the deterioration in activity due to development processing (processing fatigue replenishment), and a replenisher that compensates for oxidative deterioration over time. A so-called two-liquid separation replenishment system, in which the replenisher and the replenisher (time-related fatigue replenisher) are refilled using separate replenishers, is generally widely adopted in automatic developing machines for photolithography and the like. However, the above method has the disadvantage that it is necessary to control the replenishment balance of the two liquids, which complicates the equipment and operation.

On the other hand, a method is known in which a high contrast image is obtained by processing with a developer having a high sulfite ion concentration.

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

This method makes it possible to maintain a high sulfite ion concentration in the developing solution, allowing for stable processing with enhanced preservability.However, silver halide photographic light-sensitive materials containing hydrazine compounds In order to obtain high contrast, the developer used must have a relatively high pi value, which tends to cause fogging, and in order to suppress this fogging, various organic inhibitors are contained in high concentrations. The drawback is that sensitivity comes at a cost.

Therefore, there is a strong desire for silver halide photographic materials that can provide high-contrast images, have low fog, and have high sensitivity.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material containing a hydrazine compound, which can provide high-sensitivity, high-contrast images and provide high-quality halftone dots regardless of the size of the halftone dot area. An object of the present invention is to provide a silver photographic material.

[Structure of the invention]

The above object of the present invention is achieved by a silver halide photographic material containing a compound represented by the following general formula [I] and a hydrazine compound.

General formula (1) 0 l [In the formula, R1 and R2 represent a substituted or unsubstituted alkyl group. ] Hereinafter, the present invention will be specifically explained.

First, specific examples of the compound represented by the general formula [■] will be given, but the present invention is not limited thereto.

(l) (2) (3) (4) (5) (6) OH 0H (7) (8) (9) (lO) (11) The hydrazine compounds preferably used in the present invention include the following: Examples include compounds represented by general formula (n) or general formula (I[I).

General formula (II) General formula (III) R
, N H N H C H O R , N H N
H C O R , where R and R2 each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group.

The aryl group represented by R+ and R2 includes a bezene ring or a na7talene ring, and this ring may be substituted with various substituents, and preferred substituents include straight chain and branched alkyl groups. (Preferably those with 1 to 20 carbon atoms, such as methyl group, ethyl group, isobrobyl group, n-dodecyl group, etc.)
, an alkoxy group (preferably one having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, etc.), an aliphatic acylamino group (preferably one having an alkyl group having 2 to 2 liters of carbon atoms, such as an acetylamino group, heptylamino group, etc.) group, etc.), aromatic acylamino group, etc. In addition to these, for example, a substituted or unsubstituted aromatic ring as described above may be used.
--S-,, O S02NH- -NHC
It also includes those bonded with a linking group such as ONH- CHzCHN-.

These hydrazine compounds can be combined with reference to the description in US Pat. No. 4,269,929.

The hydrazine compound can be contained in the emulsion layer or in the hydrophilic colloid layer adjacent to the emulsion layer, or even in other hydrophilic colloid layers, but is preferably contained in the emulsion layer or in the layer adjacent to the emulsion layer. It is to be made to contain.

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, ketones, etc., and the amount of addition is 1 mole of silver halide. per lXIO' ~ IXlO' mortet
f) F), good'! L, <Ha IXIO-' ~I
XIO−” mole range.

Examples of particularly preferred hydrazine compounds are as follows.

(H-1) ■-Honoleminole-2-phenylenehydrazine (H-2
) ■-Formy-2-(4-methoxyphenyl)hydrazine (H-3) l-formyl-2-(4-promophenyl)hydrazine (H-4) l-formyl-2-(4-ethylphenyl)hydrazine ( H-5) l-formyl-2-(4-methoxyphenyl) hydrazine (H-6) l-formyl-2-(4-acetoad7enyl) hydrazine (H-7) l-formyl-2-(4- (butylamidophenyl) hydrazine (H-8) l-formyl-2-(4-phenylacetamido7enyl) hydrazine (H-9) ■-formyl-2 (4-dimethylaminophenyl) hydrazine (H-10) l -Formyl-2-(4-acetamido-2-methylethioureido)hydrazine (H-II) l-Formyl-2-(4-(3-7enyl-thioureido)phenylene)hydrazine (H-12) l- formyl-2-(4-(3-ethyl-thioureido)7enyl]hydrazine (H-13) l-formyl-2-(4-(4-(3-7)
phenylthioureido) phenyl]carbamyl 7-functional di-nole} hydrazine (H-14) l-formyl-2 - {4 - (3 - (4,
5-dimethylthiazol-2-yl)thioureylene]
7enyl}hydrazine (H-15) 1-formyl-2-(4-(phenylthiocarpamyl)
phenyl]hydrazine (H-16) l-formyl-2-(4-(N-methylbenzothiazol-2-yl)thioureylene7-enyl]hydrazine (H-17) ■-formyl-2- {(4-( 1,3-dimethylbenzimidazole-2-ylthioureylene]phenyl} hydrazine (H-18) l-formyl-2-((4-(5-methyl-2-thioimidazolin-3-yl)pheny) }Hydrazine (H-19) !-Formy-2-((4-(3-n-butylureido)hydrazine (H-20) l-formyl-2-{4-(3-(p-chloro7enyl)ureido) 7enyl}hydrazine (H-
21) l-formylu2-(4-{3-(p-(
2-Mercaptotetrazol-3-yl)7enyl]thioureylene}phenyl)hydrazine (H-
22) 1-formyl-2(4-(ω-(N-sulfoprobylbenzothiazol-2-yl)propylamino]phenyl}hydrazine (H-23) l-formyl-2-(4-{3-p - (7enylenyl)hydrazine (H-24) l-formyl-2-(4-(2,4-di-tertpentyl7enoxymethylamide)7enyl]hydrazine (H-25) l-formyl-2- (4 -(3-(p-ethyl7enyl)ureido]7enyl Ihydrazine (H
-26) l-formyl-2-(4-(3-(2-methoxy,cy7enyl)ureido)phenyl}hydrazine (H-27) l-formyl-2-(4-(3-ethylureido)7 enyl]hydrazine (H-28) 1-formyl-2-(4-(3-propylureido 7-enyl)hydrazine (H-29) ■-formyl-2-(4-(3-(p-methoxyphenyl)ureido) -2-methoxyphenyl}
Hydrazine (H-30) l-formyl-2-{4-[3-(p-methoxyphenyl>ureido]-2-methoxy7-dyl}
Hydrazine (H-31) l-formyl-2-{3-(3-(p-chloro7enyl)ureido]7enyl}hydrazine (H-3
2) l-formyl-2-(4-(3-n-butylureido)phenyl) hydrazine (H:33) l-formyl-2-(4-(3-dodecylureido)phenyl)hydrazine (H-34) l -Formyl-2-(4-(3-year-old tadecylureido)phenyl)hydrazine (H-35) l-Formyl-2-(4-(3-(hexanoyl)waleido)phenyl}hydrazine (H-36) 1 -Formyl-2-+4-(3-(benzyl)ureido]phenyl}hydrazine (H-37) l-Formyl-2-(4-(3-(pyridin-2-yl)ureido)7enyl}hydrazine (H- 38
) l-formyl-2-{4-(3-(thiophenyl-2-
yl)ureido]phenyl}hydrazine (H-39) l-formyl-2 - {4-(3-(4-methylthiazol-2-yl)ureido]7enyl}hydrazine (H-40) l-formyl-2 - {4-(3-(5-nitro7enyl)ureido]7enyl}hydrazine (H-41
) 1-nhexylacetylamino-4-(2-acetynolehydrazino)benzene (H-42) i-(p-chlorobenzoyl)-2-7enylhydrazine (H:43) 1-(p-cyano benzoyl)-2-phenylhydrazine (H-44) 1-(p-carpoxybenzoyl):2-7enylhydrazine (H-45) 1-(3.5-dichlorobenzoyl)-2-7enylhydrazine (H -46) l-(2-formylhydrazino)-4-(N-dimethylamino)benzene (H-47) l-(2-formylhydrazino): 4-(2-formylhydrazino)penzylbenzene Various silver halides can be used in the silver halide emulsion layer used in the silver halide photographic light-sensitive material (hereinafter referred to as light-sensitive material) of the invention. Examples include silver chloride, silver bromide, salt, silver iodide, silver iodobromide, and silver chloroiodobromide. In particular, the effect of the present invention is remarkable for silver bromide and silver iodobromide, with less silver iodide (A
gl 5 mol% or less) is particularly effective for highly sensitive photosensitive materials.

The silver halide emulsion of the silver halide emulsion layer of the light-sensitive material of the present invention may be prepared by a silver halide emulsion suspended in a hydrophilic colloid by a known method, such as a single silver halide emulsion by a neutral method or an ammonia method. Emulsion preparation method by jet method, double jet method, etc.: 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" L.
Op m , particularly preferably from 0.1 to 0.7 μm and at least 75% of the total number of particles, particularly preferably 80%
It is preferred that the above contains silver halide having a grain size of 0.7 to 1.3 times the average grain size.

Furthermore, as a silver halide emulsion containing polyvalent metal ions (for example, iridium, rhodium, etc.), US Pat.
No. 271.157, No. 3,447.927, No. 3,5
Emulsions such as those according to No. 31,291 can also be used. Silver halide emulsions are made from sulfur compounds, gold compounds (
Sensitization can be carried out by chemical sensitization using chloroauric acid salts, gold trichloride, etc.).

A polymer latex consisting of a homo- or copolymer such as alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. is added to the silver halide emulsion layer or other hydrophilic colloid layer to improve the stability of the photographic material and the physical properties of the film. It may also be included for this purpose.

Color sensitivity can be imparted to a desired photosensitive wavelength range using a dye. As the sensitizing dye, commonly used ones such as methine dyes and styryl dyes such as cyanine, hemicyanine, rhodacyanine, merocyanine, oxanol, and hemioxonol can be used.

In the silver halide emulsion applied to the present invention, those represented by the following general formula [■] or (V) are useful as stabilizers or fog suppressants.

General formula (IV) In the general formula [v], R. ,
R,, Rゎ and R4 may be the same or different, and each represents a hydrogen atom, a halogen atom, a ditro group,
R. and R. may be combined to form a 5- or 6-membered closed ring structure.

Specific examples of compounds represented by the above general formula include the following.

(S-1') 4-hydroxy-6-methyl-1.2,3.3a,7-
Tetrazaindene (S-2) 4-hydroxy-5-ethyl-6-methyl-1.3.3
a. 7-tetrazaindene (S-3) 2-mercabutomethyl-4-hydroxy-6-methyl-
1.3,3a. 7-tetrazaindene (S-4) 2-carpoxy-4-hydroxy-6-methyl-1.3
．． 3a,7-tetrazaindene (S-5) 2,4-dihydroxy-6-methyl-1,3,3. ,7
-Tetrazaindene (S-6) 2-amino-5-carboxy-4-hydroxyl 3 3a, 7-tetrazaindene (S-7) 5-carboxy-4-hydroxyl 3 3a, 7-tetrazaindene (S-8) 2-Methyl-4-hydroxy-6-methyl-l 3 3a, 7-tetrazaindene (S-9) 4-hydroxy-5-cyanol 3 3a, 7-atrazaindene (S-10 2- Bis(4-hydroxy-6-methyl 1 3 3a 7-tetrazainden-9-inole)-1,2-dihydroxyethane (S-13) 5-amino-7-hydroxy-2-p-methoxyphenyl-1. 2.3.4.6-Pentazaindene The above compounds can be added during and/or at the end of the silver halide physical ripening. Silver chloride can be present in a hydrophilic colloid layer such as gelatin during the process of elongation and shaping. Furthermore, it may be added immediately before, during and/or after chemical ripening, or it may be added at the time of preparing the coating solution. A generally preferred method of addition is to add 1 mole of silver halide at the end of chemical ripening.
~lxlO-1 mol, more preferably IXIO-'~I
It can be added in the range of XIO-'' mole. When adding the above compound to the emulsion, it can be added by dissolving it in accordance with the method for adding the compound represented by the general formula.

Furthermore, the light-sensitive material of the present invention may contain the following general formula CVI) or [■] as an anti-capri agent or stabilizer.
S+″Shike〈Yasu general formula〔■〕 General formula〔■〕 Ar-OH HO Ar-O
H [wherein, Ar represents an aromatic ring, and the aromatic ring is an alkyl group (having 1 to 25 carbon atoms), a halogen atom, a hydroxy group,
It may be substituted with a hydroxyalkyl group (the alkyl group may be substituted with a hydroxy group or a halogen atom), an aldoxime group, or the like. When compounds having the structures shown by [■] and [■] are used in combination, a remarkable antifogging 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-dihydroxyna7talene (7) 2.3-dihydroxynaphthalene (8) Gentisaldoxime (9) 2.5-Dihydroxyacetophenone oxime (10) Gentisamide (11) N-Methylgentisamide (12) N- (β-hydroxyethynole)gentisamide (13)N (n-hexadecyl)gentisamide (
l4) Salicylaldoxime (15) Resorcyaldoxime (17) Hydroquinone aldoxime The above compounds are disclosed in US Patent No. 2.675.314 and British Patent No. 62344.
No. 8, JP-A No. 52-11029, etc. can be referred to for the synthesis.

In addition, fog suppressants commonly used in silver halide emulsions can also be used in the silver halide photographic emulsion of the present invention. Any of the above-mentioned hydrazine compounds, polyalkylene oxide compounds, fog suppressants or stabilizers are generally used in an amount of l x 10 per mole of silver halide.
-' to a concentration of 101 moles/1 mole of silver, more preferably 5
A concentration of X10' to 5 X 10-'' moles/l silver can be used.

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

The photosensitive material of the present invention has the following general formula [■
The polyethylene oxide compound represented by the following formula can be contained in the silver halide emulsion and/or in the hydrophilic colloid layer adjacent to the emulsion layer.

General formula [■] HO (cH, cH, o). H [In the formula, n represents an integer of 10-100. ] Also, the following general formula Cff which is a block polymer of polyalkylene oxide) General formula CI! ) [0(CI, CH20), (Ctl-CH!O) b(
CB! Ctl20), Hi CH. [In the formula, b is an integer of 10 to 50, a and C are each a+
c represents an integer from 5 to 60, and the polyoxyethylene group is 10 to 70% by weight of the weight of the block polymer.
occupies ] Alternatively, a compound represented by the following general formula [X] may be contained in the emulsion layer and/or in a hydrophilic colloid layer adjacent to the emulsion layer.

General formula [X] [In the formula, R is an alkyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms in the alkyl group, an arylcarbonyl group (for example, benzoyl, p-methylbenzoyl, etc.), etc. represent. In the formula, d represents an integer from 10 to 100. ] Polyalkylene oxide polymers such as those described above are useful for the purposes of the present invention.

These compounds can be synthesized by condensing polyols such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene polymers with aliphatic alcohols, phenols, fatty acids, ethylene oxide, propylene oxide, and the like. The polyalkylene oxide chain in the molecule may be a block copolymer divided into two or more parts instead of one. At this time, the total polymerization degree of the polyalkylene oxide must be IO or more,
100 or less is preferable.

Next, specific examples of polyalkylene oxide compounds to be applied to the present invention will be shown. -2) nc. H. o(CH.CH20)nH (n=20) (P-3) nl4H, 70(CHzCH30)nH (n=30) (P-4) nC. ．． H, @O(CH2CH,0)nH (n=30) (P-5) (p-6) (P-7) (P-8) (P-9) (P-10) (P-11) (P-12) (n=50) (P-13) HO(CHzCHxO)Q (CHzCH2CH2CH
20) Ill(CH2CHzO)nH(ff+n-23
, m-21) (p-14) 80(CH zcH *O)Q (CH zcH ZC
H2CH20)m(Cl{,cl{to)nH
((2+n-38,m-153 (P-15) (p-16) (p-17) (P-18) nC+ zH* sS(CHCHzO)Q(CHzCH
zO)mHCH. CQ=7. m=30) (P-19) (p-20) (P21) (P-22) (P-23) CH. HO(CH.CHzO)Q(CH,CHO)m(CH,
CHzO)nH(a1n-15, m-20) (P-24) The amount of the polyalkylene oxide compound used in the present invention is preferably 10+g to 3g per mole of silver halide, and the timing of addition is as follows: Although any time during the process of producing the photographic emulsion of the present invention can be selected, it is preferable to add it after the second ripening is completed.

The silver halide photographic emulsion that can be applied to the present invention contains, for example, aldehydes (formaldehydes, glyoxals, glutaraldehydes, mucochloric acid, etc.) and N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.) that are commonly used as hardening agents. , dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1.3.5-trichlorohexahydro-s-1 riazine, bis(vinylsulfonyl) methyl ether, etc.), active halides (2.4 -dichloro-6-hydroxy-S-triazine, etc.) can be used alone or in combination, and thickeners, matting agents,
Commonly used coating aids can be used. Further, as the binder, a commonly used hydrophilic binder having protective colloidal properties can be used.

When the present invention is applied to color photosensitive materials, commonly used couplers, ultraviolet absorbers, fluorescent whitening agents, image stabilizers, antioxidants, lubricants, sequestering agents, emulsifying dispersants, etc. can be used.

The light-sensitive material of the present invention has layers other than the silver halide emulsion layer, such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a subbing layer, an auxiliary layer, an anti-irradiation layer, and a backing layer. Supports commonly used include baryta paper, polyethylene-coated paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, and the like, each of which can be appropriately selected depending on the intended use of the photosensitive material.

Examples of developing agents used in developing the silver halide photographic material according to the present invention include the following. HO-
(CH-CH). - Typical OH-type developing agents include hydroquinone, as well as catechol, birogallol and its derivatives, ascorbic acid, chlorohydroquinone, promohydroquinone, methylhydroquinone, 2.3-cyfuromohydroquinone, 2.5- diethynolehydroquinone, catechone,
4-chlorocatechol, 4-7z diluatecohol,
Examples include 3-methoxytecol, 4-acetyl birogallol, and sodium ascorbate.

In addition, as HO (CH= CI{)-NHz type developers, ortho and rose aminophenols are typical, and 4-amino-7enol, 2-amino-6-
Examples include 7-enyl 7-enol, 2-amino-4-chloro-6-phenylphenol, and N-methyl-p-aminophenyl.

Furthermore, H,N- (CHyoCH). -NH! Examples of mold developers include 4-amino-2-methyl-N,N-jethylaniline, 2,4-diamino-N,N-jethylaniline, N-(4-amino-3-methylphenyl)monomorpholine, and p-phenylenediamine. etc.

Examples of the heterocyclic developer include 3-virazolidone such as l-7enyl-3-virazolidone, l-phenyl-4,4-dimethyl-3-virazolidone, and l-7enyl-4-methyl-4-hydroxymethyl-3-virazolidone. Examples include -virazolidones, l-phenyl-4-amino-5-virazolone, and 5-aminolaucil.

Others, T. H. The Theory of the...
The Photographic Process 4th Edition (The Theo
ry of Photographic Processes
s Fourth Editor 6n) No. 291-334
Pages and Journal of the American Chemical Society
an Chemical Society) Volume 73,
Developers such as those described on page 3, 100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material according to the invention, the effects of the invention will not be impaired. Further, hydroxylamine or a hydrazide compound can be used as a preservative, and in this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g per 112 grams of the developer.

The developer used in the photosensitive material of the present invention can contain alkanolamines and glycols.

Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, etc., and triethanolamine is preferred.

The preferable content of these anolekanolamines is 2 to 300 gt' per 1 g of developer, especially developer IQ.
10 to 200 g per serving is preferable.

Examples of glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 1,5-pentanediol, and 2-methoxyethanol, with diethylene glycol being preferred. The preferred usage amount of these glycols is 10 to 10 per developer ra.
200g, especially IO~100g per developer IQ
is preferred.

The above-mentioned alkanolamines and glycols may be used alone or in combination of two or more. The photosensitive material of the present invention can be processed with a developer under various conditions, but the developing temperature is below SO'C. is preferable, especially 40℃
It is preferable that the development time be within 3 minutes, but it is particularly preferable that the development time be within 2 minutes, which often brings about good results. Processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening, neutralization, etc. may optionally be employed, and these may be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

〔Example〕

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

The technical scope of the present invention can be modified in accordance with the following embodiments.

In particular, embodiments of the present invention will be explained using a high-sensitivity silver halide photographic light-sensitive material, a so-called darkroom type silver halide photographic light-sensitive material, but the present invention is not limited thereto.

Example 1 Silver iodobromide emulsion (silver iodide 1 mole silver
(mol%) was prepared. The average grain size was 0.28 μm. The emulsion was washed with water and desalted according to a conventional method, and then sensitized with sulfur. After sensitization, 4-hydroxy-6-methyl-1.3.
3a. 1.5 g of 7-tetrazaindene, 3 g of hydroquinone and 2 g of resonoresin anoredoxime were added, each per mole of silver.

In addition, 1-phenyl-5-mercaptotetrazole was added as a capri inhibitor at a concentration of O. lg, as the current aSS agent, polyethylene glycol with 3o ethylene oxide chains (one of the end groups is dodecylbenzene) is used per mole of silver.
．． 1g was added, and sahonin was added as a coating aid, and styrene-maleic acid was added as a thickener, and the mixture was divided into lO, respectively, as shown in Table 1.
An emulsion coating solution was prepared by adding the general formula [I] shown below or its comparative compound (below) and the compound shown by the general formula [■].

The compound represented by the general formula [I] is 3 XIO-'mol/
1 mole of silver, 3×10 of the compound represented by general formula (II)
-3 mol/silver 1 mol was added.

Next, a coating solution for an emulsion protective film was prepared as follows. That is, 10Q of pure water was added to 1Kg of gelatin, heated to 40°C after swelling, and 30g of a polymer of methyl methacrynolate (average particle size 0.27μm) was dispersed in the gelatin as a matting agent. It was finished and used as a coating solution for a protective film.

Preparation of a silver halide photographic light-sensitive material The emulsion coating solution prepared above and the coating solution for a protective film were combined on a 100 μm thick polyethylene tere-7-talate support that had been subjected to subbing processing, and the amount of silver was 3 by simultaneous multilayer coating. .5g/m”, the amount of gelatin applied in the emulsion layer is 1.8g/m”
+++g2 and the amount of gelatin applied in the protective layer was 1.1g/+*'' to prepare samples Nol-NoIO shown in Table 1. The samples were hardened by adding three types of hardening agents: formaldehyde, mucochloric acid, and hynylsulfone ether.These samples were exposed stepwise to xenon light through a commercially available contact screen (gray negative 150 line). After that, it was developed using the developer formulation shown below.

The fixer used was a commercially available rapid fixer. The development processing conditions were: development at 40° C. for 20 seconds, fixing at 35° C. for 20 seconds, and washing with water at room temperature for 20 seconds.

Halftone area of the above-treated sample 1O%, 50% and 9
The quality of each halftone dot of 5% was evaluated in five grades by visual observation using a 100x magnifying glass. Regarding the evaluation points, rlJ has the lowest quality, and the quality increases in order, with rank "5" indicating the best level.

Developer recipe Ethylenediaminetetraacetic acid disodium salt 1 g Sodium sulfite 75 g Hydroquinone 15 g N-methyl-p-aminophenol (hemisulfate) 5 Sodium bromide 35-methylbenzotriazole 0.91-7 phenyl-5-mercaptotetrazole 0.1 Adjust to pH 11.5 with KOH.

The following compound was used as a comparative compound represented by general formula [1].

a: 0H b: As is clear from Table 1, by using the compound represented by the general formula [I] of the present invention in a photosensitive material using a hydrazine compound, high quality halftone dots can be obtained and at the same time high sensitivity can be obtained. It can be seen that the following can be obtained.

〔Effect of the invention〕

Sensitivity and contrast are improved in a photosensitive material containing a hydrazine compound, and high-quality halftone dots can be obtained regardless of the size of the halftone dot area.

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a compound represented by the following general formula [I] and a hydrazine compound. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 represent substituted or unsubstituted alkyl groups. ]