JPS6147943A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and image contrast by incorporating a condensation compd. from oxazoline and thiohydantoin, and a hydrazine compd. in an emulsion layer. CONSTITUTION:The condensation compd. is represented by formula I, R1, R2 being H, halogen, alkyl, OH, alkoxy, or the like, R3 being alkyl or aryl, R4 being H or alkyl, and R5 being halogen, alkyl, OH, or the like. It is embodied by 1-(2-hydroxyethyl-3-pyridin-2-yl)thiohydantoin sodium salt. The hydrazine compd. is represented by formula II or III, R1, R2 being aryl, alkyl, or the like, such as 1-formyl-2-(4-methoxyphenyl)hydrazine. The photosensitive material can be enhanced in sensitivity, contrast, and dotted image quality by incorporating the compd. of formula I and the compd. of formula II or III in the photosensitive emulsion layer.

Description

[Detailed description of the invention]

(1) Object of the Invention (Industrial Field of Application) The present invention relates to a silver image forming method that stably provides ML, especially a high-lift photographic image. (Prior Art) Generally, high-contrast photographic images are used in the photolithography process to form characters and halftone-resolved photographic images, and in the ultra-precision photolithography process to form fine line images. Among the types of silver halide photographic light-sensitive materials for this purpose, seven are known that can form photographic images with extremely high contrast. Conventionally, for example, the average particle diameter was 0.2 μm, the particle distribution was narrow, the particle shape was uniform, and the silver chloride content was high (
By processing a photosensitive material consisting of a silver chlorobromide emulsion with an alkaline hydroquinone developer having a low sulfite ion concentration, images with high contrast, high sharpness, and high resolution, such as halftone images or fine images, can be produced. Methods have been used to obtain line images. 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. There is. For this purpose, a dot image is formed by using the above-mentioned lithium-type photosensitive material and photographing the original through an intersection line screen or a contact screen, followed by development processing. For this purpose, a silver halide photographic light-sensitive material containing a silver halide emulsion with fine grains and uniform grain size and shape is used, but even when this type of silver halide light-sensitive material is used, When processed with a general black and white developer, the quality of halftone dots, etc. is inferior to when developed with a Lith type developer. Therefore, the sulfite ion concentration is extremely low,
It is processed with a developer called a Lith type developer, which uses hydroquinone as the developing agent. However, since the lithium-type developer is susceptible to auto-oxidation and has extremely poor storage stability, there is a strong need for a control method to maintain constant development quality even during continuous use. Much effort has been made to improve constancy. As a method to improve this, in order to maintain the stability of the above-mentioned Lith-type developer, there is a replenisher (processing fatigue replenisher) that compensates for the deterioration in activity due to development processing, and a replenisher (processing fatigue replenisher) that compensates for the oxidative deterioration over time. A so-called two-liquid separation replenishment system, in which the replenisher (replenishment due to fatigue over time) and the replenisher (replenishment due to aging) are replenished 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 W 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. According to this method, it is possible to maintain a high concentration of sulfite ions in the developer, and it is possible to stably process with improved preservation. However, developing solutions used for silver halide photographic light-sensitive materials containing hydrazine compounds tend to generate capri because it is necessary to have a relatively high pH value in order to obtain high dust resistance. High concentrations of various organic inhibitors have the disadvantage of sacrificing sensitivity. Therefore, there is a strong desire for silver halide photographic materials that can provide images with high image contrast and have low capri and high sensitivity. (Objective of the Invention) The present invention provides a silver halide photographic light-sensitive material containing a hydrazine compound, which enables high-sensitivity, high-contrast images to be obtained, and provides high-quality halftone dots regardless of the size of the halftone dot area. The object of the present invention is to provide a silver halide photographic material that can be used as a silver halide photographic material. (2) Structure of the Invention The object of the present invention is achieved by a silver halide photographic material containing a combination of a compound represented by the following general formula (14) and a hydrazine compound. General formula (1) % formula % where, R1 and R3 are hydrogen atoms and halogen atoms (
(e.g., chlorine atom, bromine atom, etc.), optionally substituted alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, hydroxyethyl group, etc.), optionally substituted alkoxy group having carbon number Wk1 to 8 (for example, methoxy group, ethoxy group e), phenyl group, naphthyl group, sulfo group, or carboxy group, R1 and R2 may be combined to form a 6-membered ring, and on this ring there is a halogen atom, lower alkyl It may be substituted with a group, a hydroxyl group, a hydroxyalkyl group, a phenyl group, an alkoxy group, a carboxy group, etc. R, is an optionally substituted alkyl/l/ group (e.g., methyl group, ethyl group, sulfoethyl group, sulfopropyl group, sulfamidoethyl group, sulfobutyl group, etc.) or an optionally substituted alkenyl group (e.g., allyl group). base, etc.)
represents. R6 has 1 or more carbon atoms which may be substituted! 2 represents an alkyl group, and the substituent is preferably a hydroxy group, a carbamide group, etc., and this alkyl group has 10-, -0CO-, -Nl (-, etc.), lower alkyl group between its carbon chains. (e.g., methyl group, ethyl group, etc.), hydroxyl group, human mixyalkyl group (e.g., droxyethyl group), alkoxy group (e.g., methoxy group, ethoxy group, etc.)
, which may be substituted with a sulfo group or a carboxy group) The following compounds are listed as specific examples of the compound represented by the general formula [1], but the compounds are not limited to these. (1) l-(2-diethylaminoethyl)-5-C(ethylnat(2,1-d)oxazolin-2-ylidene)ethylidene)-3-(pyridin-2-yl)-2-thiohydantoin (2) 1-(2-diethylaminoethyl)-3-(pyridin-4-yl)-5-(3-ethyl-2-penzooxazoliedene)ethylidene2-
Thiohydantoin (3) 1- (2-hydroxyethylquinone developer 4
-sulfobutyl-pyridin-2-yl)-5-C(3-
Sulfopropyl-2-penzoxolinidene)ethylidene-2-thiohydantoin sodium salt (4) 1-(2-acetylbutyl)-3-1'pyridin-2-yl)-s-((a- Sulhojeci Al-
2-penzoxazolinidene)ethylidene]-2-thiohydantoin sodium salt (s) 1-(2-hydroxyethyl-3-(pyridin-2-yl)-5-((
3-Sulfob-tetrapyru-2-penzoxazolinidene)ethylidene]-2-thiohydantoin sodium salt (6)
1-(2,3-dihydroxypropyl)-3'-(
pyridin-2-yl)-5-((3-sulfamidoethyl-2-penzoxazolinidene)ethylidene-2-
Thiohydantoin sodium salt (7) 1-(2-hydroxyethoxyethyl)-3
-(pyridin-2-yl)-5-((3-sulfobutyl-5-chloro-2-penzoxazolinidene)ethylidene-2-thiohydantoin sodium salt (8) 1-(2-hydroxyethoxyethoxyethyl )-3-(pyridin-2-yl)-5-[(3-sulfobutyl-5-chloro-2-penzooxazoliedene)
ethylidene)-2-thiohydantoin sodium salt (9) 1-(2-hydroxyethylaminoethyl)
-3-(4-chloropyridin-2-i/L/)-5-(
(3-Sulfobutyl-5-methyl-2-penzoxazolinidene)ethylidene]-2-thiohydantoin sodium chloride (LO) 1- (2-hydroxyethoxyethyl)-
3-<p-ethoxypyridin-2-yl-5-[(3-
Sulfobutylnaphtho(2,1-d)oxazoline-2-
ylidene)ethylidene-2-thiohydantoin sodium salt (11) 1-(2-carbamidoethyl)-3-(4
-methylpyridin-3-yl)-5-C(3-sulfobutylna7)(2,1-d)oxazolin-2-ylidene)ethylidene-2-thiohydantoin sodium salt The compound represented by the general formula m is Showa 55-45015
No. 2,742. No. 833, No. 2,756,148, No. 3,567.4
No. 58, No. 3,575,704, No. 3,615,51
No. 7, No. 3,615,519, No. 3,632,340
Those skilled in the art can easily synthesize the compound by referring to the synthesis method described in the above issue. It is appropriate that the compound represented by the general formula [IJ of the present invention is added in a silver halide emulsion in an amount of 10''-+i to 1 mol per 1 mol of silver (preferably 1O- to 10 mol added); When adding, it can be dissolved in alcohols such as methanol and ethanol, ethers, ketones, glyfurs such as ethylene glycol and diethylene glycol, and then added to the emulsion. Preferably used in the present invention. Examples of the hydrazine compound include compounds represented by the following general formula (11) or general formula (IJ). General formula (Il+ General formula (1) R,
NHNHCHOR, NUN) ICOR. In the formula, R1 and Rt each represent an optionally substituted aryl group or an optionally substituted alkyl group. The aryl group represented by R1 and R7 contains a benzene ring or a 7talene ring, and this ring may be substituted with various substituents. Preferred substituents include a straight chain or branched alkyl group (preferably a carbon 1 to 20 carbon atoms, such as methyl group, ethyl group, isopropyl i%, n-dodecyl group, etc.), alkoxy groups (preferably carbon atoms of 1 to 20 carbon atoms, such as methoxy group, ethoxy group, etc.), aliphatic acylamide 7 Group (preferably one having an alkyl group having 2 to 21 carbon atoms, such as 7 acetylamides, 7 heptylamides, etc.)
, 7 aromatic acylamide groups, etc., and in addition to these, for example, substituted or unsubstituted aromatic rings such as those mentioned above (100NB-, -8-, -0-, -80,N)! −. It also includes those bonded with a linking group such as -NHCONH-, -C)lICHN-. 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 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 hydrophilic colloid layer adjacent to the emulsion layer. It is a matter of coercion. The hydrazine compound can be added after being dissolved in alcohols such as methanol and ethanol, glyfurs such as ethylene glycol and diethylene glycol, ethers, ketones, etc., and the amount added is 1 mole of halogenated fa. Hit

The range is from o-6 to 10-1, preferably from 10-4 to IO-. Examples of particularly preferred hydrazine compounds are as follows. (H-1) 1-formyl-2-7enylhydrazine (H-2) 1-formyl-2-(4-methoxyphenyl)hydrazine (H-3) 1-formyl-2-(4-bromophenyl)hydrazine (H-4) 1-formyl-2-(4-ethylphenyl)hydrazine (H-5) 1-formyl-2-(4-methoxyphenyl)hydrazine ()I-6) 1-formylIL'-2- (4-acetamido 7eni/I
/) and drazine (H-7) l-formi-2-(4-butylamidophenyl/L/)
Hydrazine 1-formyl-2-(4-phenylacetamidophenyl)hydrazine (B-9) 1-formyl-2-(4-dimethylaminophenyl)hydrazine (H-10) 1-formyl-2-(4-acetamido- 2-methyl-
phenyl)hydrazine (I(-11) 1-formyl-2-(4-(3-7enyl-thioureido) phenyldihydrazine (H-12) 1-formyl-2-(4-(3-ethyl-thio) ureido)phenyl]hydrazine(I(-13) 1-formyl-2-(4-(4-(3-7enylthioureido)phenyl)carbamyl7enyl)
Hydrazine (H-14) 1-formyl-2-(4-(a-(4,s-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)thioureylene phenyl]hydrazine (H-17) 1-formyl-2-((4-( 1,3-dimethylbenzimidazole-2-ylthioureylene phenyl)
Hydrazine ()T-18) 1-formyl-2-((4-(5-methyl-2-thio-
imidacillin-3-yl)phenyl])hydrazine (T(-19) 1-formyl-2-((4-(3-n-butylureido)phenyl)hydrazine(T(-20) 1-formyl-2-( 4-(3-(p-chlorophenyl)ureido]phenyl)hydrazine(I(-21) 1-formyl-2-(4-(3-Cp-(2-mercapto-tetrazol-3-y/l/) phenyl cothioureylene)phenyl)hydrazine rH-22) 1-formyl-2(4-(ω-(N-sulfopropylbenzothiazol-2-yl)propylaminocophenyl)hydrazine ()I-23) 1-pormyl -2-(4-(3-Cp-(phenylsulfaminophenyltoureylene)phenyl)hydrazine (H-24) 1-formyl-2-C4-(2,4-di-tert-pentylphenoxymethylamido)phenyl [hydrazine (H-25) 1-formyl-2-(4-(3-(1)-ethylphenyl)ureido] phenyl)hydrazine (H-ga) 1-formyl-2-(4-(3-(2) -・Methoxyphenyl)ureido]phenyl)hydrazine 1-formyl-
2-(4-13-ethylureido)phenyl]hydrazine (H-route) 1-formyl-2-(4-1'3-propylureidophenyl]hydrazine (H-29) 1-formyl-2-(4- (3-(p-methoxyphenyl)ureido]phenyl)hydrazine ()I-30) l-formyl-z-(4-C3-(p-methoxyphenyl)ureylcy2-methoxyphenyl,)hydrazine (H-31 ) 1-Formi"-2-(3-(3-(p-chlorophenyl)ureido)phenyl)human0radizine()I-32) 1-formyl-2-C4-(3-nbutylureido)phenyl]hydrazine ()!-33) 1-Formyl-2-C4-(3-dodecylureido)phenyl]hydrazine (H-34) 1-formyl-2-C4-(3-octadecylureido)phenyl]human Radine (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()I-38) 1-formyl-2-(4-(3-(thiophenyl A/-2)
-yl)ureido]phenyl)hydrazine (H-39) 1-formyl-2-(4-(3-(4-methylthiazol-2-yl)ureido]phenyl)hydrazine ()I-40) 1-formyl- 2-(4-(3-(s-nidophenyl)ureido]phenyl)hydrazine (H-41) 1-nhexylacetylamino-4-(2-a7tylhydrazino)benzene (H~42) 1-( p-chlorobenzoyl)-2-phenylhydrazine (H-43) 1-(p-cyanobenzoyl)-2-phenylhydrazine 1-(p-carboxybenzoyl)-2-phenylhydrazine (H-45) 1-(3 ,5-dichlorobenzoyl)-2-7enylhydrazine 1-(2-formylhydrazino)-4-(N-dimethylamino)benzene (H-47) 1-(2-formylhydrazino)-4- (2-Formylhydrazino)benzylbenzene Various silver halides can be used in the silver halide emulsion layer used in the silver halide photographic light-sensitive material C of the present invention (hereinafter referred to as light-sensitive material). Examples include silver chloride, silver bromide, silver bromide, silver iodobromide, and silver chloroiodobromide. In particular, the effect of the present invention is remarkable for silver bromide and silver iodobromide;
(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 methods such as jet method and double jet method 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.
04m, particularly preferably 0.1 to 0.74m,
and at least 75% of the total number of particles, particularly preferably 80
% or more preferably contains silver halide having a grain size of 0.7 to 1.3 times the average grain size. Furthermore, U.S. Patent No.
, 271,157, 3,447, 927, and 3,531,291 can also be used. Silver halide emulsions are usually made using a sulfur compound,
Sensitization can be achieved by chemical sensitization using gold compounds (chloroauric acid salts, gold trichloride, etc.). A polymer latex consisting of a homo- or copolymer of 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 dimensional stability of photographic materials and to improve film properties. It may also be included for this purpose. The silver halide emulsion to which the present invention is applied can be imparted with color sensitivity in a desired wavelength range by using a sensitizing 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, the following general formula (capital)] or (V) is used as a stabilizer or a capri inhibitor.
Those shown are useful. General formula OV) General formula [η formula, R&
, R1), Ro and Rd may be the same or different, and each represents a hydrogen atom, a halogen atom, a nido tetragroup, an amino group, a cyano group, a hydroxyl group, a carboxyl group, an alkoxy group, an acyl group, or R represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group;
b and Ro may be combined to form a 5R 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-1,3,3a. 7-chitrazaindene (S-2) 4-hydroxy-5-ethyl-6-methyl-1,3,3
a.? -Tetrazaindene (S-3) 2-mercaptomethyl-4-hydroxy-6-methyl-
1,3,3a,7-chitrazaindene (S-4) 2-carboxy-4-hydroxy-6-methyl-1,3
,3a,7-chitrazaindene (S-5) 2,4-dihydroxy-6-methyl-1,3゜3a,7
-Chitrazaindene (S-6) 2-amino-5-carboxy-4-hydroxy-1,3
, 3a, 7-chitrazaindene (S-7) 5-hydroxy-4-hydroxy-1,3゜3a, 7-
Chitrazaindene (S-8) 2-methyl-4-hydroxy-6-methyl-1,3,3
a, 7-thitrazaindene (S-9) 4-and-doxy-5-cyano-1,3,3a, 7-thitrazaindene (S-10) 3-chloro-4-hydroxy-6-methyl-1,3, 3
a, 7-chitrazaindene (S-11) 2,4-dihydroxy-6-methyl-1,3゜3a,
7-chitrazaindene (S-12) 1,2-bis(4-hydroxy-6-methyl-1,3,
3a, 7-tetrazainden-2-yl), -1
, 2-dihydroxyethane (S-13) 5-amino-7-hydroxy-2-p-methoxyphenyl-1,2,3,4,6-pentaazaindene Or it can be added at the end. Silver halide can be present during the growth and formation process in a hydrophilic colloid layer such as gelatin. Furthermore, it may be added immediately before, during and/or after chemical ripening, or may be added when preparing a coating solution. A generally preferred method of addition is LO-6 to to-1 per mole of silver halide at the end of chemical ripening.
, more preferably in the range of LO″″ to 10−. When adding the above compound to the emulsion,
It can be added by dissolving the compound according to the method for adding the compound represented by the general formula [13]. Furthermore, the photosensitive material of the present invention can be used as an anti-capri agent or a stabilizer having the following general formula (2) or (4) general formula (2).
General formula (b) Ar -OHHO-Ar-OH C In the formula, 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, or a hydroxyalkyl group (alkyl group). may be substituted with a hydroxy group or a halogen atom), an aldoxime group, etc. ] When used in combination with a compound having the structure shown below, a remarkable capri-inhibiting 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 (Gentisamide (11) N- Methylgentisamide (12)N-(
β- and droxyethyl) gentisamide (13) N-(n-hexadecyl) gentisamide (1
4) Salicylaldoxime (15) Resorcyaldoxime (16) Hydroquinone monobenzoate (17)
Hydroquinone aldoxime The above compound can be synthesized with reference to the descriptions in US Pat. No. 2,675,314, British Patent No. 623,448, JP-A-52-11029, and the like. In addition, capri inhibitors commonly used in silver halide emulsions can also be used in the 71'' silver halide photographic emulsion of the present invention. Any of the hydrazine compounds, goryalkylene oxide compounds, fog suppressants or stabilizers mentioned above are generally used in amounts of 10 to 10 g ([41 moles per
-' to 1 O-1 mole/silver mole, more preferably 5 x to-' to 5 x LO-2 mole/silver mole. 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 (diethyl ether, dipropyl ether), ketones such as acetone, dioxane, petroleum ether, or nonionic, anionic, or cationic surfactants. It may also be added after being dispersed in a spot solvent. The light-sensitive material of the present invention may contain a polyethylene oxide compound represented by the following general formula as a development regulator in the silver halide emulsion and/or in the hydrophilic colloid layer adjacent to the emulsion layer. General formula term) 10 ((Jl, CB, O)n) 1 [where n is 1
Represents an integer from 0 to 100. ] Also, the following general formula [IX
) General formula [IKJ CH8 [wherein b is an integer from 0 to 50, a and C are each a+
C represents an integer from 5 to 50, and the polyoxyethylene group represents the weight of the block polymer [0-=70
Occupies the outermost area. ], or furthermore, a compound represented by the following general formula [X] can be contained in the emulsion layer and/or in the woody colloid layer adjacent to the emulsion layer. General formula (XJ [wherein R represents 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 (eg, benzoyl, p-methylbenzoyl, etc.), etc. In the formula, d represents an integer from 0 to 100. Polyalkylene methoxide polymers such as those described above are useful for the purpose of the present invention. These compounds include polyethylene glycol, polypropylene glycol, polyoxytetramethylene It can be synthesized by condensing polyols such as polymers with aliphatic alcohols, phenols, fatty acids, ethylene oxide, propylene oxide, etc.The polyalkylene oxide chain in the molecule is split into two or more places instead of one. A block copolymer may also be used.In this case, the total degree of polymerization of the polyalkylene oxide must be 0 or more, and preferably 100 or less.Next, specific examples of the polyalkylene oxide compound applied to the present invention are as follows. However, the present invention is not limited to these. [Specific examples of polyalkylene oxide compounds] (I-1
) no(cH,cH,o)n)I (n = 3
5) (I-2) nC,H@0(C)12CH10)nHin-”=Additional
nC61170(CHIC)120)nB (n
== 30) nc12H2y, 0(C)12CI(t
o) nH (n = 30) (I-5) (I-6) (n = (capital)] (I-8) HO(CH2CH2O)z (CI(2) m(C)l
tC)120)nHO""t CH20)j (C
HCHt O)m (CHtCHt O)n H(I
-10') HO(C)1. CH,0)j (C)ICH,O)m(
C) (,CH,O)n)1CI(. (z+fi=so, m=35)(I-11
>Do (C)1. CI, O) t (C) ICH, 0)
Tn(cH!cnto)nB woodcutter 0. +. =15.
. =□5] Do(C)I,CH,O)j rcHcH,O)m(C
H,C)(,0)nH0・”°3..=9..=15
゜HO(CH,CB,0)fi (cH,cH,cn,c
H,o)fn(CD,C)1.0)nE(!+n=23
．． m=21) (I-,14) HO(OH,CH,O)A (OH,CB,CD,CH
2O)m (CH,CH,O)nH(j+n=A, m=
15) HO(CH,CH20)i (CHC)(20)m(C
)1. CH,0)nH” CH20CR. (A+n=15.m=15) (r −16) HO(cH4H,o )z (C)(C)(,O)m(
CT(,CH,O)nBmengcn′. 0H''('+n=30.m=15)(I
-17) CHs (j==7.to=1 (I -18) n C,2I-1,,S (CHCH2O)z (OB
, CD, O) m H [CH3 (A==7, m=30) (I -19) 0 HOOCC horse CH, Co(C)l attack 0)z (CH,
CH,C)I,C)(,O). (CI(2C)120) CC)1. CB, C0OH
(L+n=15.m=15) (I −20) 0 (CH,CI(,O) CCH,CH,COOH(A
+ 11=ls, m=20) (knee 21
) (n = 30) (f+n=90) HOrCH,CH20)z (CH,CHO)In(C
)l, CHtO)nH (j+n=15.m=20) coHO(CHtCH20)j (CHtCHO)m (C
H20HtO)n H(1-+n=25.m=chrysanthemum) The amount of the polyalkylene oxide compound used in the present invention is preferably 10η to 3I per 1-1 silver halide, and the time of addition is one. Any time during the process of producing the photographic emulsion of the invention can be selected, but it is preferable to add it after the second ripening is completed.The silver halide photographic emulsion applicable to the present invention is usually used as a hardening agent. For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde,
mucochloric acid, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5-triacroyl-hexahydro-5-) liazine , bis(vinylsulfonyl)methyl ether, etc.), active halides (2,4-dichloro-6-hydroxy-s-triazine, etc.), 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 covalent properties can be used. When the present invention is applied to color photosensitive materials, it is usually used as a coupler, ultraviolet absorber, fluorescent brightener, image stabilizer, antioxidant, lubricant, sequestering agent, emulsifying dispersant, etc. In the light-sensitive material of the present invention, layers other than the silver halide emulsion layer include a storage layer, an intermediate layer, a filter layer, an anti-halation layer, a subbing layer, an auxiliary layer, and an irradiation prevention layer. , a backing layer, etc., and the support to be used may be appropriately selected from baryta paper, polyethylene paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc., depending on the intended use of the photosensitive material. The photosensitive material of the present invention uses HO-(C)l=c as a developer.
'Hhen-OH type, )(i-(C=C)n-N type, developers having a heterocycle, and other commonly used developers can be used. HO-(CH=C)I)n Typical -OH type developers include catechol, pyrogallol and its derivatives, and ascorbic acid, as well as hydroquinone, chlorohydroquinone, p-mohydroquinone, and isopropyl A.
・Hydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Dimethylhydroquinone, 2,3-dibromohydroquinone, 2,5-dihydroxyacetophenone, 2,5
-diethylhydroquinone, 2,5-di-p-7enethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-7
enylcatechol, 4-7 enyl-catechol, 3-methoxycatechol, 4-acetyl-pyrogallol, hydroquinone monosulfonate, methyl-hydroquinone monosulfonate, chlorohydroquinone heptanosulfonate), 2,5-dimethylhydroquinone monosulfonate, 3 - dibromohydroquinone monosulfonate,
Examples thereof include 4(2'-hydroxybenzoyl)pyrogallol and sodium ascorbic acid. Typical examples of HO-(CH=CH-containing-N4 type developers are ortho and loose amine phenols or aminopyrazolones; 4-aminophenol, 2-aminophenol, 2-aminophenol,
6-phenylphenol, 2-ami/-4-10rho6
-phenylphenol, 4-amino-2-phenylphenol, 3,4-diaminophenol, 3-methyl-4
, 6-lyaminophenol, 2.4-cyamylsorcinol, 2.4.6-)lyaminophenol, N-methyl-p-aminephenol, N-β-hydroxyethyl-
Examples include p-aminephenol, p-hydroxyphenylaminoacetic acid, and 2-aminonaphthol. Examples of H,N-(C=C)n-NH type developers include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, N-
(4-amino-3-methylphenyl)-morpholine, p
-7enylenediamine, 4-amino-N,N-dimethyl-3-hydroxyaniline, N,N,N/,N'-tetramethylparaphenylenediamine, 4-amino-N-ethyl-N-(β- hydroxyethyl)-aniline, 4-
Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-7niline, 4-amino-N-ethyl-(β
-Methoxyethyl)-3-methyl-aniline, 4-amino-3-methyl-N-ethyl-N-(β-methylsulfonamidoethyl)-aniIj:/, 4'-amino-N-
Butyl-N-r-sulfobutylaniline, 1-(4-aminophenyl)-pyrrolidine, 6-amino-1-ethyl, 1,2,3,4-tetrahydroquinoline, 9-7 minoidylolidine, etc. Can be mentioned. As a developer having a heterocycle, for example, 1-phenyl-
3-pyrazolidone (phenidone), 1-7enyl-4-
Amino-5-pyrazolone, 1-(p-aminophenyl)
-3-amino-pyrazoline, 1-phenyl-2-methyl-4-amino-5-virazolone, 1-7 enyl 4.4
1-dimethyl-3-pyrazolidone (dimezone), 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone (dimezone-S), 1-phenyl-4゜4-dihydroxymethyl-3-pyrazolidone, 1-7 enyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4-methyl-4-propyl-3-birasoliton, 1
-p-chlorophenyl-4-methyl-4-ethyl-3-
Pyrazolidone, 1-p-acetamidophenyl-4,4
-diethyl-3-pyrazolidone, 1-p-betahydroxyethyl 7ethyl A--4,4-dimethyl-3-pyrazolidone, 1-p-methoxyphenyl-4,4-diethyl-3-pyrazolidone, 1-p -) Ryl-4,4-dimethyl-3-pyrazolidone and the like. Others include T. H. James, The Theory of Self-Operation Photographic Process, 4th Edition (The T.
theory of the Photographic
Process. Fourth Edition) pages 291-334 and Journal of the Life American Chemical
Society (Journal of the Amer)
ican Chemical Society ) No. 73
vol., p. 3100 (1951") K can be effectively used in the present invention. These developers may be used alone or in combination of 2w1 or more, but 2w1 or more may be used in combination. It is preferable to use a combination of more than one species. A preferred combination is a combination of hydroquinone and phenidone, and hydroquinone and dimezone;
Hydroquinone is preferably used in a range of 5I to 5)l/1-1, and phenidone or dimezone is preferably used in a range of 0.05N to 51/j-. Further, even if a preservative such as a sulfite salt such as sodium sulfite, potassium sulfite, or ammonium sulfite is added to the developer used in the photosensitive material of the invention, the effects of the invention will not be impaired. This can be mentioned as one of the characteristics. Suitable sulfite concentrations are between 0.06 and 1 gram ion/l. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, pH adjustment and buffering functions should be provided using caustic alkali, alkali carbonate, or amines used in general black and white developers, inorganic development inhibitors such as brompotali, metal ion scavengers such as ethylenediaminetetraacetic acid, methanol, ethanol, Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylarylsulfonate,
It is optional to add surfactants such as natural saponins, saccharides or alkyl esters of the above-mentioned compounds, hardening agents such as glutaraldehyde, formalin and gluoxal, and ionic strength regulators such as sodium sulfate. pH
The value can be arbitrarily set from 9 to 12, but from the viewpoint of stability and photographic performance, it is preferably used within the range of pH to 1. The developer used in the photosensitive side film of the present invention can contain alkanolamines and glycols. Examples of the alkanolamine include monoethanolamine, jetanolamine, triethanolamine, etc., and triethanolamine is preferred. The preferred content of these alkanolamines is developer I.
I! 2 to 300.17 per developer 1e, and particularly preferably 10 to 200.9 per developer 1e. Examples of glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 5-bentanediol, and 2-methoxyethanol, with diethylene glycol being preferred. The preferred amount of these glycols used is 11! Per [0
~2007, especially 20 to 100 per gram of developer
fl is preferred. The above alkalamines and glyfurs may be used alone or in combination of two or more. Processing of the photosensitive material of the present invention with a developer can be carried out under various conditions, but the development temperature is preferably 50"C or less, particularly preferably around 40"C, and the development time is preferably completed within 3 minutes. Generally, but preferably within 2 minutes often brings about good results.Processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening, neutralizing, etc. It is optional to adopt these processes, and they can be omitted as appropriate.Furthermore, these processes may be so-called manual development processes such as plate development and frame development, or mechanical development processes such as roller development and hanger development. (Example) The present invention will be explained in more detail with reference to Examples below. The technical scope of the present invention is not limited in any way by the following Examples, and various embodiments are possible. In particular, embodiments of the present invention will be explained using a high-sensitivity silver halide photographic material, a so-called darkroom type silver halide photographic material, but the present invention is not limited thereto in any way. Example 1 A silver iodobromide emulsion (61 iodides per mole of silver) was prepared by a simultaneous mixing method.
1 mol%) was prepared. The average grain size was 0.28 μm. This emulsion was washed with water and desalted in a conventional manner, and then sensitized with sulfur. After sensitization, 4-hydroxy-6-methyl-1,3 was added as a stabilizer.
, 3a, 7-? ) Razainden 1.5, 9. 39 of hydroquinone and 21 of resorcinaldoxime were added per mole of silver. Furthermore, 1-phenyl-5-mercaptotetrazole was added as a fog inhibitor at 0.1N1 per mole of silver, and polyethylene glycol (ethylene oxide chain I) was used as a development regulator.
one of the terminal groups is dodecylbenzene) per mole of silver,
An emulsion was prepared by adding saponin as a coating aid and a styrene-maleic acid copolymer as a thickener. This emulsion was divided into [0 and the general formula (1) shown in Table 1]
Alternatively, a comparative compound (see below) and a compound shown in the general formula (2) were added to prepare an emulsion coating solution. The compound represented by the general formula (13 is 3 X 10-' mol/silver 1 mol, the compound represented by the general formula [IJ is 3 X
10-3 mol/silver 1 mol was added. Next, a coating solution for an emulsion protective film was prepared as follows. That is, 10 liters of pure water in gelatin IK9! was heated to 40°C after swelling for 7W, and a polymer of methyl methacrylate (average particle size 0.27 prn) was added as a matting agent.
Disperse E in gelatin, 201! Finished and protected H,
It was made into a tear coating liquid. Preparation of silver halide photographic light-sensitive material 1. The emulsion coating solution prepared above and the coating solution for protective film were combined on a processed polyethylene terephthalate support having a thickness of Zoo am, and silver halide 3. 51/m', the amount of gelatin applied in the emulsion layer is 1.8
1/rr? Samples 1 to 10 shown in Table 1 were prepared by coating the protective layer so that the amount of gelatin applied was 1.1 J/♂. During multilayer coating, three types of hardeners, formaldehyde, mucotetralic acid, and ethyleneimine, were added to the protective film coating solution to harden the film. These samples were subjected to stepwise exposure to xenon light through a commercially available normal contact screen (gray negative 150 line), and then developed using the developer formulation shown below. The fixer used was a commercially available rapid fixer. The development processing conditions were 4 seconds at 40°C for development and 2 seconds at 35'C for fixing.
0 seconds, and water washing was for 20 seconds at room temperature. The halftone dot quality of each halftone dot area of 10%, (%), and 95% of the treated sample was evaluated in five grades by visual observation using a 100x magnifying glass. As for the evaluation score, "1" is the lowest quality,
The quality increases in order, and rank "5" indicates the best level. Developer formulation Ethylenediaminetetraacetic acid disodium salt Sodium sulfite 75. 9 Hydroquinone
15 1N-methyl-p-aminophenol (hemisulfate a salt) 5.9 Sodium bromide 3.095-Methylbenzotriazole 0.9g1-phenyl-5-
Mercaptotetrazole 0.19 Adjusted to pH 11.5 with KOH. The following compound was used as a comparative compound represented by the general formula (IJ). a 1-(2-hydroxyethoxyethyl)-3-phenyl-5-((3-sulfobutyl-2-penzoxazolinidene) Ethylidene 2-thiohydantoin sodium salt b 1-(2-diethylaminoethyl)-3-ethyl-5-((3-sulfopropyl-2-penzooxazoliedene)ethylidene 2-thiohydantoin sodium salt c 1- (2-human tetraxyethyl)-3-ethyl-5
-((3-sulfoethyl-2-penzoxazolinidene) ethylidene 2-thiohydrancy Table -1 As is clear from Table 1, the photosensitive material using the hydrazine compound has the general formula (1) of the present invention. It can be seen that high-quality halftone dots and poor sensitivity can be obtained at the same time by adding the compound represented by hydrazine. (3) Effects of the Invention Sensitivity and contrast are improved in light-sensitive materials containing hydrazine compounds. Furthermore, 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 characterized by containing a combination of a compound represented by the following general formula [I] and a hydrazine compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 are hydrogen atoms, halogen atoms, optionally substituted alkyl groups with 1 to 8 carbon atoms, hydroxy groups, and alkoxy groups. , represents a phenyl group, a naphthyl group, a sulfo group or a carboxy group, and R_1 and R
_2 may be combined to form a 6-membered ring. R_3 represents an optionally substituted alkyl group or allyl group, and R_4 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms. R_5 represents a pyridyl group which may be substituted with a halogen atom, a lower alkyl group, a hydroxy group, a hydroxyalkyl group, an alkoxy group, a sulfo group or a carboxy group. ]