JPS6147949A - Image forming method - Google Patents

Abstract

PURPOSE:To form an image having high contrast and sensitivity by developing photosensitive material contg. a thiohydantoin compd. and a hydrazine compd. with a developer contg. specific concns. of a sulfurous acid ion and a potassium ion. CONSTITUTION:The photosensitive material is prepared by incorporating the thiohydantoin compd. shown by the formula I and the hydrazine compd. shown by the formula II or III with silver iodide and silver bromide. The developer is prepared by compounding >=0.2g ion/l sulfurous acid ion and >=0.35g ion/l potassium ion with a developing agent of hydroquinone etc. The photosensitive material is developed with the developer at 11-12pH. Since the silver halide photosensitive material contg. the hydrazine compd. is developed with the developer contg. a high concn. of the sulfurous acid ion and having an improved preservative property, the excellent image having high sensitivity and good dotted image quality is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention (Field of Industrial Application) The present invention relates to an image forming method, and particularly to a silver image forming method that stably provides a high contrast photographic image.

(Prior art) Generally, high-contrast photographic images are used to form letters and halftone-resolved photographic images in the photolithography process, and fine line images in the ultra-precision photolithography process. It is known that certain types of silver halide photographic materials can form photographic images with extremely high contrast.

Conventionally, for example, a photosensitive material consisting of a silver chlorobromide emulsion with 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 %) has been processed using sulfite ions. A method of obtaining an image with high contrast, high sharpness, and high resolution, such as a halftone dot image or a fine line image, is carried out by processing with an alkaline hydroquinone developer having a low concentration.

This type of silver halide photosensitive material is known as a lithium 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 halftone dot image is formed by using the above-mentioned Lith photosensitive material and photographing an original through an intersection line screen or contact screen, and then performing a development process.

For this purpose, a silver halide photographic 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 photographic 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 developer. Therefore, it is processed with a developer called Risu developer, which has extremely low sulfite ion ae and uses hydroquinone as a developing agent. However, since Lith 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 (3G). Significant efforts have been made to improve the persistence of.

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. (chronological fatigue replenishment) and replenishment using separate replenishment solutions. The so-called two-component replenishment system 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.

According to this method, the concentration of sulfite ions can be kept high in the developer, and stable processing can be performed with improved preservability.

However, the developer used for silver halide photographic light-sensitive materials containing hydrazine compounds requires a relatively high pH value in order to obtain high contrast, which tends to cause force 7. Since the method contains a unique organic inhibitor at a high concentration, it has the disadvantage that sensitivity cannot be obtained. Therefore, there is a strong desire for a system that can provide high-contrast images and low capri and high-sensitivity photographic characteristics.

(Object of the Invention) An object of the present invention is to provide a method for forming an image in which a silver halide photographic light-sensitive material containing a hydrazine compound is processed with a developer containing a high concentration of sulfite ions, to produce photographs with high sensitivity and high halftone dot quality. An object of the present invention is to provide an image forming method that can obtain characteristics.

(2) Structure of the Invention The object of the present invention is to develop a silver halide photographic material containing a combination of a compound represented by the following general formula (I) and a hydrazine compound in a developer having the following conditions (a) to →. This is accomplished by an image forming method that processes.

(b) Sulfite ion concentration is 0.2 g ions/l or more (in) Potassium ion concentration is 0.35 g ions/l
l or more (ノ → pH is 11 to 12.0 General formula [Engine] In the formula, 几■ and R2 are each a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), or an optionally substituted carbon number of 1 ~8 alkyl groups (e.g. methyl 2!ti, ethyl group, hydroxyethyl group, etc.), optionally substituted alkoxy groups having 1 to 8 carbon atoms (e.g. methoxy group, ethoxy group, etc.), phenyl group, naphthyl group , represents a sulfo group or a carboxy group, R1 and R2 may be combined to form a hexacyclic ring, and on this ring, a halogen atom, a lower alkyl group, a hydroxy group, a hydroxyalkyl group, a phenyl group, an alkoxy group, It may be substituted with a carboxy group or the like.

R3 is an optionally substituted alkyl group (e.g., methyl group, ethyl group, sulfoethyl group, sulfopropyl group, sulfamidoethyl group, sulfonyl group, etc.) or an optionally substituted alkenyl group (e.g., allyl group) etc.).

R4 represents an optionally substituted alkyl group having 1 to 12 carbon atoms, and the substituent is preferably a hydroxy group, a carbamide group, etc., and this alkyl group has 10-1-OCO- between its carbon chains. Includes those in which 1-NH- and -N are present.

几5 is a halogen atom (for example, a chlorine atom, an A atom, etc.),
Even if each is substituted with a lower alkyl group (e.g. methyl group, ethyl group, etc.), a hydroxy group, a hydroxyalkyl group (e.g. hydroxyethyl group), an alkoxy group (e.g. methoxy group, ethoxy group, etc.), a sulfo group or a carboxy group. Represents a good phenyl or pyridyl group.

The compound represented by the general formula (I) is disclosed in JP-A No. 55-4501.
The method described in No. 5, and U.S. Patent No. g 2,74λ833, U.S. Pat.
575,704, 3,615,517, 3,615
, 519, 3,632,340, and can be easily synthesized by those skilled in the art.

The compound represented by the general formula (I) of the present invention is suitably added in a silver halide emulsion in an amount of 104 to 1O-1 mol (preferably 10'' to 1O-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.

Specific examples of the compound represented by the general formula [I] include the following compounds, but the compounds are not limited thereto.

1111-(2-diethylamineethyl)-5-((ethylnaphtho(Z,1-d)oxazolin-2-ylidene)ethylidene)-3-(pyridin-2-yl)-2-thiohydantoin(211-(2- diethylaminoethyl)-3-(pyridin-4-yl)-5-(3-ethyl-2-benzoxo→nozolinidene)eguliden]-2-thiohydantoin(311-(2-hydroxyethyl)-,3-(4- Sulfobutyl-pyridin-2-yl)-5-((3-sulfopropyl-2-penzoxolinidene)ethylidene 2-thiohydantoin sodium salt (41x-(2-acetylbutyl)-3-(pyridine-
2-yl)-5-((3-sulfodiethyl-2-penzoxazolinidene)ethylidene]-2-thiohytantoin sodium salt (s) 1-(2-hydroxyethyl-3-(pyridine- 2-yl)-5-((3-sulfopropyl-2-thiohydantoin sodium salt -16)1-(2.3
2-Thiohydantoin sodium salt (7) 1-(2- Hydroxyethoxyethyl)-3-(pyridin-2-yl)-5-((3-sulfo7/3/L/-s-Glo-2-penzoxazolinidene)ethylidene-2-thiohydantoin sodium Salt 1811-(2-hydroxyethoxyethoxyethyl)
-3-(pyridin-2-yl)-5-((3-sulfobutyl-5-chloro-2-pensoxazolinidene)ethylidene-2-thiohydantoin sodium salt (9) 1-(2-hydroxyethyl aminoethyl)-3
-(4-chloropyridin-2-yl)-5-C(3-sulfobutyl-5-methyl-2-penzoxazolinidene) ethylidene-2-thiohydantoin sodium salt (111-(2-hydroxyethoxyethyl )-3-(
p-Ethoxypyridin-2-yl-5-[(3-sulfobutylnaphtho(2,1-d)oxazolin-2-ylidene)ethylidene-2-thiohydantoin sodium salt al) 1”(2-calhami)/z methyl -3-(4
-methylpyridin-3-yl)-5-((3-sulfobutylnaph l-[&1-d]oxazolin-2-ylidene)edylidene]-2-thiohytantoin sodium salt The following metal hydrazines are preferably used in the present invention: Examples include compounds represented by the general formula [11] or [1].

General formula (II) NHNHCHO General formula (1111% formula% In the formula, R1 and 2 each represent an optionally substituted aryl group or an optionally substituted alkyl group.

The aryl group represented by the R1 window and Rt includes a benzene ring or a naphthane 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 group, n-dodecyl group, etc.), alkoxy groups (preferably those with 1 to 20 carbon atoms,
For example, methoxy group, ethoxy group, etc.), aliphatic acylamino group (preferably those having an alkyl group having 2 to 21 carbon atoms, such as 7 acetylamino groups, heptylamino group, etc.),
Examples include aromatic acylamino groups, and in addition to these, for example, the above-mentioned substituted or unsubstituted aromatic rings include -CONH
1-S-1-O-1-802NH-1-NHCONH-
It also includes those bonded by a linking group such as 1-CH2CHN-.

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, in the hydrophilic colloid layer adjacent to the emulsion layer, or even in other hydrophilic colloid layers, but preferably in the emulsion layer or in the emulsion layer number ζ adjacent to the emulsion layer. It is to be contained in the layer.

The hydrazine compound can be added after being dissolved in alcohols such as methanol and ethanol, glycols such as ethylene glycol and diethyl glycol, ethers, ketones, etc. It is from 10@-6 to 10@-1 per mole of silveride, preferably from 10 to 10. Examples of particularly preferred hydrazine compounds are as follows.

(H-1) 1-formyl-2-phenylhydrazine (H-2) 1-formyl-2-(4-methoxyphenyl)hydrazine (H-3) 1-formyl-2-(4-bromophenyl)
Hydrazine (I(-4) 1-formyl-2-(4-ethylphenyl)hydrazine (H-5) 1-formyl-2-(4-methoxyphenyl)hydrazine (H-6) 1-formyl-2-( 4-acetamidophenyl)hydrazine (H-7) 1-formyl-2-(4-methylamidophenyl)hydrazine (H-8) 1-formyl-2-(4-phenylacetamidophenyl)hydrazine (H-9) 1 -formyl-2-(4-dimethylamino-
phenyl)hydrazine (H-1O) 1-formyl-2-(4-acetamido-2-methyl-phenyl)hydrazine (H-11)l
-Formyl-2-C,4-(3-phenyl-thioureido)phenyl]hydrazine () [-12) 1-pormyl-2-[:4-(3-ethyl-thioureido)phenyl]hydrazine (H-13) 1-formyl-2-(4-
(4-(3-phenylthioureido)phenylcarbamylphenyl)hydrazine()(-14) 1-formyl-2-1(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-methylbenzothiazole-2
-yl)thioureylenephenyl]hydrazine (H-17)1-formyl-z-(C4-(l, 3
-dimethylbenzimidazole- ureylene phenyl)hydrazine (H-18) 1-formyl-2-+[:4-(5-methyl-2-thio-imidacillin-3-yl-)phenyl]
) hydrazine CH-19) 1-formyl-2-1(4-(3-n-butyfureido)phenyl]) hydrazine (H-20)
! -formyl-2,-(4-(3-(p-chlorophenyl)unido]phenyl)hydrazine (H-21) l-formyl-2-(4-(3
-[p-(2-mercapto-tetrazol-3-yl)
phenylkothioureylene)phenyl)hydrazine()I-22) 1-formyl-2(4-(ω-(N
-Sulfopropylbenzothiazol-2-yl-)propylaminocophenyl)hydrazine (H-23) 1-formyl-2-(4-(3-(p-(phenylsulfamiphenyl)-unylene)phenyl)hydrazine (H -24) l-Formi Jl/-2-(4-(14-
di-tert-pentylphenoxymethylamido)fer]hydrazine (H-25) 1-formyl-2-(4-(3-(p
-ethylphenyl)ureido]phenyl)hydrazine (H-26) 1-formyl-2-14-(3-(2-methoxyphenyl)unido]phenyl)hydrazine (H-27) 1-formyl-2-(4- (3-2-prohylureido)phenyl]hydrazine (H-28) 1-formyl-2-(4-(3-prohylureidophenyl)hydrazine (H-29), 1-formyl-2-(4-[:3 −(p
-methoxyphenyl)ureido] phenyl 1 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-dodecylunido)phenyl]
Hydrazine (H-34) 1-formyl-2-('4-(
3-octadecylureido)phenyl]hydrazine ()
i-35) 1-formyl-2-(4-(3-(hexanoyl)ureido) phenyl 1 hydrazine (H-36
) 1-formyl-2-(4-(3-(benzyl)ureido) phenyl)hydrazine (H-37) ■-formyl-2-i4-(3-(pyridin-2-yl)ureido)
phenyl)hydrazine ()1-38) 1-formyl-2-(4-(3-(
Thiophenyl-2-yl)ureido]phenyl)hydrazine (H-39) 1-formyl-2-(4-[3-(4-methylthiazol-phenyl)hydrazine ()I-40) 1-formyl-2-( 4-[3-(
5-nitrophenyl)ureido]phenyl) and drazine (H-41) 1-nhexylacetylamino-4-
(2-acetylhydrazino)benzene (H-42)
1-(9-chlorobenzoyl)-2-phenylhydrazine (H-43) 1-(p~cyanobenzoyl)-2-
Phenyl dorazine (H-44) 1-(p-carboxybenzoyl)-
2-7enylhydrazine (H-45) 1-(3,5-dichlorobenzoyl)-2-phenylhydrazine (H-46) 1-(2-formylhydrazino)-4
-(N-dimethylamino)benzene (H-47) 1-(2-formylhydrazino)-4
-(2-Pormylhydrazino)benzylbenzene Various silver halides can be used in the silver halide emulsion layer of the silver halide photographic light-sensitive material (hereinafter referred to as light-sensitive material) used in the present invention. Examples 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 high-sensitivity light-sensitive materials containing little silver iodide (AgI 5 mol % or less).

The silver halide emulsion may be prepared by suspending the silver halide emulsion in a hydrophilic colloid by a known method, such as a single jet method using a neutral method or an ammonia method, or a double jet method. used.

The average grain size of the silver halide contained in the silver halide emulsion layer used in the present invention is 0.1 to 1.0 μm.

Particularly preferably, the grain size is 0.1 to 0.7 μm, and at least 75%, particularly preferably 80% or more of the total number of grains contains silver halide having a grain size of 0.7 to 1.3 times the average grain size. It is preferable.

Furthermore, as silver halide emulsions in which polyvalent metal ions (for example, iridium, rhodium, etc.) are adsorbed, U.S. Pat.
．． Emulsions such as those according to No. 531,291 can also be used. Silver halide emulsions are usually made using sulfur compounds,
Sensitization can be achieved by chemical sensitization using a gold compound (chloroaurate, gold trichloride, etc.).

Polymer latex consisting of a homopolymer 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 the photographic material and improve the physical properties of the film. It may be included for.

The silver halide emulsion of the light-sensitive material used in the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. Sensitizing dyes include cyanine, hemicyanine,
Commonly used methine dyes and styryl dyes such as rhodacyanine, merocyanine, oxanol, and hemioxonol can be used.

The silver halide emulsion used in the present invention has a stabilizer or a capri suppressor represented by the following general formula: s Ra
C and R may be the same or different, and each represents a hydrogen atom, a halogen atom, a nitro group,
Represents an amine group, cyano group, hydroxyl group, carboxyl group, alkoxy group, acyl group, or substituted or unsubstituted alkyl group, aryl group or heterocyclic group, Rh and R
c may be bonded 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-1,3゜3a
, 7-chitrazaindene (S-2) 4-hydroxy-5-ethyl-6-methyl-
1, 3, 3a, ? -Tetrazaindene (S-3)2-
Mercaptomethyl-4-hydroxy-6-methyl-1,
3,3a,7-tetrazainde(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-ami/-5-carboxy-4-hydroxy-1,3,3a,7 -Chitrazaindene (S-7) 5
-carboxy-4-hydroxy-1,3,3a,7-
Chitrazaindene (S-8) 2-methyl-4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene (S-9) 4-hydroxy-5-cyano-1,3゜3a
, 7-chitrazaindene (S-10) 3-chloro-4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene (8-11)
2. ．． 4-dihydroxy-6-methyl-1,3,3a
, 7-chitrazaindene (S-12) 1,2-bis(4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene-2
-yl) -1,2-dihydroxyethane (8-13) 5-amino-7-hydroxy-2-p-methoxyphenyl-1,! 3.4.6-Pentazaindene The above compound can be added during and/or at the end of physical silver halide ripening. 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 or after chemical ripening, or may be added during production of coating liquid E14.

A generally preferred method of addition is from 104 to 10-1, more preferably from 10" to 10" per mole of silver halide at the end of chemical ripening.
It can be added in a range of 10-2. When adding the above-mentioned 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 [I].

Furthermore, the photosensitive material used in the present invention has an antifoggant or a stabilizer containing the following general formula (%) [In the formula, Ar represents an aromatic ring, and the aromatic ring is an alkyl group (having 1 to 25 carbon atoms), a halogen atoms, hydroxy groups,
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 used in combination with a compound having the structure shown below, a remarkable fog suppressing effect can be obtained. Specifically, the following compounds can be mentioned.

(1) Hydroquinone (2) Methylhydroquinone (3) Chlorohydroquinone (4) Hydroquinone monosulfonate (5) 2,
5-diethylhydroquinone + 61 1,4-dihydroxynaphthalene (712,3-dihydroxynaphthalene (8) gentisaldoxime (912,5-dihydroxyacetophenone oxime aO) gentisamide (ill N-methylgentisamide & 21N-(β
-Hydroxyethylgentisamide (13N-(n-hexadecyl)-gentisamide)
Salicylaldoxime (151 resorcyaldoxime (161 hydroquinone monobenzoate a7) Hydroquinone aldoxime The above compound is US patent λ67
No. 5,314, British Patent No. 623.448, JP-A-5
You can make threats by referring to the descriptions in No. 2-11029 and the like.

In addition, any of the above-mentioned hydrazine compounds, polyalkynes, etc., which can be used in the silver halide photographic emulsion of the photosensitive material used in the present invention, can also be used in the developing solution of the present invention. The oxide compound, capri inhibitor or stabilizer is generally used in a proportion of 10-4 to 10-1 mole/silver per mole of silver halide, more preferably 5X10-4 to 5X1G'2 mole/silver.
Silver can be used at 1 molar concentration.

Known methods for preparing additives can be used to add these additives to the silver halide emulsion. That is,
L1-high alcohols such as methyl alcohol, ethyl alcohol, ethers (diethyl ether, diethyl ether), ketones such as acetone, dioxane, petroleum ether, or nonionic, anionic, or cationic surfactants. It may be added after being dispersed in a boiling point solvent.

In the light-sensitive material used in the present invention, a polyethylene oxide compound represented by the following general formula can be contained as a development regulator in the silver halide emulsion or in the hydrophilic colloid layer adjacent to the emulsion layer.

HO(CH20H20)nH [where n is 10 to Zoo! Expressing the number Il,
It is a block polymer of polyalkylene oxide with the following general formula % formula %) [wherein b is an integer from 1O to 5o, a and C are each a+C
represents an integer such that 5 to 501, and the polyoxyethylene group accounts for 10 to 70% by weight of the amount of block polymer i.
occupies ], or a compound represented by the following general formula can be similarly included.

[In the formula, 几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 (for example, benzoyl, p-methylbenzoyl, etc.). In the formula, d represents an integer 'Ik from lO to 100. ] Polyalkylene oxide polymers such as those described above are useful for the purposes of this invention.

These compounds include polyols such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene polymers, aliphatic alcohols, phenols, fatty acids, and ethylene oxide.

It can be synthesized by condensing 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 needs to be 10 or more, and preferably 100 or less.

Next, specific examples of polyalkylene oxide compounds will be shown, but the invention is not limited thereto.

[Specific examples of polyalkylene oxide compounds] ('1-
1) HO(CH2CH20)nH(n = 35
)(1-2) nc4Hso(C)f2cH20)n
H (n = 20) (1-3) nCH170 (CH
20H20) IH (n = 30) (l-8) HO(CHzCHzO)l! (CH2)in(CH2C
H20)nCOCH2CH2COOH(1+n =70
．． m=5) HO(CI-fzcHzo)z(C1(CH20)m
(CI(zcHzo)nHl-13 (1+n = 15.mx17) (1-to) HO(CHzCHzO)tccHcHto>mCCHz
CH20) flH product [j+n=30. m-depth 35] )10(CHzCHzO)/(C)lcHzO)(y,
(CH20H20)nH02H.

(1+ n =15 e m 15 EHO(CH2
0H20)l (CHCHx O)m (CH2CH2
O) nHzHs (1+ n = 30, m = 15) HO(CH20H20)/ (CHzCH2CH2CH
20) m(CH2CH20)nH(1+ n =23.
m = 21), HO(CH20H20)/(CH
2CH2CHzCHzO)m (CH2CH20)nH
(1-15) HO(CHzCHzO)/(CHCHzO
) m(CHzCHzO)nHCH200H3 (/ + n = 15, m = 15] (1-16)
HO(CHzCHzO)/(CHCHzO)m(CH
2CH20) IHCHzOCHa (1+ n = 30, m = 15) (1-17)
nQ2H2ρ(CHCHzO)/(CH2CH20)m
H■ CH3 (/=7.mx30) (1-18) nc1□H2s8(CIICH,O)/
(CH2CH,0)mHCH3 (1=7, m-30) HOOCCHzCHzCO(CHzCHzO)j(CH
2CHHzCHzCHzO)m(CHzCHzO)nCC
HzCHzCOOH(1+n = 15.mm-15)H00CCH2CHzCO(CHzCHzO)z(C
I-ICHzO)(CH2CH20)nccH2cH2
cOOH(/ 10n = 15. m = 20) (n = 3o) (/ + n = 90) HO(CIhCHzO)j(CHzCHO)m(CHz
CHzO) nH (/ + n = 15, m = 20
)HO(CH2CH20)/ (CH2CHO)m (
CH2CH20) nH(1+ n = 25, m =
30) The amount of the polyalkylene oxide compound added is preferably from 10 g to 31 g per mole of silver halide, and the timing of addition can be selected at any time during the process of producing the photographic emulsion of the present invention. , is preferably added after the second ripening is completed.

The silver halide photographic emulsion of the light-sensitive material used in the present invention contains commonly used hardening agents, such as aldehydes (formaldehydes, glyoxals, glutaraldehydes, mucochloric acid, etc.), N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-) IJ acroyl-hexahydro-S-triazine, bis(vinylsulfonyl) methyl ether, etc.), active halides (λ4
-dichloro-6-hydroxy-8-)riazine, etc.), etc.) can be used alone or in combination, and thickeners,
Commonly used matting agents, coating aids, etc. can be used. Further, as the binder, a commonly used hydrophilic binder having protective colloidal properties can be used.

Duty r! A'f: Usually used as a coupler, ultraviolet absorber, fluorescent whitening agent, image stabilizer, antioxidant, lubricant, metal ion sequestrant, emulsifying dispersant, etc. when applied to color photosensitive materials. In addition to the silver halide emulsion layer, the light-sensitive material used in the present invention includes a protective layer, an intermediate layer, a single filter layer, an anti-halley 217 layer, a subbing layer, an auxiliary layer, an irradiation prevention layer, and a backing layer. The support may have a coating layer, etc., and the support to be used may be appropriately selected from baryta paper, polyethylene ethylene-coated paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc. depending on the intended use of the photosensitive material.

The developer used in the present invention is HO-(C
M = C1, I) similar to n-OH, HzN (C=
C) A commonly used developer such as n-NH2m or a developer having a petero ring can be used.

HO-(CH=CH)n-0) (as a type developer,
Compounds represented by the following general formula are useful.

0H (Ji-1 In the formula, Rr, , R? and R8 are each a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a sawn or unsubstituted heterocyclic group, -〇-几9 crystal or -8-1'L9 group, where 几9 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group%111 represents 0 or 1.

)(0-(CH=CH)n-OHm developers include catechol, pyrogallol, its g4 form, and ascorbic acid, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, and methylhydroquinone. tree/
Z3-dichlorohydroquinone, 2.5-dimethylhydroquinone, 2.3-dibromohydroquinone, 2
．． 5-dihydroxyacetophenone, λ5-diethylhydroquinone.

λ5-p-phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-9
0-locatechol, 3-phenylcatechol, 4-phenyl-catechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, hydroquinone monosulfonate, methyl-hydroquinone monosulfonate, chlorohydroquinone monosulfonate, 2,5-dimethylhydroquinone monosulfonate , 3-dibromohydroquinone monosulfonate, 4(2'-human mixybenzoyl)pyrogallol, ascorbic acid sorta, and the like.

Typical HO-(CH=CM)n-NH second base developers include ortho and para aminophenol or aminopyrazolone, 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4 -90 rho 6-phenylphene/-/L/, 4-7 minnow 2-phenylphenol, 3.4-diaminophenol, 3-methyl-4,6-q aminophenol, 2.4-cyamylsorcinol, 2 .4.6-triaminophenol, N-
Methyl-p-aminophenol, N-β-hydroxyethyl-p-aminophenol, p-hydroxyphenylaminoacetic acid, 2-aminonaphthol, etc.

Examples of the H2N-(C=C)n-NHz type developer include 4-amino-2-methyl-N, N-diethylaniline, λ4-diamino-N, N-diethylaniline,
N-(4-amino-3-methylphenyl)-morpholine, p-phenylenediamine, 4-amino-N, N-dimethyl-3-hydroxyaniline, N, N, N', N'-
Tetramethylparaphenylenediamine, 4-amino-N
-ethyl-N-(β-hydroxyethyl)-aniline,
4-Aminol-3-methyl-N-edyru-N-(β-hydroxyethyl)-aniline, 4-amino-h-ethyl-
(β-methoxyethyl)-3-methyl-aniline, 4-
Amino-3-methyl-N-ethyl-N-(β-methylsulfonamidoethyl)-aniline, 4-amine-N-butyl-N-r-sulfobutylaniline, 1-(4-aminophenyl)-pyrrolidine, 6-amino-1-ethyl,
1. Otsu 3,4-tetrahydride a-quinoline, 9-aminoyllolidine, etc.

As a developer having a heterocycle, a compound represented by the following general formula aAlζ is useful.
Represents a phenyl group substituted with a group such as a chloro group, an amino group, a methylamino group, an acetylamino group, or a methoxy group. or an alkyl group substituted with a substituent such as a hydroxy group, a carboxy group or a sulfo group. Specifically, the following compounds may be mentioned.

l-Phenyl-3-pyrazolidone (phenidone) 1-phenyl-4-amino-5-pyrazolone 1-(p-aminophenyl)-3-aminopyrazoline 1-phenyl-3-methyl-4-amino-5- Pyrazolone l-phenyl-4,4'-dimethyl-3-pyrazolidone (dimezone) 1-phenyl-4-methyl-4-hydroxymethyl-3
-pyrazolidone (dimezone-8) l-phenyl-4,4
-dihydroxymethyl-3-pyrazolidone 1-phenyl-5-methyl-3-pyrazolidone 1-p-
Aminophenyl-4-meg-4-propyl-3-pyrazolidone t-p-chlorophenyl-4-methyl-4-ethyl-3
-pyrazolidone 1-p-acetamidophenyl-4,4-diethyl-3
-pyrazolidone 1-p-h-lhydroxyethylphenyl-4゜4
-dimethyl-3-pyrazolidone 1-p-methoxyphenyl-4,4-diethyl-3-pyrazolidone 1-p-1-zyl-4,4-dimethyl-3-pyrazoli
Tong et al.

Others: The Theory of Oz by T. H. James
The Photographic Process 4th Edition
ory of the Photographic P
rocess, Fourth Edition) 2nd
91-334 and Journal of the American Chemical Society.
eAmerican Chemical 5ociet
y) Developers such as those described in Vol. 73, No. 3100Ti (1951) can be effectively used in the present invention. These developers may be used alone or in combination of 2g1 or more, but it is preferable to use two or more types in combination. A preferred combination is a combination of hydroquinone and phenidone or hydroquinone and dimezone, with NoA hydroquinone having a concentration of 5y to 509/l. Furthermore, it is preferable to use phenidone or dimezone in a range of o, osy to 511/l. Further, even if WcM or salt such as sodium sulfite, potassium sulfite, or ammonium sulfite is used as a preservative in the developer used in the present invention, the effects of the present invention will not be impaired, and the In addition, hydroxylamine and hydrazide compounds may be used as preservatives.In addition, pH adjustment using caustic alkali, alkali carbonate, or amines, etc. used in general black and white developers. Inorganic development inhibitors such as brompotali, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, sodium alkylarylsulfonate, natural saponin, It is optional to add surfactants such as saccharides or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, and gluoxal, and ionic strength adjusting agents such as sodium sulfate.

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

Examples of the alkanolamine include monoethanolamine, jetanolamine, triethanolamine, etc., and triethanolamine is particularly preferred. The preferred content of these alkanolamines is developer solution 1.
) per 2 to 300 I, especially 1 per developer
The glycols used in the present invention include, for example, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, 5-bentanediol, 2-methoxyethanol, etc. Diethylene glycol is preferred. The preferred amount of these glycols to be used is 1O to 200.9 per 1 liter of developer, especially in developer 11
20 to 1001 is preferable.

The above alkanolamines and glycols may be used alone or 2. s or more may be used in combination.

The developer used in the present invention can contain an organic capri inhibitor.

Preferred organic capri inhibitors include the following general formula (IV):
, (V), or [■] at least one
It is preferable to contain seeds, and at least two or more of the above chemical compounds may be used in combination.

General formula (iV) [In the formula, G represents a nitrogen atom or a methine group, H represents a nitrogen atom or a carbon atom, J represents a sulfur atom, l! 1
represents an elementary atom or an imino group, and when H is a carbon atom, F represents a water atom or an alkyl group. However, at least one of G and I is an i1 elementary atom, and when G represents a methine group, J is an imino group. n is 01E or 1
When H is a nitrogen atom, n is O, and when H is a carbon atom, n is 1.几 and 4 represent a hydrogen atom, a halogen atom, a lower alkyl group having 3 or less carbon atoms, a lower alkoxy group having 3 or less carbon atoms, a hydroxyl group, a carboxy group, a sulfonic acid group, or a nitro group. ] General formula [V] [wherein, X is a hydrogen atom, a halogen atom, an alkyl group, a nitro group, -COOM', -803M', -OH
or each group of -CONH2, M' represents a hydrogen atom or a lower alkyl group having 3 or less carbon atoms, and n is 1 or 2.
, W′ represents a sulfur atom, an oxygen atom, or an imino group, L , M represents water, an alkali gold IA atom, or an ammonium salt, L , R represents a hydrogen atom, and C atoms are 3 or less. represents a lower alkyl group, a lower alkoxy group having 3 or less carbon atoms, a hydroxy group, a carboxy group, a /X rogen atom, or a sulfonic acid group. ] General formula (Vl) [In the formula, M2 is a hydrogen atom, an alkali metal atom, or -NH
4 groups, X is 1000M", -8ChM", -O
represents each group H or -CONHz, M' is a hydrogen atom,
It represents an alkali metal atom or -NH4 group, and R16 represents a hydrogen atom or a lower alkyl group having 3 or less carbon atoms.

n is 0.1 or 2. ] Preferred examples of the compound represented by the above general formula (IV) include the following.

(1) 5-nitroindazole (2) 6-nitroindazole (3) 5-methylbenzotriazole (4) 6-methylbenzotriazole (5) 5-nitropenzimidazole (6) 6-nitropenzimidazole Next, general Examples of preferred compounds represented by formula [V] are listed below, but are not limited thereto.

(112-mercaptobenzimidazole-5-sulfonic acid (2) 2-mercaptobenzimidazole (3) 2-mercapto-7-methylbenzitriazole-5-sulfonic acid (4) 2-mercapto-7-acetyl-penzimidazole- 5-sulfonic acid sodium salt (5) 2-mercapto-5-methylbenraimiguzole (6) 2-mercapto-5-nitropenzimidazole (712-mercapto-6-acetylbenzimidazole-5-sulfonic acid ammonium salt +8 ) 2-mercapto-7-chloropenzimidazole-5-sulfonic acid (912-mercapto-7-bromobenzimidazole-5-sodium sulfonate (112-mercapto-5-sulfonic acid-7-carboxylic acid)benzimidazole (lη 2 -Mercapto-7-hydroxybenzimidazole-5-sulfonic acid (lη) 2-Mercapto-7-ethylbenzimidazole-5-sulfonic acid Next, specific examples of the compound represented by the general formula (Vl) are shown below. , but not limited to.

(1) 1-phenyl-5-mercaptotetrazole 1211-(3-sulfonic acid-4-methyl)phenyl-
5-mercaptotetrazole sodium salt 1311-(
3-Sulfonic acid-7-chloro)phenyl-5-mercaptotetrazole sodium salt 1411-(p-Sulfonic acid)phenyl-5-mercaptotetrazole ammonium salt (5) 1-(1-chloro-4-sulfonic acid)phenyl-
5-mercaptotetrazole sodium salt (611-(
3-Sulfonic acid-4-methyl) phenyl-5-mercaptotetrazole potassium salt 1711-(p-sulfonic acid) phenyl-5-mercaptotetrazole potassium salt (811-(p-methoxy)phenyl-5-mercaptotetrazole 1911-( p-hydroxy)phenyl-5-mercaptotetrazole α01l-(p-hydroxyethoxy)phenyl-5-
Mercaptotetrazole (u) 1-(3,5-dicarbamyl)phenyl-5-mercaptotetrazole α21l-(p-carbamyl)phenyl-5-me.

Lucaptotetrazole (1:1 l-(p-carbamyl)phenyl-5-mercapto-tetrazole) The compound represented by the general formula (IV) is 10 to 10-1 mol, more preferably 10' to 10 =
mol, the compound represented by (V) or CVI) is 104 to 1 mol, more preferably lO'' to 1 mol, per developer li.
O-2 mol, and the preferred total content of these development inhibitors is 10 to 10-1 mol per developer, particularly preferably 10 to 107 mol per liter of developer. or.

It is preferable that the development inhibitor is dissolved in an alkanolamine and/or a glycol before being added to the developer.

The processing with the developer in the present invention is carried out under various conditions5.
However, the development temperature is preferably 50° or less,
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 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 hand skin image processing such as plate development and frame image processing.

Mechanical development such as roller development or hanger development may be used.

(Example) EXAMPLES The present invention will be described in detail below with reference to Examples.

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 Silver iodobromide emulsion (1 mol of silver, 1 mol of silver
(mol%) was prepared. The average grain size was 0.28 μm. This emulsion was washed with water and desalted according to a conventional method, and then sensitized with sulfur. After sensitization, hydroquinone 3II, resorcinaldoxime 2I and 4-hydroxy-6-methyl-1 were added as stabilizers.
, 3,3a, 7-thitrazaindene compounds were added per mole of silver, respectively.

Furthermore, 1-phenyl-5-mercaptotetrazole is added as a capri inhibitor at 0.1.9% per mole of silver. As a development regulator, polyethylene glycol having 30 ethylene oxide chains (one of the terminal groups is dodecylbenzene) was added at 0.00% per mole of silver. In addition, an emulsion was prepared by adding saponin as a coating aid and styrene-maleic acid copolymer as a thickener. This emulsion was divided into 10 parts, and a compound represented by the general formula [I] or a comparative compound shown in Table 1 and a compound represented by the general formula [U] were added to each part to prepare an emulsion coating solution. The compound represented by the general formula [I] is 3X10" mole/silver 1 mole, and the compound represented by the general formula [13] is 3X10" mole/silver 1 mole.
3 mol/silver 1 mol was added.

Next, a coating solution for a protective film was prepared as follows. That is, 101 parts of pure water was added to 1 kg of gelatin, and after swelling, 40 parts of pure water was added to 1 kg of gelatin.
A polymeric material of methyl methacrylate (average particle size 0.27 μm) was dispersed in 30FY gelatin as a matting agent and finished to 201 to obtain a coating solution for a protective film.

Preparation of silver halide photographic light-sensitive material The above-prepared emulsion coating solution and protective film coating solution were combined on a polyethylene terephthalate support with a thickness of 100 μm that had been subjected to subbing processing, and silver N was coated simultaneously by multilayer coating.
51/m', the amount of gelatin applied to the emulsion layer was 1.8. ! i
+/m", and the amount of gelatin applied to the protective layer is 1.
Sample layers 1 to 1 shown in Table 1 were coated so that the
/l610 was created. At the time of multilayer coating, hardening agents 3861 of formaldehyde, mucochloric acid, and ethyleneimine were added to the protective film coating solution to harden the film.

The samples /l61~/%10 were subjected to stepwise exposure with xenon light through a commercially available normal contact screen (gray negative 150 line), and then five types (A, B%C1D and B) shown in Table 2 were obtained. It was developed using a developer solution. A commercially available quick fixer was used as the fixer. The development processing conditions are
Development was performed at 40° C. for 20 seconds, fixing was performed at 35° C. for 20 seconds, and washing was performed at room temperature for 20 seconds.

Halftone dot area of the above-treated samples: 10%, 50% and 95
% of each halftone dot quality 1 was visually observed using a 100x magnification looper to give a 5-grade evaluation. As for the evaluation score, "1" is the lowest quality, and the quality increases sequentially, and the rank "5" indicates the highest level.

Shishi-1 Umbrella comparison compound: 1-(2-hydroxyethoxyethyl)
-3-phenyl-5-((3-sulfomethyl-5-chloro-2-penzoxazolinidene)ethylidene]-2-
Thiohydant inna, thorium salt table-2! ! -2 to clear 5, sulfite ion concentration.

Preferable results can be obtained when the potassium ion concentration and pH are within the range of the present invention (3) Effects of the invention In an image forming method in which a photosensitive material containing a hydrazine compound is developed with a high concentration of sulfite ions, the sensitivity and halftone quality is improved.

Claims (1)

[Scope of Claims] A silver halide photographic material containing a combination of a compound represented by the following general formula [I] and a hydrazine compound is processed with a developer having the following conditions (a) to (c). Characteristic image forming method. (a) Sulfite ion concentration is 0.2 g ions/l or more (b) Potassium ion concentration is 0.35 g ions/l
(c) pH is 11 to 12.0 General formula [I] ▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms, halogen atoms, and the number of optionally substituted carbon atoms, respectively. 1 to 8 alkyl group, hydroxy group, alkoxy group, phenyl group, naphthyl group, sulfo group or carboxy group, R_1 and R
_2 may be combined to form a 6-membered ring. R_3 represents an optionally substituted alkyl group or alkenyl group, and R_4 represents a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms. R_5 represents a phenyl group or a pyridyl group, each of 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. ]