JPH01200352A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To give the high sensitivity and the high contrast photographic characteristic to the title material, and to improve the pressure sensitization of the material by incorporating specified hydrazine compd. and compd. in a surface latent image type silver halide emulsion layer and/or an another constituting layer mounted on a supporting body, respectively. CONSTITUTION:The surface latent image type silver halide emulsion layer is mounted on the supporting body, and the hydrazine compd. shown by formula I and the compd. shown by formula II are incorporated in the emulsion layer and/or the another constituting layer contd. in the sensitive material, respectively. In formula I, R1 is an aliphatic or an aromatic group, R2 is hydrogen atom or alkyl group, etc., G1 is carbonyl or sulfonyl group, etc., A1 and A2 are both hydrogen atoms or one of the groups is hydrogen atom, while another of the groups is alkyl sulfonyl group etc. which may be substituted. In formula II, X is hydroxy group, etc., R<3> and R<4> are each hydrogen atom or alkyl group, etc., R<8> is hydrogen atom or a group capable of substituting. Thus, the sensitive material having the high sensitivity and the super high contrast photographic characteristic and the improved pressure sensitization is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides ultra-high contrast images used in the field of photolithography.
This invention relates to a silver halide photographic material that can be rapidly formed using a highly stable processing solution.

(Prior Art) It is well known that certain silver halides can be used to form extremely high contrast photographic images, and methods for forming such photographic images are used in the field of photolithography.

For example, silver chloride bromide (at least the silver chloride content!
By processing a lithium-type silver halide light-sensitive material consisting of a lithium-ion silver halide photosensitive material consisting of a sulfite ion with a hydroquinone developer containing an extremely low effective concentration of sulfite ions (usually less than 11 mol/l of O), image areas and non-image areas can be clearly distinguished. A method is known for obtaining line drawings or halftone dot images with high contrast and high blackening density. However, with this method, the concentration of sulfite in the developer is low, so the developer is extremely unstable to air oxidation, and various efforts and ingenuity are required to keep the developer activity stable. Met.

This eliminates the instability of image formation caused by lithographic development,
There is a need for an image forming system that can be developed with a processing solution that has good storage stability and provides ultra-high contrast photographic characteristics, and is disclosed in US Pat. /Ar, P77,
Same c, JJ/, No. 117, Same≠, 2λ≠, ≠O1, Dou, Kohiro 3,73 No., Dou ψ, λ7 Ko, No. 606, Dou, 31/.

No. 71/ etc. contain a surface latent image type silver halide photographic light-sensitive material containing 10% of an acylhydrazine compound at pH 10,
j ~/2. A system has been proposed for forming an ultra-high contrast negative image with γ of more than 10 by processing with a developer having good storage stability and containing a sulfite preservative of 73 or more J mol/i J mol. This new image forming system has the advantage of being able to use highly sensitive silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chloride or silver chlorobromide. There is.

The use of hydroquinone or substituted polyhydroxybenzene as a method for improving pressure sensitization in ultra-high contrast imaging systems using acylhydrazine compounds is disclosed in JP-A-1-3.

The use of substituted hydroquinones, especially hydroquinones substituted with thio groups, to improve sensitivity and contrast was disclosed in JP-A-Sho! ≠−≠Otλ is shown as υ11.

In addition, in 1973, it was discovered that a sensitive material containing a pyrazolidone-based developing agent was processed with a developing solution containing an indazole-based stabilizer.
-/31, 7th edition.

These JP-A-62-2//Hiroshi J, lq,? Goo≠04.
No. 2 and No. 60-/Jt74cO both use a hydrazine compound, but the compounds corresponding to the general formula (II) of the present invention are different.

In addition, as a patent for using an aminophenol compound as a compound similar to the general formula (n) of the present invention, JP-A-Sho≠2
-1? /λ≠, same! 2-/10 kota, same ta-iirz
These systems do not use hydrazine compounds and have a different structure from that of the present invention.

(Objective of the Invention) The object of the present invention is to use a developing solution with good storage stability, to achieve high sensitivity, extremely high contrast photographic characteristics with r exceeding IO, and to provide improved pressure sensitization with halogenated Our objective is to provide silver photographic materials.

(Structure of the Invention) The object of the present invention is to have a surface latent image type silver halide emulsion layer on a support, and to provide hydrazine represented by the following general formula (I) in the emulsion layer and/or other constituent layers. This was achieved by a silver halide photographic material containing a compound represented by the following general formula (n).

First, the hydrazine derivative of general formula (I) used in the present invention will be explained.

General formula CI) IA2 In the formula, R□ represents an aliphatic group or an aromatic group, and R2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarbonyl group. Go represents a carbonyl group, sulfonyl group, sulfoxy group, -P- group, or iminomethylene group, and Person 1 and A2 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In general formula (I), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 7 to 30 carbon atoms.
20 straight chain, branched or cyclic alkyl groups. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. In addition, this alkyl group is an aryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfo/amide group, or a carbonamide group.

In the general formula (I), the aromatic group represented by B□ is a monocyclic or monocyclic heptaryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be fused with a single ring or a complete aryl group to form a teroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Examples include an inquinoline ring, a benzimidazole ring, a thiazole ring, and a menjibuazole ring, among which those containing a benzene ring are preferred. - Particularly preferred as R1 is an aryl group.

The aryl group or unsaturated heterocyclic group of R may be substituted, and nine representative substituents include a linear, branched or cyclic alkyl group (preferably one with carbon number/-20). ), aralkyl group (preferably a monocyclic or monocyclic alkyl group having 1 to 3 carbon atoms), alkoxy group (
(preferably those having 7 to 7 carbon atoms), substituted amino groups (preferably amino groups substituted with alkyl groups having 1 to λ0 carbon atoms), acylamino groups (preferably those having 2 to 30 carbon atoms), sulfones. Amide group (preferably carbon number 1~
30), ureido group (preferably 7 to 7 carbon atoms)
30).

The alkyl group represented by R2 in the general formula CI) is preferably an alkyl group having a carbon number of ~μ to
It may have a substituent such as a halogen atom, cyan group, carboxy group, sulfo group, alkoxy group, or phenyl group.

The aryl group represented by R2 is preferably a monocyclic or bicyclic aryl group, and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxy group, a sulfo group, or the like.

The alkoxy group is preferably an alkoxy group having carbon number/-r, and may be substituted with a norogen atom, an aryl group, or the like.

The aryloxy group is preferably monocyclic, and the substituent includes a halogen atom.

As the amine group, unsubstituted amine, no group, and carbon number 1 to I
Q is preferably an alkylamino group or an arylamino group,
It may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, etc.

The carbamoyl group is preferably an unsubstituted carbamoyl group, a furkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, and may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, etc. is preferably an alkoxycarbonyl group or an aryloxycarbonyl group having 1 to 10 carbon atoms, and may be substituted with an alkyl group, a nitrogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R2, when G is a carbonyl group, preferred are a hydrogen atom, an alkyl group (e.g.
methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.),
Aralkyl group (e.g., 0-hydroxybenzyl group), A)-,' group (e.g., phenyl group, 3.!-
(dichlorophenyl group, o-methanesulfonamidophenyl group, ≠-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when G1 is a sulfonyl group, R2 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group) or substituted amino group (e.g.
dimethylamino group, etc.) are preferred.

When G1 is a sulfoxy group, R2 is preferably a cyanobenzyl group or a methyltheobe/zyl group, and a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or a phenyl group are preferable, and a phenoxy group is particularly preferable.

When Go is an N-substituted or unsubstituted iminomethylene group,
Preferred R2 is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R2, in addition to the substituents listed for R1, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, etc. can be applied.

G in general formula (I) is most preferably a carbonyl group.

A1 and A2 are a hydrogen atom, an alkylsulfonyl group having a carbon number of 2Q or less, and an arylsulfonyl group (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is 10,! or more) ), an acyl group having a carbon number of λO or less (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is 10,! or more, or a linear, branched, or cyclic unsubstituted and a substituted aliphatic acyl group (substituents include, for example, a halogen atom, an ether group, a sulfonate group, a carbonamide group, a hydroxyl group, a carboxy group)
Examples include sulfonic acid groups. )) A hydrogen atom is most preferable as A1 and A2.

Rlt or R2 in the general formula (I) may have a ballast group incorporated therein which is commonly used in immobile photographic additives such as Kabucy.

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

R1 or R2 in the general formula CI) may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Examples of such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups.

3ts, toy issue, douan, 4! ! 3≠7, JP-A No. 233, JP-A No. 200゜237,
same! ? -20/, 04L, r, same! Turco oi, o
ats issue, same jP-20/, 04c7 issue, same! Tar x
oi, ohiro issue, same Tatako 0/, 0≠2 issue, Tokukai Sho t
/-/70.7JJ No. 61-270. Ha No. 1, No. 6
Kota U J No. 101, Special Application No. 62-47, No. 62-
Examples include the groups described in No. 67.101 and No. 67.110.

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

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

1-/')! -ri! -3) I-Hiro) I-J') 1-J) ■-7) 1-r)! -2) CHzCH2CH2SH [-10) 1-/ / ) 1-/λ) 1-/Hiroshi) 1-/ j' ) 1-/ J) 1-/7) 1-/r) 1-/ri) 1 -2o')! -2/)! -ko2) ■-23)! -2 Hiroshi)! -1ri■-kot) i-27)! -Kol)! -2F) 1-J O) 1-J/) ■-32) 1-3 Hiro) 1-3t) 1-s +) In addition to the above-mentioned hydrazine derivatives, RESEARCHDISCLO8URE■
tem λ3j16 (/rit3 year ii issue, P, j≠6
) and the documents cited therein, as well as U.S. patents≠, or
o, KoQ7 No., same μ, Kotori, Pλ No., same≠, 27t
, 34≠ issue, same≠, λ7r, 7hiro issue, same≠, 31j,
No. 101, same≠, 4tjri.

3 hiro 7, doyu, rto, tsr, same≠, ≠7r,
No. y2r, British Patent 2,0//, 39/B.

Unexamined Japanese Patent Publication No. 1986-1973 No. 73, 4/-/70゜733
No., A/-270.7 Hirosan No., T Kota Hiro No., E
Pco/No. 7,310, special request Shoj/-17! , 23≠ issue,
Same 4/-2! /, Datko-go, A/-Koro-t, No. 11,
6/-274, 2I3, t2-47. ! , No. 21, 62-67°! No. O, same, A, j-47, 110
No. 6λ-sr.

J-13, 6λ-t3o, xiri, 6--l≠
3. Those described in Hiroshi No. 62, T2-ITT, and IIY can be used.

Next, the compound of general formula (n) used in the present invention will be explained.

R4 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted alkylcarbonyl group, Represents an unsubstituted carbonyl group, a substituted or unsubstituted carbanoyl group, R, R,
R.

R8 represents a hydrogen atom or a substitutable group.

R%R4 may be the same or different, or may be linked to form a nitrogen-containing heterocycle (for example, heptulfolino group, py is lydino group, pyrrolidino group, imidazolyl group, piperazino group, etc.).

Hydrogen atoms are most preferred as R and R.

R%R, R, R [may be the same or different, and R and R may be linked to form a ~7-membered carbocycle or heterocycle, and these rings are saturated.

It can be either sum or unsaturated.

Substitutable groups for R%R%R%R include halogen atoms (fluorine, chlorine, bromine), alkyl groups (preferably those with carbon numbers/-20), and aryl groups (preferably those with carbon numbers 4 to 20). ), alkoxy groups (preferably those with a carbon number of 0 to 0), aryloxy groups (preferably those with a carbon number of 6 to 0), alkylthio groups (
Preferably carbon number/~coO), arylthio group (
(preferably one having j-20 carbon atoms), an acyl group (preferably one having 2 to 20 carbon atoms), an acylamino group (preferably one having 2 to 20 carbon atoms), an acylamino group (preferably having 20 to 6 carbon atoms), benzoylamino group), nitro group, cyano group, oxycarbonyl group (preferably an alkoxycarbonyl group with carbon number/~-〇, aryloxycarbonyl group with carbon aa to coO), carboxy group, sulfo group, ureido group ( Preferably a luureido group in alkali having 1 to 20 carbon atoms,
an aryl ureido group having t-coQ carbon atoms), a sulfonamide group (preferably an alkylsulfonamide group having 1 to λO carbon atoms, an aryl sulfonamide group having t-10 carbon atoms)
, a sulfamoyl group (preferably a furkylsulfamoyl group having 1 to 2Q carbon atoms, a 7-lysul7-ammoyl group having carbon aj to 0), a carbamoyl group (preferably a carbon number /
-,20 alkylcarba% A' group% 7-arylcarpamoyl group having 6 to 0 carbon atoms), acyloxy group (preferably one with carbon number/-,20), amino group (unsubstituted amine, preferably Secondary or tertiary substituted with an alkyl group having 1 to 20 carbon atoms, or a 7-aryl group having 6 to 20 carbon atoms
7-mino group), carbonate ester group (preferably carbon number /
N20 alkyl carbonate group, carbon number t to coO aryl carbonate group), sulfonyl group (preferably furkylsulfonyl group having 1 to 20 carbon atoms, 7-arylsulfonyl group having 4 to 10 carbon atoms), sulfinyl group (preferably a furkylsulfinyl group with carbon number/~coO, carbon number 6
~2° 7-arylsulfinyl group).

Examples of the ring-forming compound in which R5 and R are bonded include cyclopentane, cyclohexane, cycloheptane, cyclopentene, cyclohexadiene, cyclohebutadiene, indane, norbornane, nor6lunene, pyridine, etc. It may have.

Further, the total number of carbon atoms in R%R%R%R is preferably from / to 10, and it is preferable to substitute the following, and among those represented by X, an OH group is more preferable.

It is preferable that at least one of R%R and R%R is other than a hydrogen atom, and it is more preferable that X is an OH group and R%R is a hydrogen atom.

Preferred specific examples of the compound represented by the general formula (II) are shown next, but the scope of the present invention is not limited thereto.

11-/[-j ■-1 11-. 4[-J[-7 ■-≠ ■-r 1-#[-/J [-10il-/Hiroshi17-//l-/! 1-/ko 11-/4■-/7[-
2/ 1l-illll-λλ 1st 1[-/ta [[-,2J■-koo
11-λ≠71-m2jlI-kota■-koAl1-30 [-,2711-J/■-λr 1-3ko11-J
,! fJ-, 1711-J Hiroshi
([−311−3! ) is preferably contained in an amount of /x10-5 mole to !x70-2 mole per 7 moles of silver halide, etc./x1o-5 mole to λ
A preferable addition amount is in the range of xIO moles.

Further, the compound represented by the general formula (n) is silver halide 1
It is preferable to contain from 10-5 mol to 10-' mole, especially from 10-' to 10-' mole! ×
A preferable addition amount is in the range of 10 moles.

When these compounds of general formulas (I) and (II) are incorporated into a photographic light-sensitive material, they may be incorporated into aqueous solutions if they are water-soluble; ethyl)
It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as a ketone (eg, acetone).

When added to a silver halide emulsion solution, it can be added at any time from the start of chemical ripening to coating, but it is preferable to add it after chemical ripening, especially when the coating is prepared for coating. It is preferable to add it to the liquid.

There are no particular restrictions on the halogen composition of the silver halide emulsion used in the present invention, as long as it has high image contrast and high blackening density. For example, silver chloride, silver bromide,
Silver chlorobromide, silver iodobromide, silver iodochloride, silver iodochlorobromide, etc. are used.

The method for preparing the silver halide emulsion used in the present invention is described in "chimie et al." by P. GIafkides.
Physique PhotographyJ(
Published by Pau1Monte1 37 years), G, F, Du
Written by ffin1'-Photographic Emu
lsion ChemIstryJ (The Foca
I Press, /17J), V, L.

“Making” by Zelikman et al.
andCoating Photographic
Emuls[onJ(The Focal Pres.
The method described in U.S. Patent No. 1, 2, 0, 07, 02
It can be prepared by using the conversion method described in the specification of No. 0, etc., or the core/shell emulsion preparation method described in British Patent No. 1.0.27, 1416.

As a method of reacting the water-soluble silver salt (silver nitrate aqueous solution) and the water-soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used.

As one type of simultaneous mixing method, a method of keeping the pAge constant in the liquid phase in which silver halide is produced, that is, a controlled double jet method can also be used. .

It is also possible to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetrasubstituted thiourea. In the controlled double jet method and the secondary grain formation method using a silver halide solvent, the crystal shape is regular. It is easy to make a silver halide emulsion with a narrow grain size distribution.

The silver halide grains in the photographic emulsion used in the present invention are
Although it is possible to have a relatively wide grain size distribution, it is preferable to have a narrow grain size distribution, and especially for silver halide grains, the size of the grains that account for 0% of the total grain size is the average grain size. It is preferable that the emulsion is within 0% of the size (such an emulsion is generally called a monodisperse emulsion).

The silver halide grains used in the present invention are preferably fine grains (for example, 0.7 μm or less), and are WKO.

It is preferable that the value is less than or equal to .mu.

Silver halogenide grains in photographic emulsions have regular crystal bodies such as cubes and octahedrons.

It is also possible to have irregular crystals such as spherical or plate-shaped, or a composite of these crystal shapes.

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

Formed separately. Two to one or more halogenated emulsions may be mixed and used.

In the silver halide emulsion used in the present invention, cadmium salt,
A sulfite salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, etc. may be present.

The silver genide emulsion used in the present invention has been chemically sensitized. In addition to gold sensitization, sulfur sensitization, ring element sensitization, and noble metal sensitization methods can be used in combination.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a gold complex. There is no problem in containing noble metals other than pure metals, for example, complex salts of platinum, palladium, iridium, etc. Specific examples include U.S. Patent x, tttpr,
It is described in Oto No., English Painting Patent No. 4/r, Ot No. 1, etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. A specific example is U.S. Pat. No. 3,741. RIlAp issue,
Same, No. 271.9117, Same, 2, l110, A
,! '5' issue, same co, 721,641, same! ,! 0
/ ,, No. 113, same J, t! It is described in the No. t, Yrt issue and is a friend.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof are given in US Pat.

pr'y, rro, a, rig, tyr, co.

913.40P, Ko, 213,610, -1t ≠
, No. t37.

Furthermore, Jin's silver halide emulsions have increased sensitivity and are sensitive to the desired wavelength range! 1. ′J:f: can also be optically sensitized for the purpose of increasing compatibility. As a method for optical sensitization, sensitizing dyes such as cyanine dyes and merocyanine dyes are used alone or in combination to effect spectral sensitization and superchromatic sensitization.

These techniques are described in U.S. Patent No. 2. trr, r4
No. t1, No. 2.21, No. 3, No. 3.327,
No. 060, No. J, Adz, No. A3s, MJ, j
, 2r, FJ41 issue, Machikosho 413-123 issue, same μ
μ-/4'OJO number, sign opening Shoj, t-! It is written in Koro issue etc.

The photographic emulsion used in the present invention may contain a foaming compound for the purpose of preventing fogging during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing the overall photographic performance. . Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. ! ! J. Benzotriazoles, 2.

Trobenzotriazoles, Mercaptonato 2zole M
(7-phenyl-!-mercaptotetrazole on ¥!p), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthione; azaindenes, such as triazaindenes,
Tetraazaindenes (with hydroxyl substitution (')
s' * 3a + 7) tetraazaindenes)
, hantaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Many compounds known as antifoggants or stabilizers can be added.

Among these, preferred in poetry are benzotriazoles (eg, nermethylbenzotriazole) and nitroindazoles (eg, !-nitroindazole). Finally, these compounds may be included in the treatment liquid.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethyl hydantoin, etc.), dioxane derivatives (co, 3-dihydroxy dioxane, etc.) etc.), activated vinyl compound (/, J, J-) lyacryloyl-hexahydro-3-triazine, /J-
vinylsulfonyl-2-pronol, etc.), active halogen compounds (29 μm dichloro-6 dihydroxy-S-
triazine, etc.), mucodecogenic acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

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

For example, saponins (steroids), alkylene oxide conductors (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene Non-ionic substances such as glycolalkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alcohol esters of sugars, etc. Surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzenesulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates , sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids;
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides; complexes such as alkyl amine salts, aliphatic or aromatic bronchial ammonium salts, pyridinium, and imidazolium. Cationic surfactants such as cyclic bronchial ammonium salts and aliphatic or hetero-Rk containing phosphonium or sulfonium salts can be used.

In particular, the surfactants preferably used in the present invention are polyalkylene oxides described in Japanese Patent Publication No. 72, and having a molecular size of Htoo or more.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

As the treatment N solution used in the present invention, a dihydroxybenzene-based developing agent is used as a developing agent, and a p-type developing agent is used as an auxiliary developing agent.
It is preferable to use an aminophenol-based developing agent or a 3-pyrazolidone-based developing agent.

The main dihydroxybenzene-based development systems used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, co, 3-dichlorohydroquinone, co, 3
-dibromohydroquinone, .co,j-dimethylhydroquinone and the like, among which hydroquinone is particularly preferred.

Examples of /-phenyl-3-pyrazolidone or its derivatives as an auxiliary developing agent include /-phenyl-3-pyrazolidone, /-phenyl-kutukudimethyl-3-pyrazolidone, l-phenyl-hiro-methyl-guhydroxymethyl. -3-pyrazolidone, l-phenyl-≠, Hiro-dihydroxymethyl-3-pyrazolidone, l-phenyl-!
-Methyl-3-pyrazolidone, /-p-aminophenyl-pyrazolidone, Hiro-dimethyl-3-pyrazolidone, /-p-tolyl-μ1 μm dimethyl-3-pyrazolidone, and the like.

Examples of p-aminophenol auxiliary developing agents include N-methyl-p-aminophenol, p-aminephenol, N
-(β-hydroxyethyl)-p-aminophenol,
Examples include N-(4L-hydroxyphenyl)glycine, coatatyl-p-aminophenol, and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferred. .

Dihydroxybenzene type developing agent is usually 01 Oj mol/
Preferably, it is used in an amount of l to o, r mol/l. ,
In addition, when using a combination with dihydroxybenzenes to/-phenyl-3-pyrazolidones or p-amino-phenols, the former to, or mol/l, S-0, J
'mol/1. It is preferred to use the latter in the following amounts: t''0-ot mol/.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfite can be used in an amount of 0.3 mol/l or more, but if too large a quantity is added, it will precipitate in the developer and cause gold contamination, so the upper limit is preferably 0.2 mol/l.

The developer of the present invention may contain a tertiary amine compound, particularly a compound described in US Pat. No. 2, No. 2, as a development accelerator.

In the developer of the present invention, in addition to H buffers such as boric acid, star sand, tribasic sodium phosphate, and tribasic potassium phosphate, pH buffers described in Fukuoka Shotota 3133 may be used. can.

Potassium bromide 1. Development inhibitors such as potassium iodide; organic core agents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethyl formamide, methyl cellosolve, hexylene glycol, ethanol, methanol I! - indazole compounds such as ditroindazole, λ-mercaptobenzimidazole-j-sodium sulfonate,! - benzene such as methylbenztriazole) IJ anti-cazori or black pepper inhibitor such as azole-based compounds; may be used as a whole; when using compounds such as troindazole, dihydroxybenzene-based development Generally, it is dissolved in advance in a separate part from the part containing the main drug and sulfite preservative, and when used, the painted part is mixed and water is added. Furthermore, if the part where j-nitroindazole is dissolved is made alkaline, it will be colored yellow and will be convenient to handle.

Furthermore, a toning agent, a surfactant, a water softener, a hardening agent, etc. may be included as necessary. The pH of the developer is preferably one with a high pH of 2 or more, more preferably,
J-, /2, j.

As the fixing agent, those having compositions that are used in one role can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminilla-A salt such as aluminum sulfate, light bread, etc. as a hardening agent. Here, the amount of water-soluble aluminum salt is usually O~J, Of! At/l. In addition, as an oxidizing agent, ethylenediaminetetraacetic acid Fe (
III) Complex salts may be used.

The processing temperature is usually selected between /r'c and ro'c, but it may also be lower than 10C or above JO6C2j.

It is preferable to use an automatic processor for the processing of the present invention, but in that case, the total time from loading the photosensitive material until it comes out through the steps of development, fixing, washing, and drying is 0 seconds to 7 seconds. . Negative gradation photo with sufficient high contrast even in a short time of 20 seconds ￥fv! E is obtained.

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

Example 1 Silver nitrate aqueous solution, potassium bromide, potassium iodide aqueous solution,
In the presence of ammonia, the average particle size was
, 2 micron monodispersed cubic silver iodobromide emulsion (silver iodide z
, Omolti, silver bromide S, Omolti).

After chemical ripening, this silver iodide emulsion was sulfur sensitized by adding 1 mole of sodium thiosulfate (J x 10' mol Ag).
-di(3-sulfopropyl)-terether-oxacarbocyanine sodium salt" per 7 moles of silver.
Spectral sensitization was performed by adding molar amount.

Furthermore, as a stabilizer ≠-hydroxy-6-methyl-/,
Using J, Ja, 7-titrazaindene as a coating aid, the following compounds and saponin, and as a vinyl sulfone curing agent, CH2=CI(So□CH2C0NH(CH2door cabinet CO)
CH25o□C1(=CH2(n=J,j), sodium polystyrene sulfonate as the thickener, 0.30777m'' of a dispersion of polyethyl acrylate as the trunk polymer, and the following compound O0≠Q
fi/m”.

Additionally, 0.0% of /-phenylmercaptotetrazole was added as an anti-fouling agent. After adding 1 mole of silver to each /f, the following compound was added as a hydrazine compound, t, oxto
'Added 17 mole AP.

Furthermore, the compound of general formula (It) was added in the amount shown in Table 7.

Furthermore, as a comparative sample, an emulsion was prepared in which hydroquinone was added to the compound of general formula (n).

The protective layer includes gelatin, sodium dodecylbenzenesulfonate, silicone oil, 7 (Sakai surfactant, colloidal silica, polyethyl acrylate dispersion, polymethyl methacrylate (particle size λ, !μ) matting agent, and polystyrene. Gelatin aqueous solution consisting of sodium sulfonate thickener as gelatin coating amount / , 491 /
m2, and emulsion as coating silver amount! ,6
The emulsion layer and the protective layer were coated at the same time so that the ratio was 9/1yh2.

Two samples were prepared for each of these samples, and one sample had a sapphire needle of 0.02 mm for the purpose of pressure sensitization testing. A load was applied to the shoulder φ, ≠, 6, r, 10f, and a suction was applied. The other 7 sheets are for the purpose of measuring the sensitivity of sensitometry, r.I prepared one with nothing attached to it.

These two samples were exposed to tungsten light at 30CJO for 5 seconds through an optical wedge for sensitometry, then developed for Jr0CJO seconds with a developer having the following composition, fixed, washed with water, and dried. (For the development process, an automatic processor FCx-660F manufactured by Fuji Photo Film Co., Ltd. was used.) The results are shown in Table 7.

0 sensitivity evaluation method fog+density on the characteristic curve 1. The sensitivity was read from the exposure amount at point j.

Evaluation method of Or From the point of fog + density O, j of the characteristic curve, fog + density J
, 0 points were connected with a straight line and the r value was determined from the slope of this straight line.

The value γ (exposure amount at the location of logcfog+density 0.3) corresponds to image quality and is preferably 10 or more.

Evaluation method for 0-scratch sensitization The degree of smack-scratch sensitization was visually observed and evaluated in a portion having a slight pack-ground concentration corresponding to the foot of sensitometry.

As the load of the needle for making sushi scratches was increased, the load at which sushi scratch sensitization began to be observed was recorded. The larger this value is, the stronger the resistance to scratches is, and it is preferably 6P or more.

The results shown in Table 2 show that the samples using the compounds of the present invention have extremely improved sensitivity and sensitization, with almost no decrease in sensitivity and r.

In addition, hydroquinone was used as a comparative compound with the general formula (II
It can be seen that the sample of the compound of the present invention used in Example 1 had a smaller degree of sensitization and lowered sensitivity than the sample of the present invention, indicating that the compound of the present invention is superior.

Example λ A silver chloroiodobromide emulsion (silver iodide 0.0.
1 molti, silver bromide 30 mol%) was prepared. This silver chloroiodobromide emulsion contains (NH4)3Rhcg as a rhodium salt,
was added to the halogen aqueous solution so that /X10-7%/-E: kAg was contained. At the same time, K as an iridium salt
3 I rα6 was added to the halogen aqueous solution to contain 4 cxio mol/Ag 1 mol. This halogen aqueous solution and a silver nitrate aqueous solution were mixed for about 10 minutes to prepare a monodisperse cubic emulsion with an average grain size of 0.2 μm.

After washing and desalting this emulsion, add sodium thiosulfate j×l0-5
After sulfur sensitization was carried out by adding 1 mole of AP, gold sensitization was carried out by adding 1 mole of potassium chloroolet) (X10-') AP.

This emulsion was added with t-(a-hydroxyethoxyethyl)-J-(pyridine-coyl)-z-((
J-sulfobutyl-! -chloro-2-penzoxazolinidene) ethylidenefuucochiohydantoin potassium salt t-3 x 1O mol/AP 1 mol, as a stabilizer -hydroxy-4-methyl-/, J, Ja, 7-titrazainde 7f/, j'j! , hydroquinone as J P s
Resorcinaldoxime JP, /-phenyl-! -Mercaptotetrazole was added to each volume of 7 moles of silver.

Furthermore, the following compounds and saponin were added as coating aids:
α:'H□So2CH=CH2(Hg-2,3), sodium polystyrene sulfonate as a thickener, and a dispersion of polyethyl acrylate as a latex polymer were added.

Furthermore, as a hydrazine compound /, 2×10 mol 1 mol Ag was added.

Further, the compound of general formula (If) or no-hydroquinone was added in the amount shown in Table 1.

The protective layer includes gelatin, sodium dodecylbenzenesulfonate, silicone oil, fluorosurfactant, colloidal silica, polyethyl acrylate dispersion, polyacrylamide (molecular weight wa=zooo), polymethyl methacrylate (particle size 2,! The gelatin aqueous solution consisting of the matting agent of μ) and the thickener of sodium polystyrene sulfonate was adjusted so that the coating amount of gelatin was /, A / -, and the emulsion was adjusted to have a coating silver amount of 3.6 / -. The layer and the protective layer were applied simultaneously.

These samples were stained in the same manner as in Example 7, exposed and developed, and then evaluated in the same manner as in Example 7.

The results are shown in Table-2.

The results in Table 2 show that even in silver chloroiodobromide emulsions sensitized with silver sulfur, the samples using the compounds of the present invention have extremely improved sensitization without impairing sensitivity or r. .

Furthermore, compared to the comparative compound hydroquinone, the compound of general formula (n) of the present invention exhibits less deterioration in sensitivity and r, and has improved sushi scratches.

Claims (1)

[Scope of Claims] A surface latent image type silver halide emulsion layer is provided on a support, and the emulsion layer and/or other constituent layers contain the following general formula (I
) and the following general formula (I
A silver halide photographic material containing a compound represented by I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic group or an aromatic group, and R_
2 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxydicarbonyl group, and G_1 represents a carbonyl group, a sulfonyl group, a sulfoxy group, ▲ Numerical formula, chemical formula, table, etc. ▼ group or iminomethylene group, A_1, A
Both of _2 represent a hydrogen atom, one of which is a hydrogen atom, and the other of which is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents OH or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^3 and R^4 are hydrogen atoms, alkyl groups, Represents an aryl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbonyl group, arylcarbonyl group or carbamoyl group, R^5, R^6
, R^7 and R^8 each represent a hydrogen atom or a substitutable group.