JPH01200245A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material which is super-hard- contrasted by a developing soln. of <=11.2pH by incorporating a specific compd. into a silver halide emulsion layer or other hydrophilic colloid layer. CONSTITUTION:The negative type silver halide photographic sensitive material which is super-hard-contrasted by the developing soln. having <=11.2pH is obtd. when >=1 kinds of the compds. respectively expressed by general formulas I, II are incorporated into the silver halide emulsion layer or hydrophilic colloid layer on the base of a photosensitive material. In formula I, Z': a nonmetallic atom group necessary for forming 5-, 6-membered heterocycles, R': an aliphat. group, X: the structure expressed by formula III, Q: a nonmetallic atom group necessary for forming 4--12-membered nonarom. hydrocarbon rings, Yn: n-pieces of counter ions for charge balance; In formula II, X: a divalent heterocycle contg. N, O, Ce, and S, A: a divalent combination group for atoms and atom groups of C, N, O, and S, B: an amino group and N-contained heterocycle, (n): 0 or 1, M: an H atom., alkali metal, alkaline earth metal, quaternary ammo nium salt, quaternary phosphonium salt, amidino group or group which is cloven under an alkaline condition.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic material and a method of forming an ultra-high contrast image using the same, and in particular to a silver halide photographic material used in a photolithography process. It concerns photographic materials.

(Prior art) In the field of graph ink and arc, in order to improve the reproduction of continuous tone images using halftone images or the reproduction of line images, images exhibiting photographic characteristics of ultra-high contrast (especially commas of 10 or more) are used. A forming system is required.

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and contains sulfite as a preservative so as not to inhibit its infectious development properties. is used in the form of an adduct with formaldehyde, and the concentration of free sulfite ions is extremely low (usually less than 0.1 molf 1).

Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

U.S. Pat. No. 4,224,401 and U.S. Pat.
, 168,977, 4,166.742, 4,311,781, 4.272,606, 4,211.857, 4.243,739 There is a method using a hydrazine derivative described in et al. According to this method, photographic properties with ultra-high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developer, the stability of the developer against air oxidation is better than that of the lithium developer. A dramatic improvement in comparison.

However, in order to form ultra-high contrast images using hydrazine derivatives, pH Hll must be 2 or higher, and as a result, the developing agent is easily oxidized, and the pH also fluctuates due to absorption of CO2 in the air. Easy to do,
The drawback was that it was difficult to obtain stable photographic properties. Therefore, in order to maintain the stability of the developer, there has been a desire for a method that allows ultra-high contrast images to be obtained at a pH of 2 or less and in the presence of a high concentration of sulfite.

There is a strong desire for means to promote high contrast with hydrazine, and JP-A No. 61-167939 discloses phosphonium salt compounds, JP-A No. 61-198147 discloses disulfide compounds, and JP-A No. 60-140340 discloses amines. type compounds are disclosed as contrast enhancing agents. However, even when these compounds are used, it is difficult to promote high contrast at pH 11.2 or lower.

On the other hand, when trying to obtain a photosensitive material for bright room use with a low degree of anger using a hydrazine compound, for example, silver halide photosensitive materials containing water-soluble rhodium salts are disclosed in JP-A-60-83038 and JP-A-60-162,246. Disclosed. However, if enough rhodium is added to reduce the sensitivity,
The high contrast caused by the hydrazine compound was inhibited, and a desired sufficiently high contrast image could not be obtained.

Therefore, a means for promoting high contrast has been desired, and in particular, a method for achieving high contrast at pH 11.2 or lower has been desired.

OBJECTS OF THE INVENTION The object of the present invention is to provide a silver halide photosensitive material that achieves ultra-high contrast when the pH of the developer is 11.2 or less. The aim is to provide a frame with ultra-high contrast silver halide photosensitive materials that can maintain high performance.

Structure of the Invention The above object of the present invention is to have at least one silver halide emulsion layer on a support, and to contain at least a compound of the following general formula [I] in the emulsion layer or other hydrophilic colloid layer. This was achieved by a negative-working silver halide photosensitive material characterized by containing at least one compound represented by the following general formula [■].

General formula (1) In the formula, Zl represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle. This heterocycle may further be fused with an aromatic ring or a heterocycle.

R1 is an aliphatic group, and X is -C- or -N-.

Q represents a nonmetallic atomic group necessary to form a 4- to 12-membered non-aromatic hydrocarbon ring or a non-aromatic heterocycle. However, among the substituents of R1, W fA W and Q of Zl,
At least one contains an alkynyl group. Furthermore, R1, Z
A small number of l and Q (one of which may have an adsorption promoting group to silver halide. Y is a counter ion for charge balance, and n is the number necessary for charge balance. be.

To explain in more detail the nucleating agent represented by the general formula CI), the heterocycle completed by z' is, for example, quinolinium, benzimidazolium, pyridinium, thiazolium, selenazolium, imidazolium, tetrazolium, indolenium, pyrrolinium, Mention may be made of phenanthridinium, isoquinolinium, and naphtopyridinium nuclei. Zl may be substituted with a substituent, and examples of the substituent include an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, and an alkylthio group. group, ruthio group, acyloxy method, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group,
Cyano group, ureido group, urethane group, carbonate ester group,
Examples include hydrazine group, hydrazone group, and imino group. As the substituent for Zl, for example, at least one substituent is selected from the above substituents, but in the case of two or more substituents, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents.

Furthermore, as a substituent for Zl, a heterocyclic quaternary ammonium group completed with Zl via a suitable linking group Ll may be included. In this case, it takes a so-called dimer structure.

Preferred examples of the heterocyclic core completed with Zl include quinolinium, benzimidazolium, pyridinium, acridinium, phenanthridinium, naphtopyridinium, and isoquinolinium cores. More preferred are quinolinium, naphtopyridinium, and benzimidazolium nuclei, and most preferred is quinolinium.

The aliphatic group for R1 is preferably an unsubstituted alkyl group having 1 to 18 carbon atoms or a substituted alkyl group having 1 to 18 carbon atoms in the alkyl moiety. Examples of the substituent include those described as the substituent for Zl.

R1 is preferably an alkynyl group, most preferably a propargyl group.

Q is an atomic group necessary to form a 4- to 12-membered non-aromatic hydrocarbon ring or non-aromatic heterocycle.

These rings may be further substituted with the groups mentioned for the substituents of Zl.

Examples of non-aromatic hydrocarbon rings in which X is a carbon atom include rings such as cyclopenkune, cyclohexane, cyclohexene, cyclohebutane, indane, and tetralin.

Non-aromatic heterocycles include those containing nitrogen, oxygen, sulfur, selenium, etc. as heteroatoms, and for example, when X is a carbon atom, tetrahydrofuran, tetrahydropyran, butyrolactone, pyrrolidone, tetrahydrothiophene, etc. A ring can be given. When X is a nitrogen atom, examples include rings such as pyrrolidine, piperidine, pyridone, piperazine, perhydrothiazine, tetrahydroquinoline, and indoline.

The ring nucleus formed by Q is preferably when X is a carbon atom, especially cyclopenkune, cyclohexane,
These include cycloheptane, cyclohexene, indane, tetrahydropyran, and tetrahydrothiophene.

The alkynyl group in which at least one of the substituents for R' and Z' and the substituent for Q corresponds to 3 has already been described in part, but to explain in more detail, it is preferable that the alkynyl group has 3 carbon atoms. 2 to 18 groups, such as ethynyl group, propargyl group, 2-fuJ-nyl group, 1-methylpropal-t'JLJ5.1゜l-dimethylpropargyl group, 3-butynyl group, 4-pentynyl group, etc. be.

Furthermore, these may be substituted with the convex substituent mentioned as a substituent for Zl.

As these alkynyl groups, propargyl groups are preferable, and it is particularly preferable that R1 is a propargyl group.

The adsorption promoting group to silver halide that R', Q and Zl substituents may have is preferably one represented by X'-(-L'-)-.

Here, XI is an adsorption promoting group to silver halide, and [
41 is a divalent linking group. m is 0 or 1. Xl
Preferred examples of the adsorption-promoting group to silver halide represented by the formula include a thioamide group, a mercapto group, and a 5- or 6-membered nitrogen-containing heterozygote group Q)J.

These may be replaced by those mentioned as substituents for Zl. The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.).

Examples of the mercapto group of ,3
, 4-oxadiazole, etc.) are preferred.

The 5- to 6-membered nitrogen-containing silane ring represented by ×1 is composed of a combination of nitrogen, oxygen, sulfur, and carbon,
Preferably, those that generate iminochemicals include benzotriazole and aminothiatriazole.

The divalent linking group represented by Ll is C1N, S
, O. Specifically, for example, an alkylene group, an alkenylene group,
Alkynylene group, arylene group -o-1-S-1-N
I(-1-N-1-CO-1SO2 (these groups may have a substituent), etc. alone or in combination.

■ -NH3O! NH-1-(alkylene)-C-NH-1
-(arylene)-soz NH-1 -(arylene)-NHCNH-1 -(arylene)-CNH- is preferred.

Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanine ion BF, - Examples include ion, PF, -ion, etc.

Among the compounds represented by General 2 (1), those having a group that promotes adsorption to silver halide are preferred, particularly when 25X' is a thioamide group, azur group, or a heterocyclic mercapto group. preferable.

Examples of these compounds and their synthesis methods are disclosed in, for example, Japanese Patent Application No. 6
No. 2-17,984 and the patents or documents cited therein.

Specific examples of compounds represented by general formula (1) are listed below, but the present invention is not limited thereto.

□ C11□CE=CH spoon Cll1C-Cll (+-4) 噸 CIl□CmiC1+ CII□C=CH (+-81 CII□C=CI+ (+-9) CII□C3CH CIl, CmiCI+ CII□C3CH ! 11 cozc=c.

(+ -14) CII□C=C11 c++tc=c.

CII□CECH (1-18> In the present invention, when the compound represented by general formula (1) is contained in a photographic light-sensitive material, alcohols (e.g. methanol, ethanol), steres (e.g. ethyl acetate), ketones It may be used as a water-miscible 411 i8 medium such as (eg, acetone), or if it is water-soluble, it may be added to the aqueous colloid solution as an aqueous solution.

When added to a photographic emulsion, it is preferably added at any time from the start of aging to before coating, or after the completion of chemical ripening.

In the present invention, the agent represented by the general formula CI] may be contained in the hydrophilic layer adjacent to the silver halide emulsion layer, but it is preferably contained in the silver halide emulsion layer. The amount added depends on the properties of the silver halide emulsion used, the chemical structure of the formulation, and the development conditions and can vary over a wide range, but is approximately 1 liter per mole of silver in the halogenating agent.
A range of X10-6 moles to about 10" moles is useful in practice, with a preferred range of about 1X10-.' moles to about 1 x 1 mole per mole of root.

The compound represented by the general formula (II) according to the present invention will be described in detail: General formula (II) MS(-X+, 1A-B) The compound represented by the above general formula (II) will be described in further detail.

The heterocycle of X may be a 5- or 6-membered heterocycle containing at least one of nitrogen, oxygen, selenium, or sulfur, and may be fused with a carbon aromatic ring or a heteroaromatic ring. The heterocycle is preferably aromatic, such as tetrazole, triazole, thiadiazole, oxadiazole, selenadiazole, imidazole, thiazole, oxazole, henzimidazole, henzthiazole, henzoxazur, henzselenazole, pyrimidine, etc. be. Among these, tetrazole and thiadiazole are particularly preferred.

These heterocycles also include nitro groups, halogen atoms (e.g. chlorine atoms, bromine atoms, etc.), mercapto groups, cyano groups,
Substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, propyl group, t-butyl group, cyanoethyl group, methoxyethyl group, methylthioethyl group, etc.)
, aryl group (e.g. phenyl, 4-methanesulfonamidophenyl J5.4-methylphenyl group, 3,4-
dichlorophenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. evahensyl group, 4-methylbenzyl group, phenethyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, etc.) ), aryloxy groups (e.g. phenoxy group, 4-methoxyphenoxy group, etc.), alkylthio groups (e.g. methylthio group,
ethylthio group, methoxyethylthio group), aryldio group (e.g. phenylthio group), sulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (e.g. unsubstituted carbamoyl group, methylcarbamoyl group) , phenylcarbamoyl group, etc.), sulfamoyl group (e.g. unsubstituted sulfamoyl group, methylsulfamoyl, phenylsulfamoyl group, etc.), carbonamide group (e.g. acetamide group, benzamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, henzenesulfonamide group, p-toluenesulfonamide group, etc.), acyloxy group (e.g. acetyloxy group, hendyloxy group,
etc.), sulfonyloxy groups (e.g. methanesulfonyloxy groups, etc.), ureido groups (e.g. unsubstituted ureido groups, methylureido groups, ethylureido groups, phenylureido groups, etc.), thioureido groups (e.g. unsubstituted thioureido groups). , methylthioureido group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.), heterocyclic group (e.g. 1-morpholino group, 1-piperidi/W, 2-pyridyl group, 4-pyridyl group, 2-thienyl group) 1-pyrazolyl group, -imidazolyl group, 2-tetrahydrofuryl group, tetrahydrothienyl group, etc.), oxycarbonyl group (e.g. methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (e.g. methoxycarbonylamino group) group, phenoxycarbonylamino group,
2-ethylhexyloxycarbonylamino group, etc.),
Amino group (e.g. unsubstituted amino group, dimethylamino group,
methoxyethylamino group, anilino group, etc.), carboxylic acid or its salt, sulfonic acid or its salt, hydroxyl group, etc.

The divalent linking group of A is a divalent linking group consisting of an atom or atomic group selected from carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, such as -5-1-〇-1-N -3 R6 -5OtN-1-N-502-1-N-C-N-511
I I Ra Rs Rb R71l Rs Rq R16 R2, R3, R4, R1, R6, R7, RI11 R9 and R1° are each a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, propyl group, n -butyl group, etc.), substituted or unsubstituted aryl group (e.g., phenyl group, 2-sotylphenyl group, etc.)
, a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), or a substituted or unsubstituted aralkyl group (eg, Hensyl group, phenethyl group, etc.). ), straight or branched alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, ■ = methylethylene group,
etc.), straight or branched alkenylene groups (e.g. vinylene group, ■-methylvinylene group, etc.), straight chain or branched aralkylene groups (e.g. hexylene group, etc.), straight chain or branched alkylene groups (e.g. hexylene group, etc.), For example, -CH-C=C
-CJ-1-q, etc.), arylene groups (eg, phenylene, naphthylene, etc.), and the like. The above groups represented by A may further be combined in any desired manner to form a linking group. The amine group B may have a substituent, and is preferably represented by the general formula (III).

General formula (I[l) (In the formula, R1I and R1t may be the same or different, and each is a hydrogen atom, substituted or unsubstituted, and has 1 to 3 carbon atoms.
0 alkyl group, alkenyl group or aralkyl group, and these groups are linear (for example, methyl group, ethyl group,
n-propyl group, n-butyl group, n-octyl group, allyl group, 3-butenyl group, hensyl group, 1-naphthylmethyl group, etc.), branched (e.g. isopropyl group, L-octyl group, etc.), or cyclic (for example, a cyclohexyl group, etc.).

Further, R1 and R12 may be connected to form a ring, and a saturated heterocycle containing one or more heteroatoms (for example, an oxygen atom, a sulfur atom, a nitrogen atom, etc.) therein may be used. Examples thereof include a pyrrolidyl group, a piperidyl group, and a morpholino group. Further, examples of substituents for R11 and R'2 include carboxyl group, sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, and bromine atom),
Hydroxy group, alkoxycarbonyl group having up to 20 carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, hensyloxycarbonyl group, etc.), alkoxy group having up to 20 carbon atoms (e.g. methoxy group, ethoxy group, hensyloxy group) monocyclic aryloxy groups having 20 or less carbon atoms (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy groups having 20 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.) , carbon number 20
The following acyl groups (e.g. acetyl group, propionyl group,
hendiyl group, mesyl group), carbamoyl group (e.g. carbamoyl group, N,N-dimethylcarbamoyl group,
morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,
N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), acylamino group having 20 or less carbon atoms (e.g. acetylamino group, propionylamino group, hensylamino group, mesylamino group, etc.), sulfonamide group (ethylsulfonamide group, p-
Toluenesulfonamide group, etc.), carbonamide with 20 or less carbon atoms,! 5 (e.g. methylcarbonamide group,
phenylcarbonamide group, etc.), a ureido group having 20 or less carbon atoms (for example, methylureido group, phenylureido group, etc.), and an amino group (synonymous with general formula (''XI)).

The ammonium group B may have a substituent, and is preferably represented by the general formula (rV).

General formula (TV) (Z e) p (wherein, R13, R mouth, and R15 are the above-mentioned general formula (III
), and is the same +i group as R12, and Zo
represents an anion, such as a halide ion (e.g. C
1e, Bre, ■θ, etc.), sulfonate ions (e.g. trifluoromethanesulfonate, valatoluenesulfonate, henzenesulfonate, parachlorobenzenesulfonate, etc.), sulfate ions (e.g. ethylsulfate, methylsulfate) ), perchlorate, tetrafluoroborate, etc. p represents O or 1, and is 0 when the compound forms an inner salt. ) The nitrogen-containing heterocycle B is a 5- or 6-membered ring containing at least one nitrogen atom, and these rings may have a substituent and may not be fused with another ring. You can.

Examples of the nitrogen-containing heterocycle include an imidazolyl group, a pyridyl group, and a thiazolyl group.

Examples of the alkali metal M include Na4, K', and Li+.

Examples of alkaline earth metals include CC4+, Mg'', and the like.

The quaternary ammonium salt of M has 4 to 30 carbon atoms, such as (CH3)4Ne, (CzHs)4
No, (Ca Hq) 4 Ne, Cbt (set
−(zNe(CI-13):l, CIaH:++No(
CH3)5 etc. As a quaternary phosphonium salt,
(C, t1q>aPa, CIaH*Pe(CHl)3,
C, tIscHzP*(CH3), etc.

Examples of groups that can become M=H or an alkali metal atom under alkaline conditions include acetyl group, cyanoethyl group,
Examples include methanesulfonylethyl group.

Specific examples of the compound represented by the general formula ([+)] are listed below.

O ■-3 Ku1 q■ ■-5 n-f3 H-1 H ■-8 θS N = N / (■-lO ・Hf1J ・H(IJ ■-15 T-16 ・HCl ■-17 0・HCl ■R8 U ・It(1■-19 ・It(J ■-20 0・llCN ■-22 ■-23 ■-24 ■-26 ■-27 ■-31 ・11C1 ■-32 ■-33 O ■ -34 ■-35 ■-36 n -45 (IIOCII□CIl□)JCII□CH
□511-C The optimum amount of the compound of formula (II) to be added differs depending on the type of compound, but 1. Ox 10-x ~ 0.58
/m, preferably 5. OX 10-3~0.1g/n(
It is desirable to use it within the range of . These promoters are dissolved in a suitable solvent (R20, alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

A plurality of types of these additives may be used in combination.

Further, in the present invention, a hydrazine derivative may be used in combination as a means for promoting high contrast, which is disclosed in US Pat. No. 4.47.
Examples include the hydrazine Li F form having a sulfinyl group described in No. 8,928 and the compound represented by Noshiro (X) below.

- Noshiro (X) R, -N HN H7CHO In the formula, R1 represents an aliphatic group or an aromatic group.

- In Noshiro (X), the aliphatic group represented by R1 preferably has 1 to 30 carbon atoms, particularly 1 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 sulfonamide group, or a carbonamide group.

Examples include t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group, tetrahydrofuryl group, and morpholino group.

In the general formula (X), the aromatic group represented by RI is a monocyclic or bicyclic ring group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrrolidyl group, quinoline ring,
Examples include an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a hendithiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R1 is an aryl group.

The aryl group or aromatic group of R3 may have a substituent.

Typical substituents include straight chain, branched or cyclic alkyl groups (preferably those with 1 to 20 carbon atoms), aralkyl groups (preferably monocyclic or bicyclic alkyl groups with 1 to 3 carbon atoms). ), alkoxy groups (preferably those with 1 to 20 carbon atoms), substituted amino groups (preferably those with 1 to 20 carbon atoms),
~20 alkyl group substituted), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms)
, ureido group (preferably one having 1 to 30 carbon atoms)
There are such things.

-II R1 in formula (X) may have a ballast group incorporated therein which is commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoquine group, etc. be able to.

R9 in general formula (X) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include the groups described in US Pat. No. 4,385,108, such as thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups.

Synthesis methods for these compounds are described in JP-A No. 53-20921,
No. 53-20922, No. 53-66732, No. 53
-20318 etc.

In the present invention, when the compound represented by -Noshiro (X) is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but it is preferably contained in a non-photosensitive hydrophilic colloid layer (for example, a protective layer, intermediate layer, filter layer,
It may be included in an antihalation layer, etc.). Specifically, if the compound used is water-soluble, it can be prepared as an aqueous solution.
Again j! In the case of water-soluble alcohols, esters,
As a solution of water-miscible organic solvents such as ketones,
It can be added to a hydrophilic colloid solution. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between after the end of chemical ripening and before coating. In particular, it is preferable to add it to a coating solution prepared for coating.

The content of the compound represented by the general formula (X) of the present invention is determined by the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, and the relationship between the layer containing the compound and the silver halide emulsion layer. It is desirable to determine the optimum value depending on the type of antifogging compound, etc., and testing methods for selection are well known to those skilled in the art. Usually, preferably from 10-6 mol to 1×1 O per mol of halogenated i
~1 mol, especially 10-5 to 4X10-'' mol.

-a Specific examples of the compound represented by formula <X> are shown below.

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

C2II S X-12 ■ CH.

CIl□CI1. CII□Sll Ku x-28 x-31 H Sl+ In addition, as described in U.S. Patent No. 4,478,928 and so on.

In the photographic emulsion of the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide, and silver chloride may be used as the silver halide, but silver chloride is particularly preferred. The content is preferably 50 mol% or more.

The particle size distribution may be narrow or wide.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
Regular like a tetrahedron or a rhombic dodecahedron
It may have a regular crystalline form, or it may have an irregular crystalline shape such as a spherical shape or a plate-like shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

Further, the grain size distribution of silver halide grains in the photographic emulsion is arbitrary, but may be monodisperse.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Further, the amount of these additives may be small or large depending on the intended photosensitive material.

In addition, depending on the purpose, a known silver halide solvent (for example, ammonia, Rodankali, or US Patent No. 3
No. 271157, JP-A-51-12360, JP-A-5
No. 3-82408, JP-A No. 53-1' 44319,
JP-A-54-100717, JP-A-54-15582
Thioethers and thione compounds described in No. 8 etc.) can be used.

The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, active gelatin and compounds containing sulfuric acid that can react with silver (e.g., thiosulfates, thioureas,
Sulfur sensitization method using mercapto compounds, rhodanine v4); Reduction sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); Noble metal compounds (e.g. In addition to gold complex salts, a noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as Pt, Ir, and Pd can be used alone or in combination.

The photographic emulsion of the present invention may contain various compounds for the purpose of preventing fogging during storage or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen derivatives); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptohendithiazoles, mercaptobenz; Imidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines: the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group : Thioketo compounds such as oxazolinthione: Azaindenes such as tetraazaindenes (particularly 4-hydroxy substituted tfA (1,3,3a,7)tetraazaindenes)
:Benzenethiosulfonic acid M:Benzenesulfinic acid:
A number of compounds known as antifoggants or stabilizers can be added, such as.

In the photographic material of the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using an enhancing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. Specific examples of spectral sensitizing dyes include, for example, P.

Written by Glafkidesrchemie Photogr
aphique J (2nd edition, 1957: Pau1Montel-Paris
Chapters 35-41 of ) and The Cyanine by F. M. Ilamer
and Re1ated Compounds J(I
terscience), and U.S. Patent No. 2,50
3゜776, 3,459,553, 3,177
．． No. 210, Research Disclosure
arch Disclosure) Volume 176 1764
3 (issued December 1978), Section 23 (■), Section 5, etc.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes:
Hemioxonol dyes and merocyanine dyes are useful.

The photographic material of the present invention may contain an inorganic or organic contrast agent in the photographic emulsion layer or other hydrophilic colloid layer.

For example, active vinyl compounds (1°3.5-)lyacryloyl-hexahydro-S-triazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy -5-) riazine, etc.) can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, coating prevention, slipperiness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (for example, development acceleration, high contrast, sensitization), etc. Various surfactants may be included for various purposes.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates,
polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. Nonionic surfactants such as glycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of acids: alkyl carboxylates, alkyl sulfonates, alkylhenzenesulfonates, alkylnaphthalenesulfonic acids salts, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. , carboxy group, sulfo group, phospho group, sulfate ester method, anionic surfactant containing acidic groups such as phosphate ester group, diamino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or acetic acid esters, alkylhetaines, amine oxides Ampholytic surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. Cationic surfactants can be used.

For the purpose of increasing sensitivity, increasing contrast, or promoting development, the photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary It may also contain ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, a wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, and dextran.

In order to obtain ultra-high contrast photographic characteristics using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or U.S. Pat.
It is not necessary to use a highly alkaline developer with a pH close to 10 as described in No. 9,975, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at a concentration of 0515 mol/I! Including the above, p
) (is not particularly limited and can be freely selected depending on the amount of developing agent, development inhibitor, etc., but in particular, pH
A sufficiently high-contrast negative image can be obtained with a developer having an average molecular weight of 5 to 9.0, preferably 11.2 to 9.5.

There are no particular limitations on the developing agents that can be used in the method of the present invention, such as dihydroxybenzenes (e.g. hydroquinone), 3-virapritones (e.g. 1-phenyl-3-pyrazolidone, 4゜4-dimethyl-1-phenyl- 3-pyrazolidone), aminophenols (e.g. N
-methyl-p-aminophenol) can be used alone or in combination.

In particular, the silver halide light-sensitive material of the present invention contains dihydroxybenzenes as a main developing agent and 3-3 as a protective developing agent.
Suitable for processing with developers containing pyrazolidones or aminophenols. Preferably, in this developer, dihydroxybenzenes are used in an amount of 0.05 to 0.5 mol/Il, and 3-pyrazolidones or aminophenols are used in an amount of 0.06 mol/Il or less.

Further, as described in US Pat. No. 4,269,929, the development speed can be increased and the development time can be shortened by adding amines to the developer.

The developer also contains alkali metal sulfites, carbonates,
I)H buffers such as borates, and phosphates, bromides,
It may contain a development inhibitor or an antifoggant such as an iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles). If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the above-mentioned polyalkylene oxide V4), antifoaming agents, hardening agents, and film stain prevention agents may be added. agents (for example, 2-mercaptobenzimidazole sulfonic acids, etc.).

As the fixer, one having a commonly used composition 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 aluminum salt or the like as a hardening agent.

The processing temperature in the method of the invention is usually from 18°C to 50°C.
selected between.

Although it is preferable to use an automatic processor for photographic processing, the method of the present invention allows the total processing time from the time the photosensitive material is placed in the automatic processor to the time it comes out to be 90 to 120 seconds. , sufficiently ultra-high contrast negative gradation photographic characteristics can be obtained.

In the developing solution of the present invention, JP-A-56-2 is used as a silver stain preventive agent.
Compounds described in No. 4,347 can be used. Patent application 1986-109 as a solubilizing agent added to the developer.
Compounds described in No. 743 can be used. Furthermore, as a pH buffering agent for use in developing solutions, JP-A-60-93,4
The compound described in No. 33 or the compound described in Kentoku No. 4631 can be used.

Example 1 A salt compound 11 (10.1 mol %, Br 30 mol %) was prepared using a double jet method. This silver chloroiodobromide emulsion contains (N114) JhC1 as a rhodium salt.
An aqueous halogen solution was added so that b was 5*10-6/Ag mole. At the same time, as iridium salt,
Containing 4*10-7/Ag mol of KtlrtJ6,
An aqueous halogen solution was added.

This halogen aqueous solution and silver nitrate aqueous solution were mixed at 45° C. for 60 minutes to prepare a monodisperse cubic emulsion with an average grain size of 0.25 μm.

After washing and desalting with water, this emulsion was washed with 1×l of sodium thiosulfate.
O''S mol/Ag mol was added, and gold enhancement with potassium chloroaurate was added at 1X10-' mol/Ag mol.

These emulsions contain 1-(2-hydroxyethoxyethyl)-3-(pyridin-2-yl)-5-(
(3-sulfobutyl-5-chloro-2-peizoxazolinidene)ethylidene]-2-thiohydantone potassium salt at 3X10-' mol/Ag 1 mol as a stabilizer, 4
-Hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added at 1.5 g per mole.

Furthermore, as a coating aid, the following compounds and saponin are added to C+? 1ls3CON CHzCHzSO3NaHz CI+□=C11S02CH, C0NI-1 (C112
), N11COCI(!5(hcIl=c)+2(n=
2. ．． 3) Sodium polystyrene sulfonate was added as a thickener, and a dispersion of polyethyl acrylate was added as a Latinx polymer.

Furthermore, from Noshiro [I], I-8 and l-14, respectively.
, r-15, and l-25 were added as shown in Table 1.

As the protective layer, an aqueous gelatin solution consisting of gelatin, sodium dodecylbenzenesulfonate, colloidal silica, a dispersion of polyethyl acrylate, a matting agent of polymethyl methacrylate, and a thickener of sodium polystyrene sulfonate was used as the coating amount of gelatin. , 1.6g/m
In addition, the emulsion was coated with a silver amount of 3.6 g/
The emulsion layer and the protective layer were simultaneously coated so that the thickness of the layer was m.

Each of these samples was tested with tungsten light at 3200'
After exposing for 5 seconds through an optical wedge for sensitometry, developing for 30 seconds at 38°C with a developer (A) having the following composition,
Fixed, washed with water, and dried.

(For the developing process, use the automatic developing machine FG manufactured by Fuji Photo Film ■.
-660F was used. ) [Developer (A) formulation] Hydroquinone 35.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 4.5g Potassium triphosphate
74.0g potassium sulfite
90.0g Ethylenediaminetetraacetic acid disodium salt 1.0g Potassium bromide 3.0g 5-Methylbenzotriazole 0.6g3
-Diethylamino-1-propanol 15.0g Add water
ll1 (adjusted to pH=10.6) It can be seen that the compound of the general formula [I] of the present invention increases the contrast.

Compound n-7 of the present invention was added as shown in Table 2 to the film holes prepared in Example 1.
, ■, ■, and ■ were prepared and processed in the same manner as in Example 1, and the gradation (G) and fog were measured.

As shown in Table 2, by using the compound of the present invention, 01
It is possible to obtain ultra-hard tones of 0 or more.

Example 3 In the same manner as in Example 1, only the halogen composition was changed as shown in Table 3, and grain formation was carried out to prepare an unripened silver halide emulsion.

To this emulsion, 1.5 g of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added as a stabilizer.
Added per mole of I.

Coating aids, hardeners, and thickeners were added in the same manner as in Example 1.
Compounds shown in Table 3 were selected from -Noshiro (I) and -Noshiro (II) and added.

As a protective layer, an aqueous gelatin solution consisting of gelatin, sodium dodecylhenzenesulfonate, colloidal silica, a dispersion of polyethyl acrylate, a matting agent of polymethyl methacrylate, and a thickener of sodium polystyrene sulfonate was used, with a coating amount of gelatin. as 1.6 g/
Also, the emulsion was adjusted so that the coated silver amount was 3.
The emulsion layer and the protective layer were simultaneously coated at a coating weight of 6 g/rrr.

These samples were treated in the same manner as in Example 1, and G and fog were measured.

It can be seen that even if the halogen composition is changed, the compound of the present invention provides ultra-high contrast of 010 or higher even if the image is not matured.

[Table 3] Example 4 General formula of film 6 of Example 2 [Samples were prepared as shown in Table 4 by changing only the same compound.

By using the compound of the present invention in combination, it is possible to obtain a high tone of C.10 or higher.

[Table-4] Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment

Claims (1)

[Scope of Claims] The support has at least one silver halide emulsion layer, and the emulsion layer or other hydrophilic colloid layer contains:
1. A negative-working silver halide photographic material comprising at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z^1 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle. This heterocycle may further be fused with an aromatic ring or a heterocycle. R^1 is an aliphatic group, and X is ▲ has a mathematical formula, chemical formula, table, etc. ▼ or ▲ has a mathematical formula, chemical formula, table, etc. ▼. Q represents a nonmetallic atomic group necessary to form a 4- to 12-membered non-aromatic hydrocarbon ring or a non-aromatic heterocycle. However, at least one of the substituents R^1 and Z^1 and the substituent Q contains an alkynyl group. Furthermore R^1
, Z^1 and Q may have a group that promotes adsorption to silver halide. Y is a counter ion for charge balance, and n is a number necessary for charge balance. General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, X represents a divalent heterocycle containing nitrogen, oxygen, selenium, or a sulfur atom. A represents a divalent linking group consisting of an atom or a group of atoms selected from carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. B represents an amino group, an ammonium group, or a nitrogen-containing heterocycle. n represents 0 or 1. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, an amidino group, or a group that is cleaved under alkaline conditions. ]