JPH0456843A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To rapidly and stably obtain a high-contrast image in high sensitivity by incorporating an iridium compound in an emulsion layer and adding a specified compound in an emulsion layer containing iodide higher in the surface than in the inside of silver halide grains. CONSTITUTION:The emulsion layer contains the iridium compound and the emulsion layer having the silver halide grains higher in the content of the iodide in the surfaces than in the insides contains one of the compound represented by formulae I - III in which each of R1 and R2 is an aryl or heterocyclic group; R is an organic bonding group; (n) is an integer in the range of 0 - 6; (m) is 0 or 1; R21 is an aliphatic or aromatic group or the like; R22 is H or optionally substituted alkoxy or the like; each of P1 and P2 is H, acyl, or the like; Ar is an aryl group having a diffusion-resistant group or a group for promoting adsorption of silver halide; and R31 is substituted alkyl, thus permitting a high- contrast image to be obtained rapidly and stably in high sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and particularly to a high-contrast silver halide photographic light-sensitive material.

[Background of the invention]

In general, high-contrast photographic images are used in the photolithography process to form characters and halftone-resolved photographic images, and in the ultra-precision photolithography process to form fine line images. It is known that photographic images with extremely high contrast can be formed using this type of silver halide photographic light-sensitive material.

Conventionally, for example, a photosensitive material made 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 %) was 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-type photosensitive material.

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

For this purpose, a dot image is formed by using a top lithium type photosensitive material and photographing the original through an intersection line screen or contact screen, followed by development processing.

For this purpose, a silver halide photographic light-sensitive material containing a silver halide emulsion with fine grains and uniform grain size and grain shape is used. When processed with a commercially available developer, the halftone image formation, etc., is inferior to when developed with a Lith type developer.

Therefore, it is processed with a developer called a Lith type developer, which has an extremely low sulfite ion concentration and uses hydroquinone as a single developing agent. However, Lith-type developer is susceptible to auto-oxidation and has extremely poor storage stability.
There is a strong demand for a control method that keeps development quality constant even during continuous use, and great efforts have been made to improve the retention of this developer.

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. The so-called two-liquid separation replenishment method, in which the replenisher (replenishment due to fatigue over time) and the replenisher (replenishment due to aging) are replenished using separate replenishers, is generally widely adopted in automatic developing machines for photolithography. 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.

In addition, in the Lith type development, it takes a long time (induction period) until an image appears due to development, and therefore an image cannot be obtained quickly.

On the other hand, there is a known method for quickly obtaining high-contrast images without using the above-mentioned Lith type developer. For example, U.S. Pat.
As seen in No. 3 and JP-A-51-20921, a hydrazine compound is contained in a silver halide photosensitive material. Image forming methods using these hydrazine compounds can obtain very high-contrast images; however, when photographing unexposed areas, such as black sesame seeds between halftone dots using a contact screen in photosensitive materials for printing. The appearance of dots (hereinafter referred to as black dots) can be seen.

There is also a phenomenon of illumination failure. On the other hand,
No. 129837 discloses a method of adding a hydrazide compound and an iridium compound to an emulsion containing emulsion grains with a controlled content, but this method cannot prevent the occurrence of black spots and also has problems with sensitivity and contrast. There is a problem that there is a shortage of

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material that can quickly and stably obtain high-sensitivity, high-contrast images, and which also solves problems such as illuminance failure and black spots. An object of the present invention is to provide a stable silver halide photographic light-sensitive material free from such problems.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one silver halide photographic emulsion layer on a support, the emulsion layer containing an iridium compound;
Further, the silver halide grains have a higher iodine content on the grain surface than the inside of the grain, and the emulsion layer has the following general formula [11
This is achieved by a silver halide photographic material containing at least one of the compounds represented by , [2], and [3].

General formula [I] [wherein R1 and R2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n represents 0 to 6, m represents 0 or 1, and n is 2 or more In this case, each R may be the same or different. ] General formula I [] [wherein R21 is an aliphatic group, aromatic group or heterocyclic group, R22 is a hydrogen atom, an optionally substituted alkoxy group,
It represents a heterocyclic oxy group, an amino group, or an aryloxy group, and Pl and R2 represent a hydrogen atom, an acyl group, or a sulfinic acid group. ] General formula I [[ ] % formula % [In the formula, Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group, and R3 represents a substituted alkyl group. ] The specific configuration of the present invention will be explained in more detail below.

In the emulsion grains of the present invention, the grains in which the iodine content on the grain surface is higher than the inside of the grain undergo halogen conversion using an iodine compound.

The iodide compound may be added at any point from the 95% point of grain formation to the end of grain formation, before the start of desalination, after desalination, before the start of chemical ripening, or after the end of chemical ripening. It is preferable to do this before the end of salting, particularly before the start of desalting.

The amount added is between 0.1 and 1.0 g per mole of silver, preferably between 0.3 and 0.8 g, particularly preferably between 0.5 and 0.8 g.
It is 7g. Further, the difference in normal content between the surface and the inside is higher at the surface, preferably at most 10 mol%, more preferably at most 5 mol%.

In the present invention, an iridium compound is contained, and specific examples of the water-soluble iridium compound used in the present invention include iridium chloride (IrCJ and trcL), potassium hexyridate, and ammonium hexachloroiridate. These compounds are preferably added as an aqueous solution during or after grain formation, physical ripening, or chemical ripening of the silver halide emulsion, preferably during grain formation.

The amount added is 10-2 to 10-2 per mole of silver halide.
It may be added in moles, but particularly preferably 10-' to 1
It is O-8 mol.

Next, the general formula CM, [:m:l, (II[)
(General formula CI) In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, n is O-6, m is 0
Or represents 1.

Here, examples of the aryl group represented by R1 and R2 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group, etc., but preferred as R1 and R2. is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R1 and R2. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., tomexy, ethoxy, isopropoxy, butoxy, octyloxy, dodecyloxy, etc.), acylamino groups (e.g. acetylamino, pivallylamino, penzoylamino, tetradecanoylamino, a-(2,
4-di-t-amylphenoxy/)butyrylamino, etc.)
Sulfonylamino groups (for example, methanesulfonylamino, butanesulfonylamino, toticanesulfonylamino, benzenesulfonylamino, etc.), urea groups (for example, phenylurea, ethylurea, etc.), thiourea groups (for example, phenylthiourea, ethylthiourea, etc.) , a hydroxy group, an amine group, an alkylamino group (eg, methylamino, dimethylamino, etc.), a carboxyne group, an alkoxycarbonyl group (eg, ethoxycarbonyl), a carbamoyl group, a sulfo group, and the like.

Examples of the divalent organic group represented by R include alkylene groups (for example, methylene, ethylene, tolyltylene, tetramethylene, etc.), arylene groups (for example, phenylene, naphthylene, etc.), aralkylene groups, etc. The group may include an oxy group, thio group, seleno group, carbonyl group, -N- group (R3 represents a hydrogen atom, an alkyl group, or an aryl group), a sulfonyl group, etc. in the bond. Various substitutions can be introduced into the group represented by R.

Examples of the substituent include -CONHNHR, (R4 has the same meaning as R1 and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroquine group, a carboxyne group, an acyl group, an aryl group, etc. .

R is preferably an alkylene group.

Among the compounds represented by general formula (I), preferably R1
and R2 is a substituted or unsubstituted phenyl group, and n-
A compound in which R in m-1 represents an alkylene group.

Representative compounds represented by the above general formula CI) Specific compounds ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ 0C12825n ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ =38 ■ =40 ■ tC,O.

■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ tC6H+ 1 Next, general formula [■] will be explained.PIP200 R21N N CCR42 The aliphatic group represented by R21 preferably has 6 carbon atoms.
Among the above, it is particularly a straight chain, branched or cyclic alkyl group having 8 to 50 carbon atoms. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing one or more helaro atoms therein. Further, this alkyl group may have a substituent such as an aryl group, an alkoxy group, or a sulfoxy group.

The aromatic group represented by R2+ is a monocyclic or bicyclic aryl 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.

Examples include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a virolazole ring, a quinoline ring, an inquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as R21 is an aryl group.

The aryl group or unsaturated heterocyclic group of R2□ may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably a monomer having 1 to 20 carbon atoms in the alkyl moiety). cyclic or bicyclic), alkoxy groups (
(preferably those having 1 to 20 carbon atoms), substituted amino groups (preferably amine groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (preferably those having 2 to 30 carbon atoms), sulfones. Amide group (preferably one or more carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30).

Among the groups represented by R2□ in the general formula [■], the optionally substituted alkoxy group has 1 to 20 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

Among the groups represented by R22 in general formula (n), the optionally substituted aryloxy group or heterocyclic okyne group is preferably a monocyclic group, and the substituents include a halogen atom alkyl group, an alkoxy group, Among the groups represented by R2□, which include a cyano group, preferred are an optionally substituted alkoxy group or an amino group.

A2 may be a cyclic structure containing an optionally substituted alkyl group, alkoxy group, or 10--S--N- group bond. However, R22 is never a hydrazino group.

R21 or R2□ in general formula CI) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a fninoxy group,
It can be selected from alkylphenoxy groups, etc.

R2 or R2□ in the general formula [■] may have a group incorporated therein to enhance adsorption to the silver halide grain surface. Such adsorption groups include thiourea group,
Examples include groups described in US Pat. No. 4,355,105, such as a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group. Among the compounds represented by the general formula [■], the compounds represented by the following general formula CI [-a] are particularly preferred.

General formula (II-a) In the above general formula (I[-a), R23 and R24 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxy group). pyr group, 2-cyanoethyl group, 2-chloroethyl group), optionally substituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group, pyrrolidyl group (e.g. phenyl group, p-methylphenyl group, naphthyl group, a- Hydroquinaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2pyridyl group, pyrrolidyl group, 4-methyl-2
-pyrrolidyl group), R2 is a hydrogen atom or an optionally substituted benzyl group,
Alkoxy and alkyl groups (e.g. benzyl, p-
methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group), R26 and R27 represent a divalent aromatic group (e.g. phenylene group or naphthylene group),
Y represents a sulfur atom or an oxygen atom, and L represents a divalent bonding group (e.g. -3OzCH2CH2NHSO2NH,0C
H2SO2NH,0-CH-N-), R28 represents -R/R// or -R2, R/,
R// and R2 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group), phenyl groups (e.g. phenyl group, p-methylphenyl group, p
-methoxyphenyl group), naphthyl group (e.g. α-naphthyl group, β-naphthyl group), or heterocyclic group (e.g. unsaturated heterocyclic group such as pyridine, thiophene, furan, or tetrahydro-7rane, sulfolane). R' and R'' may form a ring (for example, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

m and n represent 0 or l. When R2 represents OR2, Y preferably represents a sulfur atom.

Specific examples of representative general formulas (n) represented by general formulas CI[) and (I[-a) above ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ *-Nl (NHCCOCH2CH, SO, CH2CH,
OH■ ■ ■ 5Xi NHNtlL;U(JUIhUt12:5 t12L112LJtl■ ■ CH3 ■ =23 ■ =24 ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ しH3 ■ ■ =45 ■ ■ ■ ζ ■ ■ -54 ■ ■ ■ =49 ■ ■ ■ ■-58 ■-59 * ■ 1l -NHNHCCNHC+ 2H2S i3 ■-60 Next, among the above specific compounds, compound II -45゜■
-47 is taken as an example to show its synthesis method.

Synthesis of compound ■-45 Synthesis scheme (A) (B) tl, U (E) Compound 4-nitrophenylhydrazine 153g and 500g
Mix the diethyl oxalate of III2 and reflux for 1 hour. Ethanol is removed as the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next obtained f: crystal (A) (7
) Dissolve 50g of 1000mff by heating, and apply 50g to 1000mff under PD/C (palladium/carbon) catalyst.
Compound (B) is reduced by Psi or pressurized H2 atmosphere.
get.

22g of this compound (B) was added to 200ml of acetonitrile.
Compound (C) 2 was dissolved in a solution of 16 g of pyridine at room temperature.
4 g of acetonitrile solution was added dropwise. After filtering off insoluble matter, the filtrate was concentrated and purified by recrystallization to obtain 31 g of Compound (D).

30 g of compound (D) was hydrogenated in the same manner as above to obtain 20 g of compound (E).

10 g of compound (E) was dissolved in 100 mc of acetonitrile, 3.0 g of ethyl isothionanate was added, and the mixture was refluxed for 1 hour. After distilling off the solvent, the compound (F) 7 was purified by crystallization.
Obtained 0g. Compound (F) 5.0g in methanol 50g
Methylamine (40% aqueous solution 8rn (
1) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out and purified by recrystallization to obtain compound...-45.

Synthesis of Compound ■-47 Synthesis Scheme (B) (C) (D) (E) Compound ■-47 22 g of compound (B) was dissolved in 200 mQ of pyridine, and 22 g of p-nitrobenzenesulfonyl chloride was added into a stirring vessel. . The reaction mixture was poured with water, and the precipitated solid was taken out to obtain compound (C). Compound (C) was subjected to the same reaction as Compound I[-45 according to the synthesis scheme to obtain Compound 1-47.

Next, general formula (III) will be explained.

General formula (I[[)　　　　.

Admiration Ar-NHNH-C-R,.

In the general formula [■], Ar represents an aryl group containing at least one diffusion-resistant group or silver halide adsorption promoting group;
The diffusion-resistant group is preferably a no-last group which is commonly used in immobile photographic additives such as couplers. A ballast group is a group having a carbon number of 8 or more and is relatively inert to photography, and examples include an alkyl group, an alkokene group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose.

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

R11 represents a substituted alkyl group, or the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, and the like.

Examples of substituents introduced into these alkyl groups include alkoxy (e.g., methoxy, ethoxy, etc.), acetyloxy (e.g., dinoquine, p-chlorophenoxy, etc.), heterocyclic oxy (e.g., pyridyloxy, etc.), mercapto, alkylthio, etc. (methylthio, ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), peterocyclicthio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.) , arylsulfonyl (e.g. benzenesulfonyl etc.), heterocyclic sulfonyl (e.g. pyridylsulfonyl, morpholinosulfonyl etc.), acyl (e.g. acetyl, benzoyl etc.), cyano, chloro, bromine, alkoxycarbonyl (e.g. ethoxycarbonyl, methoxycarbonyl etc.), Aryloxycarbonyl (e.g. phenoxycarbonyl, etc.), carboxy, carbamoyl, alkylcarbamoyl (e.g. N-methylcarbamoyl, N,N-
dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-)dynylcarbamoyl, etc.), amino, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino,
naphthylamino, etc.), anrulamino (e.g., acetylamino, benzoylamino, etc.), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoquine carbonylamino, etc.), anrulamino (e.g., acetyloxy , benzoyloxy, etc.), alkylaminocarbonyloxy (e.g., methylaminocarbonyloxy, etc.), arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.) ), arylsulfamoyl (eg, phenylsulfamoyl, etc.), and the like.

Even if the hydrogen atom of hydrazine is substituted with a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, etc.), an oxalyl group (e.g., ethoxalyl, etc.), good.

Representative compounds represented by the above general formula (III) include those shown below.

■ ■ ■ ■ I[[-4 ■ ■ ■ ■ I[[-14 1[[-15 ■ ■ ■ ■ ■ ■ I[+-18 ■ ■ ■ ■ ■ ■-24 ■ ■ ■ ■-33 ■ ■ *-NHNHCCH20C)IzCHzOCHzCHz
OH ■ ■ ■-29 ■ ■ ■ ■ I [[-38 ■ -39 ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ -50 Next, a synthesis example of compound m-5 will be described.

Synthesis of compound m-5 Compound 111-5 was obtained according to the synthesis scheme of compound n-45! child .

The general formula (
1) The amount of the compounds (n) and (III) is from 5 x 10-' to 5 x 10-1 mol per mol of silver halide contained in the silver halide photographic material of the present invention. is preferred, and more preferably in the range of 5 x 10-5 to 1 x 10-2 mol.

In the method of the present invention, the hydrazide compound may be contained in the photosensitive material and/or the developer. When incorporated in a light-sensitive material, a light-sensitive silver halide emulsion layer containing a 3-pyrazolidone compound and a di- or trihydroxybenzene compound and/or a support capable of diffusing and migrating into the emulsion layer at least by the time of development. It may be contained in at least one of the other coating layers above. When included in photosensitive materials,
The amount of hydrazide compound is 1O- per mole of silver halide.
A range of 6 to 1 O-1 mole is suitable, preferably a range of lo-4 to l0-2 mole per mole of silver halide. The appropriate amount can be arbitrarily determined by considering the composition of silver halide, particle size, chemical ripeness, amount of hydrophilic colloid as a binder, and balance with additives such as stabilizers, suppressors, and accelerators. .

When the hydrazide compound is contained in the developer, the amount added is 10-'-10-2 mol, preferably 10-1 to 10-3 mol, per 112 of the developer, and the amount of addition is 10-'-10-2 mol, preferably 10-1 to 10-3 mol, and the coexisting amino compound, pH, fog inhibitor The appropriate amount is determined based on the balance.

The photosensitive material used in the method of the present invention contains a 3-pyrazolidone compound represented by the following general formula.4 In the formula, R41 represents an optionally substituted aryl group, and R42+R43 and R44 are each a hydrogen atom or Represents an alkyl group that may be substituted.

Examples of substituents for the aryl group represented by R41 include groups such as a methyl group, a chloro group, an amino group, a methylamino group, an acetylamino group, a methoxy group, and a methylsulfonamidoethyl group. Examples of the group include phenyl group, p-aminophenyl group, p-chlorophenyl group, p-acetamidophenyl group, and p-methoxyphenyl group.

The alkyl groups represented by R, 2, R, and R44 are
Can be straight chain, branched, or cyclic, preferably with 1 carbon number
~8, and its substituents include, for example, a hydroxy group,
Examples include a carboxy group and a sulfo group, such as a methyl group, a hydroxymethyl group, an ethyl group, and a propyl group.

Typical specific examples of the above 3-pyrazolidone compound are shown below.

[:A-1] l-phenyl-3-pyrazolidone [:
A-2) ■-Phenyl-4,4-dimethyl-3-pyrazolidone (A-3'l l-phenyl-4,-methyl-4-
Hydroxymethyl CA-4] 1-722-4,4-di(hydroxymethyl)-3-pyrazolidone (A-5) 1-phenyl-5-methyl-3-pyrazolidone (A-6) 1-phenyl- 4,4-dimethyl-3
-Pyrazolidone CA-7) 1-p-chlorophenyl-4-methyl-4-propyl-3-pyrazolidone [A-8) 1-p-chlorophenyl-4-methyl-4ethyl-3-pyrazolidone (A-9) 1 -p-acetamidophenyl-4,
4-diethyl-3-pyrazolidone [A-10) 1-1)-methoxyphenyl-4
, 4-diethyl-3-biratritone The present compound is preferably present in the light-sensitive silver halide emulsion layer, but it is also present in the protective film layer, intermediate layer, subbing layer or backing layer, and in non-emulsion layers. It does not matter if it is in the layer. Generally, this compound can be added by dissolving it in an organic solvent, and the amount added is 10-6 to 10-1 mol per 1 mol of silver halide, but the best range is 10-' to 10-2 mol. Show the results.

Further, in the image forming method of the present invention, it is preferable to include a di- or trihydroquine benzene compound represented by the following general formula in the photosensitive material and developer.

H υi In the above formula, R, , R, 2 and R1 are each a hydrogen atom, a halogen atom, an alkyl group (including a substituted alkyl group), an aryl group (including a substituted aryl reducing group), 0
Represents R54 or -S Rs-. R represents a hydrogen atom, an alkyl group (including substituted alkyl groups), an aryl group (including substituted allyl groups), or a heterocyclic group (including substituted heterocyclic groups). n represents 0 or l.

Specific examples of the above di- or trihydroxybenzene compounds are shown below.

CB-1) Hydroquinone [:B-2) Chloronohydroquinone CB-3]
Bromohydroquinone [B-4:] Methylhydroquinone CB-5)
2.3-dichlorono\hydroquinone [:B-6:
] 2.5-dibenzoyl amitsuno\hydroki/ CB-7) Gallic acid butyl ester CB-8)
Gallic acid ethyl ester The preferred location of this compound in the light-sensitive material is in the light-sensitive silver halogenide emulsion layer.
It may be in a non-emulsion layer such as a protective layer, an intermediate layer, a subbing layer or a backing layer. Generally, the present compound can be added by dissolving it in water or an organic solvent such as alcohols such as methanol or ethanol, glycols such as diethylene glycol or triethylene glycol, or carbons such as ascent, and the amount of addition is limited. o, oot~ per mole of silver norogenide
0.10 mol added, preferably 0.0O5-0
．． 03 moles.

The dihydroxybenzene compound contained in the developer used in the method of the present invention is most preferably nohydroquinone, which is a developing agent widely used in photographic processing, and the amount added is usually 0.05 to 0.5. Le/Q.

As the sulfite contained in the developer used in the method of the present invention, those commonly used in developer solutions for silver halide photographic light-sensitive materials can be used, and specific examples thereof include sodium sulfite, potassium sulfite, etc. , lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite, etc. Its concentration protects the developer from air oxidation,
As long as the sulfite ion concentration is sufficient to change stable photographic performance, the addition amount should be 0.0557 l/Q or more, preferably 0.1557 l/Q. It is above Q.

Furthermore, the amino compound contained in the developer used in the method of the present invention is used for the purpose of promoting high contrast, and particularly to produce a strong effect even at a relatively low pH level of the developer.

Amino compounds useful in this invention include both inorganic and organic amines. The organic amine can be an aliphatic amine, an aromatic amine, a cyclic amine, a mixed aliphatic-aromatic amine or a heterocyclic amine. 1st. Second
and tertiary amines and quaternary ammonium compounds were all found to be effective.

Particularly preferred alkanolamines for the purposes of the present invention are represented by the formula:

In the above formula, R6, is a hydroxyalkyl group having 2 to 10 carbon atoms, and RM2 and R63 are each a hydrogen atom, l −10
an alkyl group having 2 to 10 carbon atoms, a hydroquinalkyl group having 2 to 10 carbon atoms, a benzyl group or a group of the formula:

/X -CnH2n-N\Y, n in the above formula is an integer of 1-10, and X and Y are each a hydrogen atom, an alkyl group having 1-1θ carbon atoms, or 2 A hydroquinalkyl group having ~lO carbon atoms.

Another preferred class of amino compounds is the alkylamines, especially those represented by the formula:

In the above formula, R5, is an alkyl group having 1-io carbon atoms, and R65 and Ra6 are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Among the many amine compounds that can be used in carrying out the present invention, particularly representative examples are listed below.

CC-1] Triethanolamine CC-2] Jetanolamine [C-3) Ethanolamine [:C-4) 2-diethylamino-1-ethanol (C-5) 2-methylamino -■-Ethanol [:C-6] 3-diethylamino-1-propatol CC-7] 5-amino-1-pentanol [C-8
3 Diethylamine [C-9] Triethylamine CC-10) Diisopropylamine CC-11)
2-dibutylaminoethanol CC-12)
14-Cyclohexanebis(methylamine) (C-13) o-Aminebenzoic acid 1: C-14
) Aminobutanidine sulfite CC-15'l
4-amino-1-butanol (c-16)
3-pyrrolidino-1,2 propanediol (C-17) 3-(dimethylamino) -1,2
70 Panediol (C-18) 1,4-Piperazinohis (ethanesulfonic acid) [C-1913-piperidino-1,2-propanediol Note that the amount of the amine compound used in the present invention added is 0.
01-1.0 mol/Q, preferably 0, O
It is 1 to 0.04 mol/12.

It is preferable that the developer used in the method of the present invention contains 5 (or 6)-nitroindazole. This is the most effective method for preventing fog, and high sensitivity and high contrast are maintained. The amount added is 0.000 per developer Iff.
A range of 1 to 0.1 mol is appropriate.

The developer used in the method of the present invention may contain a 3-pyrazolidone compound or an ortho or p-aminophenol compound as a developer in addition to the dihydroquinebenzene compound.

In order to maintain the pH of the developer solution preferably at 10 to 12, an alkali metal hydroxide or carbonate can be added as an alkali agent. Furthermore, inorganic inhibitors such as potassium bromide, triazole compounds such as 5-methylbenzotriazole and 5-chlorobenzotriazole, and 2-mercaptobenzimidazole and 1-phenyl-5-mercaptotetrazole are used to suppress fogging caused by development. Organic antifoggants such as mercapto compounds can be used.

Further, in addition to the above-mentioned components, arbitrary additives can be used in the developer used in the method of the present invention depending on the purpose. Examples include solvents, buffers, sequestering agents, development accelerators, viscosity agents, and emulsion layer swelling inhibitors.

Examples of the development accelerator used in the present invention include compounds represented by the following formula CTVI.

General formula (IV) R1-0 CH2CH20+n H [In the formula, R1 represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n represents an integer from 1O to 200. ] Specific examples more preferable than the compound represented by the general formula CIV) will be given, but the invention is not limited thereto.

IV-I IV-2 IV-3 IV-4 IV-5 IV-6 IV-7 IV-8 HO(CI(,CH20)nil HO(CH2CH20)nH HO(CH2CH20)nH HO(CH2CH20)(IH HO(CH,C)120)nH HO(CH2(Jl,0)ttH n・10 n==30 n;50 n-7゜ n=15O n=2o.

IV-9 ■■■■-11 ■IV-12 ■■-13 These compounds are commercially available and can be easily obtained. These compounds have a content of 0.0% per mole of silver halide. It is preferable to add 1 to 4.0 moles of O. 0.02
-2 mol is more preferred.

Further, two or more types of compounds having different values of n may be included.

The development process in the method of the present invention can be carried out under various conditions, but the development temperature is preferably 50°C or less, particularly around 40°C, and the development time is generally completed within 3 minutes. However, particularly preferably within 2 minutes often brings about good results. As treatment steps other than development, for example, steps such as washing with water, stopping, stabilizing, fixing, and further, if necessary, prehardening and neutralization may optionally be employed, and these may be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

The silver halide emulsion of the light-sensitive material used in the present invention has a remarkable effect on silver bromide and silver iodobromide,
It is particularly effective for highly sensitive light-sensitive materials containing little silver iodide (AgI 5 mol %).

The degree of dispersion of emulsion grains was measured using electron micrographs and a Coulter N-4 grain measuring device.

The silver halide contained in the silver halide emulsion layer of the light-sensitive material used in the present invention has an average grain size of 0-1-1.
．． 0 p m, particularly preferably from 0.1 to 0.7 p wr and at least 75% of the total particle number, particularly preferably 8
It is preferable to contain silver halide having a grain size of 0% or more or 0.7 to 1.3 times the average grain size.

Furthermore, polyvalent metal ions (e.g. iridium, rhodium, etc.)
U.S. Patent No. 3, a silver halide emulsion containing occluded
No. 271,157, No. 3,447.927, No. 3,5
Emulsions such as those according to No. 31.291 can also be used. Silver halide emulsions can be chemically sensitized using conventional sulfur compounds, gold compounds such as chlorauric acid salts, gold trichloride, and the like.

The silver halide emulsion to which the present invention is applied can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye.

As the sensitizing dye, commonly used ones such as methine dyes and styryl dyes such as cyanine, heminanine, rhodacyanine, merocyanine, oxanol, and hemioxonol can be used.

The above dye is disclosed in U.S. Pat. No. 2,742.833 and U.S. Pat.
56゜148, 3,567.458, 3,61
5.517, 3,615゜519, 3,632
．． No. 340, No. 3,155.519, No. 3, 384
.

No. 485, No. 4,232,115, No. 3,796.5
No. 80, No. 4,028° No. 110, No. 3,752.67
No. 3, JP-A-55-45015, etc. can be referred to.

The silver halogenide photographic emulsion of the light-sensitive material used in the present invention contains commonly used hardening agents such as aldehydes (formaldehyde, glyoxal, glutaraldehyde, mucochloric acid, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.) etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.),
Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, etc.), active halides (2,4-dichloro-6-hydroxy-8-triazine, etc.), These agents can be used alone or in combination, and commonly used thickeners, matting agents, coating aids, etc. can be used.

Further, as the binder, a commonly used hydrophilic binder having protective colloidal properties can be used.

Furthermore, according to the purpose of the present invention, commonly used couplers, ultraviolet absorbers, optical brighteners, image stabilizers, antioxidants, lubricants, sequestering agents, emulsifying dispersants, etc. may be added to the photosensitive material. I can do something.

The light-sensitive material used in the method of the present invention includes layers other than the silver halide emulsion layer, such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a subbing layer, an auxiliary layer, an anti-irradiation layer, and a backing layer. The support to be used may be appropriately selected from baryta paper, polyethylene-coated paper, cellulose acetate, cellulose nitrate, polyethylene terephthalate, etc., depending on the intended use of the photosensitive material.

A polymer latex consisting of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. is applied to the photosensitive silver halide emulsion layer or other coated layer on the support to improve the properties of photographic materials. , may be included for the purpose of improving the physical properties of the film.

4-Hydroxy-6-methyl-1,3,3a,7- as a stabilizer or antifoggant in a photosensitive silver halide emulsion.
Many compounds such as citrazaindene, 1-phenyl-5-mercaptotetrazole, resorcinol oxime, hydroquinodidoxime and others can be added in amounts of 10-' to 10-1 mole per mole of silver halide.

The photosensitive silver halide emulsion layer or its adjacent layer may contain Research Disclosure (R65earchDisclosure) for the purpose of increasing sensitivity, increasing contrast, or promoting development.
Compounds described in Section XXI B-D of No. 17463 can be added.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using a simultaneous mixing method. During this mixing, 21rCI2
．． was added at 8X10' moles per mole of silver.

Further, when grain formation was 95% complete, 56.5 cc of 1% potassium iodide solution per mole of silver was added to this emulsion, and the resulting emulsion was a cubic crystal with an average grain size of 0.20 μm.

Thereafter, modified gelatin (exemplified compound G-8 of Japanese Patent Application No. 1-180787) was added, and the mixture was washed with water and desalted in the same manner as in the Example of Japanese Patent Application No. 1-180787. 40 after desalting
The pAg at °C was 7.60.

Furthermore, during redispersion, the following compounds [A] [B] EC
] Compound [A] + [B] + [(1 (Preparation of silver halide photographic light-sensitive material) Undercoat layer with a thickness of 0.1 μm on both sides (JP-A-59-1994
A silver halide emulsion layer having the following formulation (1) with a gelatin amount of 2.0 was applied on one undercoat layer of a 100 μm thick polyethylene tereftate film coated with a polyethylene tereftate film (see Example 1 of No. 1).
g/m2, silver amount is 3.2g/+2ft 6 person i:
On top of that, a protective layer of the following formulation (2) is applied so that the amount of gelatin is 1.0 g/I12, and on the other undercoat layer of the opposite side, the following formulation (3) is applied. ), apply a backing layer with a gelatin amount of 2-4 g/rn", and then apply a protective layer of the following formulation (4) on top of it with a gelatin amount of 1 g/m". Sample No.

1 to 18 were obtained.

Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0 g/m'' Silver iodobromide emulsion A Silver amount Antifoggant: Adenine stabilizer 4-methyl-6-hydroxy 1.3,3a,7-titrazaindene surfactant: Savonin: S-1 12 g/m.

25 ■g/112 30119/■2 0.1g/m" 8s+g/■2 Polyethylene glycol molecular weight 40000.1g/iris 2 Latex polymer: Compound according to the present invention or comparative compound Quantity sensitizing dye shown in Table 1: Dura mater Agent H-1 60mg/+a" Prescription (2) [Emulsion protective layer composition] Gelatin matting agent: Surfactant: Silica CHHzCOOCHz (Cal(s)CaHs(JCOO) with an average particle size of 3.5μ-
CHzCH (CzHs) CaHsSo, Na Hardening agent: Formalin prescription (3) (Backing layer composition) (a) CH2SO3H Calcium 0.9g102 3+og/m"10mg/+o" 30g/++2 Gelatin surfactant: Saponin: s - (4) [Backing protective layer composition] 2.7g/-1 0.1g/■2 6mg/+" Gelatin matting agent: Bomethacryte surfactant with average particle size of 3.0 to 5.0 μm: S- 2 Hardener: Glyoxal: H-1 1g/m" Remethyl 50mg/■2 10a+g/m" 25+g/■2 35ff1g/Otori 2 The obtained sample was subjected to halftone quality test and illumination failure test by the following method. went.

(Testing method for halftone dot quality) Attach a part of the screen (150 lines/inch) with a halftone dot area of 50% to the step wedge, place the sample in close contact with this screen, and expose the sample to a xenon light source for 5 seconds. The sample was developed under the following conditions in an automatic processing machine for quick processing using the developer and fixer listed below, and the quality of the halftone dots on the sample was observed with a 100x magnifying glass. "
5" rank, and the following "4", "3", "2", rlJ
5 ranks.

Note that the ranks rlJ and "2" are at levels that are practically unfavorable.

Black spots in the halftone dots are also evaluated in the same way, and the highest rank is ``5'' when there are no black spots in the halftone dots, and ranks are determined according to the degree of occurrence of black spots in the halftone dots. 4",
The evaluation was performed by lowering the ranks sequentially from "3" to "2" to rlJ. In addition, in ranks rlJ and "2", the black spots are also large and are at a level that is not desirable for practical purposes.

(Illuminance failure test) The obtained sample was placed in close contact with a step wedge and heated at 3200°.
exposed to tungsten light. At this time, two types of exposure were performed so that the exposure amount for I.times.10@-5 seconds and for 5 seconds were the same by adjustment using a filter. This sample was subjected to the following processing and then evaluated by the difference in the logarithm of the exposure dose of the 5 second exposed sample and 1 x 10-' seconds giving an optical density of 2.5.

In addition, the obtained sample was measured using a Konica digital densitometer FDP-65.
The sensitivity at the concentration of sample No. 3.0 was set to 10.
The relative sensitivity is expressed as 0, and the gamma is expressed as the tangent between the densities 0.3 and 3.0.

Developer formulation Disodium ethylenediaminetetraacetate mg Sodium sulfite 60g Trisodium phosphate (decahydrate) 75g Hydroquinone
22.5g N,N-diethylethanolamine 15g Sodium Bromide
3g 0.25g Torazol 0.08g -25g 5-Methylbenzotriazole 1-7enyl-5-mercaptothimethol The pH was adjusted to 112 by adding water, and the pH was adjusted to 11.7 with hydroxide.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 40mQ 7g 6.5g 6g 6g Sodium sulfite Sodium acetate trihydrate Boric acid Sodium citrate dihydrate (Composition) Pure water (ion Exchange water) Sulfuric acid (50% w/w aqueous solution) Aluminum sulfate (Affixes equivalent content 8.1% w/w aqueous solution)
7mI2 4.7g 26.5g They were dissolved in the following order, finished to IQ, and used. The po of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
40 ° CI5 Sand room arrival 35 °
Wash with C15 sand and water, dry for 10 seconds at 30℃
Dry at 50°C for 10 seconds.
The following compounds (a) to (C) were used as comparative compounds added to the silver halide emulsion layer in 1).

In addition, comparative sample No. 17 contains an emulsion that is not subjected to legal conversion, N
For No. 0 and No. 18, an internal high-density type emulsion was used.

(b) When using a fixer, add 1 set of the above composition A in 500mff of water. (c) 9-1・ As is clear from Table 1, sample N according to the present invention.

It can be seen that 6 to 15 have high sensitivity, high contrast, and good halftone dot quality and black shading in comparison.

Example 2 The same procedure as in Example I was carried out except that the sample used in Example 1 was treated with a developer having the following formulation.

Developer prescription Hydroquinone 22.5g meth
− le
0.25g ethylenediaminetetraacetic acid 1.0g sodium sulfite
75.0g Sodium hydroxide 7.9
g Trisodium phosphate (decahydrate) 75.0g5-
Methylbenzotriazole 0.25gN, N-diethylethanolamine 12.5g Add water to 112
and adjusted pl to 11.6.

As is clear from the results in Table 2, the samples according to the present invention, like Example 1, have higher sensitivity, higher contrast, better halftone dot quality, and better black shading compared to the comparison.

Example 3 The physically ripened emulsion used in Example 1.2 was sulfur sensitized according to a conventional method. Then, 6-methyl-4-
Hydroxy-1,3,3a,7-titrazaindene was added, the mixture was divided as shown in Table 3, a hydrazine compound was added, and the same formulation as in Example 1 was applied. The resulting sample was exposed to canon light for 1×10' seconds and processed according to Example 1.

Further, as a comparative example, as is clear from the results of illuminance failure in a system without Ir in Table 3, the sample of the present invention also exhibits excellent performance in terms of high illuminance characteristics.

〔Effect of the invention〕

According to the present invention, it was possible to provide an image forming method using a silver halide photosensitive material that has high sensitivity, high contrast, no illuminance failure, and less occurrence of black spots.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the emulsion layer contains an iridium compound, and the iodine content of the grain surface is is a silver halide grain that is higher than the inside of the grain,
Further, the emulsion layer has the following general formula [I], [II], [III]
A silver halide photographic material containing at least one compound represented by: General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc.
or 1, and when n is 2 or more, each R may be the same or different. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. It represents an oxy group, an amino group, or an aryloxy group, and P_1 and P_2 represent a hydrogen atom, an acyl group, or a sulfinic acid group. ] General Formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are included. ]