JPH0456842A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To rapidly obtain a high-contrast image by incorporating an iridium compound in an emulsion layer and adding a water-soluble iodide compound at a specified point of time to change its halide and further adding a specified compound in the emulsion layer. CONSTITUTION:The emulsion layer contains the iridium compound and silver halide grains are changed in the halide formation by adding the water-soluble iodide compound at the point of time when >=90% of silver halide grains have been formed, and the emulsion layer contains one of the compounds 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 is the range of 0 - 6; (m) is 0 or 1; R21 is an aliphatic or aromatic group; R22 is H or optionally substituted alkoxy, or the like; each of P1 and P2 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 in high sensitivity to be rapidly obtained.

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.

[Conventional technology]

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 silver halide photographic materials for this purpose can form photographic images with extremely high contrast.

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 halftone dot image is formed by using the above-mentioned lithium-type photosensitive material and photographing an original through an intersection 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, since the developing solution is susceptible to auto-oxidation, its stability is extremely poor.
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. A so-called two-liquid separation replenishment system, in which the replenisher (replenishment due to fatigue over time) and the replenisher (replenishment due to aging) are replenished using separate replenishers, is generally widely adopted in automatic developing machines for photolithography and the like. However, the above method has the disadvantage that it is necessary to control the replenishment balance of the two liquids, which complicates the equipment and operation.

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. 1-29837 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 reduces sensitivity. There is also a problem of insufficient contrast.

[Purpose of the invention]

Therefore, a first object of the present invention is to provide an image forming method that can quickly and stably obtain a high-contrast image.

A second object of the present invention is to provide image formation in which a high-contrast image can be stably obtained with high sensitivity and little loss of sensitivity.

A third object of the present invention is to provide an image forming method that provides images with high contrast and fewer defects such as black spots.

A fourth object of the present invention is to provide an image forming method with high contrast and no illuminance failure.

Other objects of the invention will become apparent from the following description of the specification.

[Structure of the invention]

The above objects of the present invention are as follows: 1. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, in which an iridium compound is contained in the emulsion layer, and No. 10 gene conversion is performed with a water-soluble iodide compound at 90% or more, and the emulsion layer contains at least one of the compounds represented by the following general formulas (I), (II), and (I[[). This is achieved by a silver halide photographic material characterized by the following.

General formula CI) In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents an organic bonding group, n represents 0 to 6, m represents O or 1, and when n is 2 or more, , each R may be the same or different.

General formula (n) In the formula, R2 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R22 represents a hydrogen atom, an optionally substituted alkoxy group, a heterocyclic oxy group, an amino group, or an aryloxy group. , P, and P! represents 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 /10 silver-genide adsorption-promoting group, and R31 represents a substituted alkyl group.

The specific configuration of the present invention will be explained in more detail below.

First, regarding general formulas (1), (II), (I[[), general formula (1), where R1 and R3 represent an aryl group or a heterocyclic group, and R represents a divalent organic group, n is 0 to 6, m is 0
or represents l.

Here, examples of the aryl group represented by R1 and R8 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a penzothiazoryl group, a quinolyl group, a thienyl group, etc.; Preferred is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R and R8. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., tomoxy, ethoxy, impropoxy, butoxy, octyloxy, dodecyloxy, etc.), and acylamino groups. (e.g. acetylamino, bivalylamino, benzoylamino, tetradecanoylamino, a-C2,
(4-di-1-amylphenoxy)butyrylamino, etc.)
Sulfonylamino groups (e.g., methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea groups (e.g., phenylurea, ethylurea, etc.), thiourea groups (e.g., phenylthiourea, ethylthiourea, etc.), hydroxy groups , amino group, alkylamino group (e.g., methylamino, dimethylamino, etc.), carboxy group, alkoxycarbonyl group (e.g., ethoxycarbonyl), carbamoyl group, sulfo group, etc. Divalent organic group represented by R Examples include alkylene groups (e.g., methylene, ethylene, tolyltylene,
tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene nato), aralkylene groups, etc. Aralkylene groups include oxy groups, thio groups, seleno groups, carbonyl groups, -N- groups (R3 is a hydrogen atom, It may also contain a sulfonyl group (representing an alkyl group or an aryl group). Various substitutions can be introduced into the group represented by R.

Specific compound substituents include, for example, C0NHNHR4 (R4 represents the same meaning as R8 and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, etc. .

R is preferably an alkylene group.

Among the compounds represented by general formula (1), preferably R,
and R7 is a substituted or unsubstituted phenyl group, and n=
A compound in which R in m-1 represents an alkylene group.

Representative compound c represented by the above general formula (1):
：、-・W ＼ζ〜-ME″ LCsH++ ■ E■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ ■ tc, H,.

■ ■ =35 ■ ■ ■ ■ ■ ■ -48 E■ ■ Next, the aliphatic group represented by tc, H mouth R2□, which will explain the general formula CI [), 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 R31 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 R2 is an aryl group.

The aryl group or unsaturated heterocyclic group of R21 may be substituted, and typical substituents include a linear, branched or cyclic alkyl group (preferably a monocyclic alkyl group having 1 to 20 carbon atoms). or two rings), alkoxy groups (
(preferably those having 1 to 20 carbon atoms), substituted amine groups (preferably amine groups substituted with alkyl groups having 1 to 20 carbon atoms), acylamino groups (preferably those having 2 to 30 carbon atoms), sulfonamides. Group (preferably 1 to 1 carbon atoms)
30), a ureido group (preferably a carbon number of 1 to
30).

Among the groups represented by R22 in general formula (I[), 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 CII), the optionally substituted aryloxy group or heterocyclic oxy group is preferably a monocyclic group, and the substituents include a halogen atom alkyl group, an alkoxy group, and a cyanogen atom alkyl group, an alkoxy group, and a cyanide group. Among the groups represented by R2□, preferred are an optionally substituted alkoxy group or an amine 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.

R11 or RZZ in the 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.

R21 or R2□ in general formula (n) 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 CI), the compounds represented by the following general formula [■a] are particularly preferred.

General formula (II-a) In the above general formula (I[-a), R2s and R14 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, butyl group, dodecyl group, 2-hydroxypropyl group) 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, α-hydroxy naphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group, 4-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-
2-pyrrolidyl group), R□ represents a hydrogen atom or an optionally substituted benzyl group, alkokene group, and alkyl group (e.g. benzyl group, p-methylbenzyl group, methoxy group, ethoxy group, ethyl group,
butyl group), and Ro and R17 represent a divalent aromatic group (
For example, 7-enylene group or 7-tyrene group), Y represents a sulfur atom or oxygen atom, and L represents a divalent bonding group (
For example -5OzCH2CH2NH5OzNH,0CH2
SO2NH,0--CH-N-), R1, represents -R/R// or -R2, R/
, R/ / and R3 are hydrogen atoms, optionally substituted alkyl groups (e.g. methyl group, ethyl group, dodecyl group)
, phenyl group (e.g. phenyl group, p-methylphenyl group, p-methoxyphenyl group), naphthyl group (e.g. α
-naphthyl group, β-naphthyl group) or a heterocyclic group (for example, an unsaturated heterocyclic group such as pyridine, thiophene, or furan, or a saturated heterocyclic group such as tetrahydrofuran or sulfolane), and R' and R// may form a ring (eg, piperidine, piperazine, morpholine, etc.) together with a nitrogen atom.

Specific examples of general formula CI+) I[-1 m and n represent 0 or l. When R2 represents OJs, Y preferably represents a sulfur atom.

Representative 1[ represented by the above general formula (II) and (I[-a)]
-3 ■ I[-10 ■ I[-11 ■-[2 ■ ■ ■ ■ ■ ■ ■ -23 ■ CHl C+oH21n ■ *→HNHCCOCH, CH, SO, CH, CH20H
*-NHNHCCOCH, CH, SCH, CH, OH ■ ■ ■ ■ ■ ■ O ■ ■ = 30 ■ ■ ■ ■ ■ ■ = 33 ■ ■ ■ ■ ■ ■ H3 ■ ■ ■ ■ = 47 ■ ■ ■ ■ ■ ■ - 58 ■-59 ■ * Tatsumi-NHNHCCNHC, □H0 ■ ■ ■ ■-60 I'I3 Next, the synthesis method thereof will be shown by taking compound ■■-47 as an example from among the above-mentioned specific compounds.

Synthesis of Compound ■-45 Synthesis Scheme 45゜(B) (En(A) Compound 4-nitrobuenylhydrazine 153g and 500g
Mix i of diethyl oxalate and reflux for 1 hour.

Ethanol is removed while the reaction progresses, and finally it is cooled to precipitate crystals. Filter, wash several times with petroleum ether and recrystallize. Next, 5 of the obtained crystals (A)
Dissolve 0g in 1000m+2 methanol at Calorie temperature, p
The d/C (palladium/carbon) catalyst hinge was pressurized at 50 Psi and reduced in an atmosphere of f:HxK to obtain an insulator (B).

Add 22g of this compound (B) to 200ml of acetonide
Compound (C) was dissolved in a solution of 2 and 16 g of pyridine at room temperature.
24 g of acetonitrile solution was added dropwise. Filter out insoluble matter5
After 11 days, the filtrate was concentrated and purified by recrystallization to obtain compound (D)3.
1g was obtained.

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

Compound (E) lOg to acetonitrile 100+n12
Add 3.0 g of ethyl thiocyanate to 1
Refluxed for an hour. After distilling off the solvent, the compound (F
) 7.0g was obtained. 5.0 g of compound (F) was dissolved in 50 mQ of methanol, and methylamine (8 m of 40% aqueous solution) was dissolved in 50 mQ of methanol.
Q) was added and stirred. After slightly concentrating methanol, the precipitated solid was taken out and purified by recrystallization to obtain Compound 1-45.

Synthesis of Compound 11-47 Synthesis Scheme (B) (D) (E) Compound 1-47 22 g of compound (B) was dissolved in 200 ml of pyridine, and 22 g of p-nitrobenzenesulfonyl chloride was added into a stirring vessel. The reaction mixture was poured into water, and the precipitated solid was taken out to obtain compound (C). Compound (C) was subjected to the same reaction as compound (1)-45 according to the synthesis scheme to obtain compound (1)-47.

Next, general formula (III) will be explained.

General formula (m).

Ar NHNH-cRsr In the general formula (II[), Ar is a diffusion-resistant group or a halogen (C
) It represents an aryl group containing at least one silveride adsorption promoting group, and the diffusion-resistant group is preferably a ballast group 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 may be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. I can do it.

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.

R31 represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, cyclohexyl, and the like.

Substituents introduced into these alkyl groups include alkoxy (e.g., methoxy, ethoxy, etc.), aryloxy (e.g., phenoxy, p-chlorophenoxy, etc.), peterocyclic oxy (e.g., pyridyloxy, etc.), mercapto, alkylthio (methylthio), etc. , ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), alkylsulfonyl (e.g., methanesulfonyl, butanesulfonyl, etc.), arylsulfonyl ( For example, benzenesulfonyl, etc.), heterocyclic sulfonyl (for example, pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (for example, acetyl, benzoyl, etc.), cyano, chloro, bromine, alkoxycarbonyl (for example, ethoxycarbonyl, methoxycarbonyl, etc.), aryloxycarbonyl ( (e.g., phenoxycarbonyl), carboxy, carbamoyl, alkylcarbamoyl (e.g., N-methylcarbamoyl, N,N-
dimethylcarbamoyl, etc.), arylcarbamoyl (e.g., N-phenylcarbamoyl, etc.), amino, alkylamino (e.g., methylamino, N,N-dimethylamino, etc.), arylamino (e.g., phenylamino,
naphthylamino, etc.), acylamino (e.g., acetylamino, benzoylamino, etc.), alkoxycarbonylamino (e.g., ethoxycarbonylamino, etc.), aryloxycarbonylamino (e.g., phenoxycarbonylamino, etc.), acyloxy (e.g., acetyloxy, penzoyl), ), alkylaminocarbonyloxy (e.g., methylaminocarbonyloxy, etc.), arylaminocarbonyloxy (e.g., phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl (e.g., methylsulfamoyl, etc.), Examples include various groups such as arylsulfamoyl (eg, phenylsulfamoyl, etc.).

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 (II[) include those shown below.

1[1-1 ■ 1[[-6 m-7 I[1-8 ■ ll-17 ■ 1[[-19 ■-20 ■-21 Shirishi rs ■ DI -12 ■ ■ ■ -15 I[[ -16 ■-22 ■-23 ■ -24 ■-25 ■-26 *-NHNHCCH*0CHxCH BA) CH, CH, O
H■-27 ■-28 ■-29 ■-30 ■-31 ■-36 ■-37 ■-38 ■-39 ■ ■-33 ■ -34 ■-35 ■ -40 II[-41 ■-42 ■- 43 ■-44 ■-48 ■-45 ■-49 ■-46 ■-50 ■-47 Next, a synthesis example of compound n[-5 will be described.

Synthesis of Compound I[[-5 Synthesis Scheme Compound II[-5 was obtained according to the synthesis method of Compound I[-45.

General formula C contained in the silver halide photographic material of the present invention
The amount of the compounds I), (n), and (II[) is from 5 x 10-' to 5 x io-' mol per 1 mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. Preferably, more preferably 5 x 10-1 to lX
It is in the range of 10-'' moles.

In the method of the invention, a hydrazide compound can also be added to the developer. When incorporated into a light-sensitive material, it is on a light-sensitive silver halide emulsion layer containing a 3-pyrazolidone compound and a di- or trihydroxybenzene compound and/or on a support that can diffuse and move into the emulsion layer at least until the time of development. It may be contained in at least one of the other coating layers. When included in a light-sensitive material, the amount of the hydrazide compound is lo-1 to l0- per mole of silver halide.
A range of 1 mol is suitable, preferably 1 mol of silver halide.
It ranges from 10@-4 to 10@-2 mole per mole. 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-'' mol, preferably 10-4 to 10-3 mol, per 1i2 of the developer, and the coexisting amino compound, I'Hs fog can be suppressed. The appropriate amount is determined based on the balance of agents, etc.

Next, specific examples of water-soluble iridium salts used in the present invention include iridium chloride (IrCQ and IrCQ).
Potassium hexachloroiridate, ammonium hexachloroiridate, and the like can be mentioned. These compounds are preferably added as an aqueous solution during or after grain formation, physical ripening, chemical ripening of the silver halide emulsion, and particularly preferably during grain formation. The amount added is generally 10-” to 1 mole of silver halide.
It is sufficient to add 10-1 mol, but particularly preferably 10
-1 to 10-a Mortial.

For halogen conversion by a water-soluble iodide compound at 90% or more before the completion of grain formation, preferably grain formation 9
Halogen conversion is carried out at 0% or more, more preferably at 95% or more. Furthermore, it is possible to carry out the process after particle formation, after desalination, before chemical ripening, or after completion of chemical ripening. Preferably, before desalting.

Regarding the amount added, 0.1-10g/Ag l III
Preferably between 0.3 and 0.8 g/Ag lm
off, particularly preferably 0.5 to 0.7 g/Ag 1
It is moQ.

The legal content is preferably 1OII in the outer layer than in the inner layer.
It is better to be higher than loQ%, more preferably to be higher than 5 moff%.

The photosensitive material used in the method of the present invention contains a 3-pyrazolidone compound represented by the following general formula, where R4,
represents an optionally substituted aryl group, and R4! ,
R43 and R44 each represent a hydrogen atom or an optionally substituted alkyl group.

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 7-enyl group, p-aminophenyl group, p-chlorophenyl group, p-acetamidophenyl group, p-methoxyphenyl group, and the like.

The alkyl groups represented by R4□, R4, 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) 1-7enyl-4.4-dimethyl-3-pyrazolidone (A-3) 1-722-4. -Methyl-4-hydroxymethyl (A-4) 1-722-4.4-di(hydroxymethyl)-3-pyrazolidone [A-5) l-phenyl-5-methyl-3-pyrazolidone (A- 6) 1-phenyl-4,4-dimethyl-3
-Pyrazolidone (A-7) 1-p-chlorophenyl-4-methyl-4-propyl-3-pyrazolidone (A-8) up-chlorophenyl-4-methyl-4-ethyl-3-pyrazolidone (A-9) 1 -p-acetamidophenyl-4,
4-diethyl-3-pyrazolidone [:A-10) 1-p-methoxyphenyl-4,
4-Diethyl-3-biratritone The present compound is preferably present in a light-sensitive silver halide emulsion layer, but it may be present in non-emulsion layers such as a protective layer, an intermediate layer, a subbing layer or a backing layer. I don't mind. Generally, this compound can be added by dissolving it in an organic solvent, and the amount added is 10-6 to 1O-1 mol per mol of silver halide, but the best range is 1O-' to 10-2 mol. Show the results.

The di- or trihydroxybenzene compound contained in the photosensitive material and developer used in the image forming method of the present invention is a compound represented by the following formula.

1"1M Sui In the above formula, R!l+ Rs2 and R53 are each a hydrogen atom, a halogen atom, an alkyl group (including a substituted alkyl group), an aryl group (including a substituted aryl group), a hetero-reducing group (including substituted hetero-reducing groups), O
Rz or -5-Ra, R represents a hydrogen atom, an alkyl group (including substituted alkyl groups), an aryl group (including substituted aryl groups), or a hetero-reducing group (substituted hetero-reducing group) (including). n represents 0 or 1.

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

CB-1) Hydroquinone (B-2) Chlorohydroquinone (B-3)
Bromohydroquinone [:B-4) Methylhydroquinone CB-5) 2,3-dichlorohydroquinone CB-6) 2,5-dibenzoylaminohydroquinone CB-7) Gallic acid butyl ester CB-8)
Ethyl gallic acid ester This compound is preferably present in the light-sensitive silver halide emulsion layer, but it may also be present in non-emulsion layers such as a protective film layer, intermediate layer, subbing layer or backing layer. do not have. 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 ketones such as ascent, and the amount of silver halide added is determined. o per mole, ooi ~ 0
．． 10 mol is added, preferably 0.005-0.
03 moles.

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

As the sulfite contained in the developer used in the method of the present invention, those commonly used in the developer of silver halide photographic light-sensitive materials can be used, and specific examples include sodium sulfite, potassium sulfite, sulfite, etc. Examples include lithium, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite, and the like. The concentration should be sufficient to provide a sufficient sulfite ion concentration to protect the developer from air oxidation and thereby provide stable photographic performance, and the amount added should be 0.05 mol/Q or more. However, it is preferably o, 15 mol/a or more.

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. Organic amines include aliphatic amines, aromatic amines, cyclic amines, aliphatic-y! It can be a mixed amine or a heterocyclic amine. 1st. Secondary and tertiary amines and quaternary ammonium compounds have all been found to be effective.

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

In the above formula, R, l are hydroxyalkyl groups having 2 to 10 carbon atoms, and R, and R6, are each a hydrogen atom, l -10
an alkyl group having 2 to 10 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, a benzyl group or a group of the following formula: /X -CnH,n-N\Y, where n is is an integer from 1 to 10, and X and Y are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 2 to 10 carbon atoms.

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

In the above formula, R,4 is an alkyl group having 1-10 carbon atoms, and R6s and R1, are each a hydrogen atom or an alkyl group having 1-10 carbon atoms. .

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

(C-1) Triethanolamine (C-2)
Jetanolamine CC-3) Ethanolamine (C-4) 2-diethylamino-1-ethanol (C-5) 2-Methylamino-1-ethanol (
C-6) 3-diethylamino-1-propatol 5-amino-I-pentanoldiethylamine triethylamine diisopropylamine 2-dibutylaminoethanol 1-4-cyclohexane bis(methylamine) (C-13) o-aminobenzoic acid ( C-7) 1”c-8) (c-9) (C-to) (C-11) (C-12) CC-14) Aminobutanidine sulfite (C
-15) 4-amino-1-butanol CC-16
) 3-pyrrolidino-1,2 propanediol (C-17) 3-(dimethylamino) -1,2
~Propanediol c c -18) 1,4-Piperazinohis(ethanesulfonic acid) (C-19) 3-piperidino-1,2-propanediol Note that the amount of the amine compound used in the present invention added is 0.
01 to 1.0 mol/Q, preferably 0.0
It is 1 to 0.04 mol/1.

The developer used in the method of the present invention preferably 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 0.0001 per developer IQ.
A range of -0.1 mole is suitable.

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 dihydroxybenzene compound.

The pn of the developer is preferably 10 to 12, but in order to maintain that pH, 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, ■-722-5- are used to suppress fogging during development. Organic antifoggants such as mercapto compounds such as mercaptotetrazole 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 general formula [).

General formula (IV) R1-0CH*CH*O+nH [In the formula, R represents a hydrogen atom or an unsubstituted or substituted aromatic ring, and n represents an integer from 10 to 200. ] Specific examples more preferable than the compound represented by general formula (IV) will be given, but the invention is not limited thereto.

rl/-I IV-2 IV-3 IV-4 IV-5 IV-6 IV-7 IV-8 HO (CH! CHz O) n H HO(CH,CH,0)nH HO(CH2CH20)nH HO(CH2CH20)nH HP(CH,CH,0)nH HO(CH2Cl,0)nH n=lO n=3O n=5゜ n==7゜ n=15O n・200 IV-9 rV -14 ■-i.

■-15 IV-11 1V-16 IV-12 ■-13 IV-17 These compounds are commercially available and can be easily obtained. These compounds are preferably added in an amount of o, oi to 4.0 mol per mol of silver halide L < 0.0
2 to 2 mol is more preferable.

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 (Agl 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 O-1 to 1.
．． 0 p m, particularly preferably 0.1-0.7 μm, and at least 75%, particularly preferably 80% of the total number of particles
It is preferred that the above contains silver halide having a grain size of 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, hemicyanine, rhodacyanine, merocyanine, oxanol, and hemioxonol can be used.

The above dyes are disclosed in U.S. Pat. Nos. 2,742,833 and 2,7.
56゜148, 3,567.458, 3,61
No. 5,517, No. 3,615゜519, No. 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゜110, No. 3,752,67
No. 3, JP-A-55-45015, etc. can be referred to.

The silver halide photographic emulsion of the light-sensitive material used in the present invention contains aldehydes (formaldehyde, glyoxal, glutaraldehyde,
mucochloric acid, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2゜3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine) , bis(vinylsulfonyl)
Methyl ether, etc.)ll halides <2,4-dichloro-6-hydroxy-8-triazine, etc.), etc. can be used alone or in combination, and are also commonly used as thickeners, matting agents, coating aids, etc. You can use whatever is used.

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

Furthermore, according to the purpose, the photosensitive material may contain a Kabra ultraviolet absorber, a fluorescent whitening agent, an image stabilizer, an antioxidant, a lubricant,
Those commonly used as metal ion sequestering agents, emulsifying and dispersing agents, etc. can be added.

The light-sensitive materials used in the method of the present invention include 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.

The dimensional stability of photographic materials can be improved by adding a polymeratex consisting of a homo- or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. to the photosensitive silver halide emulsion layer or other coated layer on the support. , 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 anti-capri in the photosensitive silver halide emulsion.
Many compounds such as citrazaindene, -phenyl-5-mercaptotetrazole, resorcinol oxime, and hydroquinone aldoxime can be added in an amount of 1 O -4 to 10 moles per mole of silver halide.

The photosensitive silver halide emulsion layer or its adjacent layer may contain research disclosure materials for the purpose of increasing sensitivity, increasing contrast, or promoting development.
Compounds described in section XXI) JB-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, IrCQ,
was added at 8Xlo-7 moles per mole of silver.

Furthermore, when grain formation was 95% complete, 56.6 cc of 1% potassium iodide solution per mole of silver was added to this emulsion, and the resulting emulsion was 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 of 'O was 7.60.

Further, during redispersion, the following compounds [A] [B] [C
] Compound [A] + [B] + [C] (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/l112, silver amount is 3.2 g/m'', and on top of that, a protective layer of the following formulation (2) is applied so that the gelatin amount is 1.0 g/m''. On the other side, on the other undercoat layer, a backing layer with a gelatin amount of 2.4 g/m2 was applied according to the following recipe (3), and on top of that, a protective layer according to the following recipe (4) was applied. The amount of gelatin in the layer is 1
Sample No. g/m'.

1 to 18 were obtained.

Prescription (1) (Silver halide emulsion layer composition) Gelatin
2.0 g/m" Silver Iodobromide Emulsion A Silver amount Anticaprilant: Adenine stabilizer 4-methyl-6-hydroxy-1,3,3a,7-titrazaindene Surfactant: Saponin: S-1 Polyethylene glycol Molecular weight 4000 latex polymer: 34 g/mt 25 mg/m" 30 mg/m2 0.1 g/m" 8 mg/m" 0-1 g/m2 Amount sensitizing dye shown in Compound 1 according to the invention or comparative compound: Hardener H-1 60mg/m' Prescription (2) [Emulsion protective layer composition] Gelatin matting agent: Silica surfactant with average particle size of 3.5 μm: S
-2 cnzcoocuz(czns)canssummerCHCOOCH,CH((,H8)C,H.

So, Na Hardening agent: Formalin 0.9 g/m2 3 mg/m2 10 mg/m2 30 mg/m2 Gelatin formulation (3) (backing layer composition) (a) Surfactant: Saponin: S-1 formulation (4 ) [Backing protective layer composition] 2.7g/m2 0.1g/m"6mg/m" CH, So, H Gelatin Ig/m" Matting agent: Polymethyl methacrylate with an average particle size of 3.0 to 5.0 μm 50mg/m” Surfactant: S
-210mg/m” Hardener: Glyoxal
25mg/m”: Hl
35 mg/m'' was subjected to a halftone quality test and an illuminance failure test using the following methods.

(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, followed by "4", "3", "2", "l"
5 ranks.

Note that ranks "1" and "2" are levels that are not desirable in practical terms.

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 "1" and "2", the black spots are also large and are at a level that is not desirable for practical use.

(Evaluation method of illuminance failure) 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 difference in exposure between 1 x 10-' seconds and 5 seconds was the same by adjustment using a filter. After processing this sample as described below, 5 seconds and l x t with an optical density of 2.5
Evaluation was made based on the difference in the logarithmic value of the exposure amount of the o-1′ exposed sample.

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 Ethylenediaminetetraacetic acid disodium salt g Sodium sulfite 60 g Trisodium phosphate (decahydrate) 75 g Hydroquinone
22.5g N,N-diethylethanolamine 15g Sodium bromide 5-methylbenzotriazole 1-7enyl-5-mercaptothimethol Add water to make 1Q, and adjust to 11.7% hydroxide.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% v/v 3g 0.25g Torazol 0.08g 0.25g pH adjusted with thorium) 240m (2 7g 6.5g 3g 3g Sodium sulfite sodium acetate 3 Boric acid sodium citrate dihydrate (composition) Pure water (ion-exchanged water) Sulfuric acid (50% W/W aqueous solution) Aluminum sulfate (AQlo, aqueous solution with a converted content of 8.1% W/W) 7 m
Q 4.7g When using a fixer, the above composition A1 was dissolved in 500mff of water in the order of composition, and the solution was finished to 112 before use. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
Arrived at 40 °C15 sand and mud Washed at 35 °C15 sand and water Dry at 30 °C1o seconds
50 °0 10 seconds Note that the prescription (
The following compounds (a) to (c) were used as comparative compounds added to the silver halide emulsion layer in 1).

Further, for comparative samples No. 16 and No. 17, emulsions that were not subjected to excessive conversion were used. Also, No. 18 has 80% particle formation.
At this point, halogen conversion was performed using potassium iodide.

26.5g The results of the above examples are shown in Table 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 (Preparation of silver halide photographic emulsion B) Emulsion B was prepared in the same manner as emulsion A was prepared in Example 1, except that potassium iodide was added after grain formation was completed. did.

The same evaluation as in Example 1 was performed and the results are shown in Table 2.

However, the emulsions used in Comparison No. 16 and No. 17 in Table 2 were emulsions that were not subjected to excessive conversion as in Example 1, and
o, 18 shows potassium iodide at 80% grain formation as shown in Table 2. As with Example 1, the sample of the present invention has higher sensitivity and higher contrast compared to the comparison, and also has good halftone quality and black bubbles. I understand that there is something.

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 Cannon light for 101 seconds and processed according to Example 1. Furthermore, as a comparative example, illuminance failure was confirmed in a system without iridium.

〔Effect of the invention〕

According to the present invention, it was possible to provide an image forming method using a silver halide photosensitive material which 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, the emulsion layer containing an iridium compound,
% or more with a water-soluble iodine compound, and the emulsion layer has the following general formulas [I], [II],
A silver halide photographic material containing at least one compound represented by [III]. 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 [II] ▲ Numerical formulas, chemical formulas, tables, etc. are included. group, amino group, or 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. ]