JPH08297339A - Silver halide photographic photosensitive material and its processing method - Google Patents

Abstract

PURPOSE: To provide a photoengraving silver halide photosensitive material which is excellent in processing stability in a silver halide photographic sensitive material and a contrasty negative image forming method using it. CONSTITUTION: Developing processing is performed on a silver halide photographic sensitive material exposed under the existence of a contrasting accelerator of a formula. In the formula, R<1> , R<2> , R<3> , R<4> , R<5> and R<6> represent a hydrogen atom, an alkyl group, an allyl group and a heterocyclic group, and R<1> and R<2> , and R<3> and R<4> , and R<5> and R<6> , and R<1> and R<3> may form a ring by connecting these to each other. L<1> and L<2> represent an alkylene group, an allylene group or at least two repetitive alkylene oxy groups, and A respresents a bivalent connecting group composed of an atom or an atomic group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and (m and n) represent 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a superhard tone negative image forming method using the same, and more particularly to a silver halide photographic light-sensitive material used in a photomechanical process. .

[0002]

2. Description of the Related Art In recent years, colorization and complexity of printed matter have been rapidly progressing in the field of printing photoengraving. Therefore, demands for improving the quality and stabilizing the quality of the silver halide light-sensitive material for printing (hereinafter referred to as a printing light-sensitive material), which is an intermediate medium for printing, are increasing year by year. Conventionally, a general printing photosensitive material has been imparted with so-called lith development processing suitability in order to achieve high quality. However, in the lith development, it is mechanically impossible to contain a high concentration of a sulfite ion, which is a preservative, in the developing processing solution, and therefore it is not known to those skilled in the art that the stability of the developing solution is very poor. Then it is a well-known fact. As a technique for eliminating the instability of the lith development and obtaining a high-contrast image similar to the lith development processing, the disclosure of the patent document can be seen for some attempts. For example, a technique for obtaining a high-contrast image using a hydrazine compound is disclosed in JP-A-53-16623, JP-A-53-20921, and JP-A-53-20922.
No. 53-49429, No. 53-66732, No. 55-90940,
56-67843, 57-99635, 62-73256, 62
-275247, 62-178246, 62-180361, 63-
121838, 63-223744, 63-234244, 63-25
No. 3357, No. 64-90439, JP-A No. 1-105943, No. 2-2
No. 5843, No. 2-120736, No. 2-37, No. 2-8834,
No. 3-125134, No. 3-184039, No. 4-51143, etc. The pH of the developer containing these hydrazine compounds is required to be at a relatively high level in order to obtain a high contrast image, and the developer having this high pH absorbs carbon dioxide in the air. However, the pH tends to decrease, the stability against air oxidation is not always sufficient, and the useful life of the developer is short.

To overcome these drawbacks, a lower p
For example, as disclosed in JP-A-60-179734,
62-948, U.S. Pat.Nos. 4,385,108 and 4,269,929.
No. 4,988,604, No. 4,994,365, No. 5,104,769, and the like, attempts have been made to make the hydrazine derivative more active, but improvement of the hydrazine derivative alone makes it difficult to increase the contrast at low pH. There was a limit. Therefore, the development of a contrast enhancing agent has been conventionally advanced. As described in JP-A-56-106244, JP-A-60-218642, JP-A-61-267759, etc., a method of adding a secondary or tertiary amino compound to a developing solution, JP-A-60-140340. , 62-
There is known a method of adding an amino compound to a light-sensitive material as disclosed in 222241, 63-124045 and US Pat. No. 4,975,354. However, none of them have the drawbacks that they still do not exhibit satisfactory contrast, or that they must be used in large amounts, and that the photographic performance changes greatly when the composition of the developer changes due to running or air oxidation. Therefore, it has been desired to develop a more effective accelerator.

[0004]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a light-sensitive material having a high contrast and a high image density by using a developing solution which is stable at a low pH. A second object of the present invention is to provide a photosensitive material for printing plate making containing an effective accelerator having an effect of promoting contrast enhancement in a small amount. A third object of the present invention is to provide a silver halide photographic light-sensitive material which has little change in photographic performance due to change in developer composition.

[0005]

A method of processing a silver halide photographic light-sensitive material, which comprises subjecting an exposed silver halide photographic light-sensitive material to development processing in the presence of a compound represented by the following general formula (1). Achieved by the method.

[0006]

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In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ¹ and R ³ may combine to form a ring. L ¹ and L ² are alkylene groups, and
Represents a ren group or at least two repeating alkyleneoxy groups, A represents a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom,
It represents a divalent linking group consisting of an atom or a group of atoms selected from a sulfur atom. m and n represent 0 or 1.

The general formula (1) will be described in detail below. The alkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and the alkyl group is linear or branched. Alternatively, it may be annular. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a hexyl group, a cyclohexyl group, and an n-decyl group. Also, R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ¹
And R ³ may combine to form a ring, and a saturated heterocycle containing a hetero atom (eg, nitrogen atom, oxygen atom, sulfur atom, etc.) therein, for example, piperidine ring, 2-methylpiperidine ring, You may form a morpholine ring, a piperazine ring, etc. The substituent as the substituted alkyl group may be an aryl group (eg, phenyl group, naphthyl group, etc.), an alkenyl group (eg, vinyl group, allyl group, butenyl group, etc.), an alkynyl group (eg, ethynyl group), a heterocyclic group (pyridyl group). Group, tetrahydropyranyl group, sulforanyl group, etc., hydroxy group, alkoxy group (eg methoxy group, ethoxy group, benzyloxy group, polyethyleneoxyalkyl group etc.), alkoxycarbonyl group (eg ethoxycarbonyl group, benzyloxycarbonyl group etc.) ), A carboxy group, a sulfo group, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, an aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), an acyloxy group (eg, acetyloxy group, propionyloxy). Groups, etc.), acyl groups (eg acetyl) , Propionyl group, benzoyl group, mesyl group or the like), a carbamoyl group (e.g., carbamoyl group, N, N-dimethylcarbamoyl group, a morpholinocarbonyl group, etc. piperidinocarbonyl group), a sulfamoyl group (e.g., sulfamoyl group,
N, N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc., acylamino group (for example, acetylamino group, propionylamino group,
Mesylamino group etc.), sulfonamide group (ethylsulfonamide group, p-toluenesulfonamide group etc.), ureido group (eg methylureido group, phenylureido group etc.), amino group (eg diethylamino group etc.) and the like. To be

Examples of the aryl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ include a phenyl group and a naphthyl group, which are substituents (in the term of the substituted alkyl group). Same as described). R ¹ , R ² , R ³ ,
Examples of the heterocyclic group represented by R ⁴ , R ⁵ and R ⁶ include a piperidyl group, a morpholinyl group, a furyl group, a thienyl group, a tetrahydropyranyl group, a pyridyl group, and the like. (Same as described in section)
May be provided. The alkylene group represented by L ¹ and L ² represents an alkylene group having 1 to 10 carbon atoms (for example, a methylene group, an ethylene group, a propylene group, etc.), and the substituents are an alkyl group, an aryl group, an alkoxy group, a hydroxy group. A group, a halogen atom, etc. can be mentioned. L ¹
Examples of the arylene group represented by and L ² include a phenylene group and a naphthylene group, which may have a substituent (the same as those described in the section of the substituted alkyl group). When at least two repeating alkyleneoxy groups represented by L ¹ and L ² are represented, examples of the alkyleneoxy group include ethyleneoxy group, propyleneoxy group, butyleneoxy group and the like. The divalent linking group represented by A includes -CO
^{NR 11 -, - OCONR 11 -} , - NR 11 CONR 11 -,
^{-NR 11 COCONR 11 -, - NR} 11 COO -, - CO
O -, - OCO -, - CO -, - NR 11 CO -, - SO
_{^{2 NR 11 -, - NR 11}} SO 2 -, - SO 2 -, - O-,
^{-S -, - NR 11 - (} . R 11 represents a hydrogen atom, an alkyl group, an acyl group, an alkylsulfonyl group), and the like, m and n represents 0 or 1. Further, the compound represented by the general formula (1) may form a salt such as a hydrochloride or p-toluenesulfonate. Specific examples of the compound represented by formula (1) are shown below, but the invention is not limited to the following compounds.

[0010]

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[0011]

[Chemical 4]

[0012]

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[0013]

[Chemical 6]

[0014]

[Chemical 7]

[0015]

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[0016]

[Chemical 9]

Next, specific synthesis examples of the contrast enhancing agent represented by the general formula (1) will be shown. Synthesis Example 1 Synthesis of Compound A-1 Synthesis of Intermediate (Synthesis of N, N, N ′, N′-Tetramethylchloroformamidinium Chloride) 49.4 g of tetramethylurea was added to 1,2-dichloroethane 4
After dissolving in 00 ml, at room temperature 30.0 g oxalyl chloride
Was added dropwise over 15 minutes. After stirring for 15 minutes at room temperature, 65 ℃
The mixture was stirred in the oil bath for 2 hours. About 200 reaction mixture
The crystals were concentrated under reduced pressure to ml and allowed to cool to precipitate crystals. The crystals were collected by filtration, washed with ether and then dried under reduced pressure.
0.0 g of a white, hygroscopic target product was obtained. Synthesis of Compound A-1 9.76 g of N, N, N ', N'-tetramethyl chloroformamidinium chloride was dissolved in 100 ml of methylene chloride, and 11.14 g of 3-dibutylaminopropylamine was added dropwise while stirring under cooling with ice water. did. After stirring at room temperature for 1 hour, the mixture was washed with an aqueous sodium carbonate solution and washed with water. The organic layer was dried over anhydrous sodium sulfate and then concentrated, excess amine was removed under reduced pressure, and a light brown viscous oily substance was obtained at 7.5.
g was obtained.

Synthesis Example 2 Synthesis of Compound A-29 2-diisopropylaminoethyl chloride hydrochloride 10 g
Was dissolved in 30 ml of methanol, 9.1 ml of 5.5M sodium methylate in methanol was added, 7.5 ml (0.06 mol) of tetramethylguanidine was added, and the mixture was heated under reflux for 8 hours. The sodium chloride precipitate was filtered off, and the filtrate was concentrated at 90 ° C. under reduced pressure to remove all volatile components. To this concentrate, 20 ml of methanol was added and filtered, butyl methyl ether was added and precipitated, and the same operation was repeated twice to obtain a target product of 6 g of deliquescent white crystals. Other exemplified compounds can be easily synthesized by the same method.

When the compound of the general formula (1) of the present invention is added to the photographic light-sensitive material, it is preferable to add it to the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers ( (Eg, protective layer, intermediate layer, filter layer, antihalation layer, etc.). Specifically, when the compound used is water-soluble, as an aqueous solution, and when it is poorly water-soluble, a water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone). , Methyl ethyl ketone), dimethylacetamide, dimethyl sulfoxide,
It may be added to the hydrophilic colloid solution as a solution of an organic solvent such as methyl cellosolve. When it is added to the silver halide emulsion layer, it can be added at any time during emulsion preparation, but it is preferably added after the completion of chemical ripening and before coating. Particularly preferably, it is added to the coating solution prepared for coating. The amount of addition is 1 mol of silver halide,
1.0 × 10 ^-4 ~1.0 × 10 ^-1 mol, more preferably 5.0 × 10 ^-4 ~5.0 × 10 ^- used in the range of ² moles. When the compound is added to the developer, it is preferably 5 × 10 ^{−3 to} 0.30 mol per liter of the developer.
The compound represented by the general formula (1) of the present invention has the effect of accelerating the enhancement of contrast when used in a system for obtaining a so-called contrast-rich silver image. The compound represented by the general formula (1) of the present invention is most effective in a system using a hydrazine derivative as a nucleating agent. Examples of the hydrazine derivative used in the present invention include compounds represented by the following general formula (2).

[0020]

[Chemical 10]

In the general formula (2), A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfonyl group or an acyl group, and R ₁ is an aliphatic group, an aromatic group or a heterocycle. Represents a group, G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and R ₂ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, amino. Group or general formula (3)
Represents

[0022]

[Chemical 11]

In the general formula (3), Q ⁺ represents a group containing a cationic group and A ⁻ represents an anion, but it is not necessary when Q ⁺ contains a sulfo group.

Next, the general formulas (2) and (3) will be described in detail.
Reveal In the general formula (2), A₁, A₂Is a hydrogen atom, carbon
Number 20 or less alkylsulfonyl group and arylsulfo group
Nyl group (preferably phenylsulfonyl group, or
Σ_pIs replaced so that the sum of is equal to or greater than -0.5.
Nylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably
Benzoyl group or Hammett's σ_pSum of -0.5
A benzoyl group substituted as described above), or
Straight-chain, branched or cyclic unsubstituted and substituted aliphatic acyl groups
(As the substituent, for example, a halogen atom, an ether group,
Sulfonamide group, amide group, hydroxy group, carboxy
And a sulfo group), and A₁, A₂As
Is most preferably a hydrogen atom. R₁Represented by
Aliphatic groups are straight chain, branched or cyclic alkyl groups, alkene
Group and alkynyl group. R ₁With an aromatic group represented by
Is a monocyclic or bicyclic aryl group, for example,
Examples thereof include a nyl group and a naphthyl group. R₁As a heterocyclic group of
3 to include at least one of N, O and S atoms.
10-membered saturated or unsaturated heterocycles, which are
It may be a single ring, or other aromatic ring or heterocycle.
And may form a condensed ring. Preferably as a heterocycle,
A 5- to 6-membered aromatic heterocyclic group, for example, pyridinium
Group, imidazolyl group, quinolinyl group, benzimidazo group
Ryl group, pyrimidyl group, pyrazolyl group, isoquinolinyl
Group, thiazolyl group, benzthiazolyl group is preferred.
Good.

R ₁ may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted. For example, an alkyl group,
Aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group , A halogen atom, a cyano group, a sulfo group, a carboxy group, an ammonium group, a pyridinium group, a thiuronium group, an isothioureido group and the like. When possible, these groups may be linked to each other to form a ring. Preferred as R ₁ is an aromatic group, more preferably an aryl group. or,
R ₁ may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more and relatively inactive for photographic properties, and examples thereof include an alkyl group and
It can be selected from an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Q ⁺ in the general formula (3) is a group containing a cationic group having at least one quaternary nitrogen atom,
It may be bonded to G ₁ through a straight or branched hydrocarbon chain having 1 to 4 carbon atoms, and part or all of this chain may form part of a heterocycle having a quaternary nitrogen atom. Good.
Preferred examples of Q ⁺ include trialkylammoalkyl group, pyridinium-1-ylalkyl group, 1-alkylpyridinium-2-yl group, 1-alkylpyridinium-3-yl group, 1-alkylpyridinium-4- Examples thereof include an yl group, a thiazolinium-3-ylalkyl group, an oxazolinium-3-ylalkyl group, and a 1-alkylimidazolium-3-ylalkyl group. These groups may be substituted, and as the substituent, those mentioned as the substituent for R ¹ are preferable. Further, when these groups form a ring structure, they may be condensed with another ring. A ⁻ is a counter anion of Q ⁺ , and preferred examples thereof include Cl ⁻ , Br ⁻ , p-toluene sulfonate, methyl sulfonate and the like, which has a sulfo group as a substituent of Q ⁺ and has an inner salt. It does not exist when forming.

G ₁ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and G ₁ is preferably a carbonyl group or an oxalyl group. The aliphatic group represented by R ₂ is preferably an alkyl group having 1 to 5 carbon atoms, and the aromatic group is preferably a monocyclic or bicyclic aryl group (for example, one containing a benzene ring). When G ₁ is a carbonyl group, R ₂
Preferred among the groups represented by are hydrogen atom, alkyl group (for example, methyl group, trifluoromethyl group, 3-
Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, 2-hydroxybenzyl group), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, 2-methane) Sulfonamidophenyl group, 4-methanesulfonamidophenyl group, 2-hydroxymethylphenyl group, etc.), general formula (3), and the like, with a hydrogen atom and general formula (3) being particularly preferable. R ₂ may be substituted, and as the substituent, the substituents enumerated for R ₁ can be applied. When G ₁ is an oxalyl group, preferred R ₂ is an alkoxy group (eg, methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, etc.),
Aryloxy group (for example, phenoxy group, 2-hydroxymethylphenoxy group, 4-chlorophenoxy group),
An amino group (for example, a 3-hydroxypropylamino group,
2,3-dihydroxypropylamino group, 2-dimethylaminoethylamino group, 3-diethylaminopropylamino group, etc.) and general formula (3), and the amino group is particularly preferable. R ₁ and R ₂ may be those in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include groups described in US Pat. No. 4,355,105 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group, and triazole group. R ₂ splits the G ₁ -R ₂ portion from the residual molecule,
It may be one that causes a cyclization reaction to form a cyclic structure containing an atom of the G ₁ -R ₂ moiety, and examples thereof include those described in JP-A-63-29751. Can be mentioned. Specific examples of the compound represented by the general formula (2) are shown below, but the present invention is not limited to the following compounds.

[0027]

[Chemical 12]

[0028]

[Chemical 13]

[0029]

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[0030]

[Chemical 15]

The hydrazine compound of the present invention is disclosed in, for example, JP-A Nos. 61-213847, 62-178246, 62-180361 and 62-178361.
62-260153, 63-253357, U.S. Patent No. 4,684,604
Issue No. 3,379,529, No. 4,377,634, No. 4,332,87
No. 8, No. 4,937,160, Japanese Patent Application No. 63-98803 and the like can be used for the synthesis.

The hydrazine compound of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylacetamide, dimethyl sulfoxide,
It can be used by dissolving it in methyl cellosolve or the like.
Further, by a well-known emulsification dispersion method, oil such as dimethyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate is dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Objects can be created and used. Alternatively, the hydrazine compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and then used.

The silver halide used in the light-sensitive silver halide emulsion of the light-sensitive material of the present invention is not particularly limited, but a surface latent image type silver halide emulsion is preferable, and the silver halide type is silver chloride or salt. Although silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide or the like can be used, when silver chloroiodobromide or silver iodobromide is used, the content of silver iodide is 5 It is preferably in the range of mol% or less. The form, crystal habit, size distribution, etc. of the silver halide grain are not particularly limited, but the grain size is 0.7
It is preferably μm or less. A silver halide emulsion is a sulfur compound that reacts with a gold compound such as chloroaurate or gold trichloride, a salt of a noble metal such as rhodium or iridium or a silver salt to form silver sulfide, a stannous salt, The sensitivity can be increased with a reducing substance such as amines without coarsening the particles. Also, salts of precious metals such as rhodium and iridium,
An iron compound such as red blood salt may be present during physical ripening or nucleation of silver halide grains. In particular, addition of a rhodium salt or a complex salt thereof is preferable because it further promotes the effect of the present invention of achieving photographic characteristics of ultrahigh contrast in a short developing time.

In the present invention, the surface latent image type silver halide emulsion refers to an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably the US Pat.
It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of 4,224,401. The silver halide emulsion is preferably monodispersed, and particularly preferably an emulsion having monodispersity defined in the above-mentioned US Pat. No. 4,224,401. It is preferable that the silver halide emulsion used in the present invention contains a water-soluble rhodium salt (eg, rhodium dichloride, rhodium trichloride, potassium hexachloride rhodium (III) acid, ammonium hexachloride rhodium (III) acid). The rhodium salt is preferably added before the first ripening at the time of emulsion production. The addition amount of the rhodium salt is preferably 1 × 10 ⁻⁷ mol to 1 × 10 ⁻⁴ mol per mol of silver halide. The average grain size of the silver halide used in the present invention is preferably 0.7 μm or less, particularly preferably 0.1 to 0.4 μm. The silver halide grains may have a regular shape such as a cube or an octahedron or a mixed crystal form, but a so-called monodisperse emulsion having a relatively narrow grain size distribution is preferable. The monodisperse emulsion referred to herein means an emulsion in which 90%, more preferably 95% of the total number of grains falls within a grain size range of ± 40% of the average grain size. The method of reacting the soluble silver salt and the soluble halogen salt for the preparation of the silver halide emulsion in the present invention may be a single jet method, a double jet method, a reverse mixing method of forming in the presence of excess silver ions, or the like. But for the purposes of the present invention,
A double jet method in which a soluble silver salt and a soluble halogen salt are simultaneously added in an acidic solution to form grains is particularly preferable. The silver halide emulsion thus prepared may or may not be chemically sensitized. The so-called bright room light-sensitive material to be handled in a safe light environment which can be called a bright room is easy to handle. From the viewpoint of improving the quality, it is rather preferable not to perform chemical sensitization. For chemical sensitization, ordinary sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and the like are used.

In the light-sensitive material of the present invention, the hydrazine compound is preferably contained in the silver halide emulsion layer.
It may be contained in a hydrophilic colloid layer adjacent to the surface latent image type silver halide emulsion layer. Such a layer is a layer having any function, such as a subbing layer, an intermediate layer, a filter layer, a protective layer, or an antihalation layer, as long as it does not prevent the hydrazine compound from diffusing into the silver halide grains. Good. Since the content of the hydrazine compound in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content can vary over a wide range, but for the hydrazine compound the surface can be varied. About 1 x 10 per mol of silver in latent image type silver halide emulsion
A range of ^-6 to 1 x 10 ^-2 mol is practically useful.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are
Cyanine dyes, merocyanine dyes, and composite merocyanine dyes. These sensitizing dyes may be used alone or in combination.
A combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Gelatin is advantageously used as the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. It is possible to use various kinds of synthetic hydrophilic polymer substances such as a partial or acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, and other single or copolymers. . As gelatin, lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
An enzyme-treated gelatin as described in p. 16, p. 30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used.

In the method of obtaining an ultrahigh contrast image using a hydrazine compound, a conventional safelight dye is added to an emulsion layer or other hydrophilic colloid layer in order to enable handling in a bright room. Is also good. The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles. Conventionally known as antifoggants or stabilizers such as mercaptopyrimidines, mercaptotriazines, thioketo compounds, and azaindenes;
Many compounds can be added. Among these, particularly preferred are benzotriazoles (eg 5-methylbenzotriazoles) and nitroindazoles (eg 5-nitroindazole). These compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-6). −
Hydroxy-S-triazine, etc.) or the like can be used alone or in combination. Compounds described in Research Disclosure No. 17465, Sections XXI, B to D are added to the photosensitive silver halide emulsion layer or its adjacent layer for the purpose of increasing sensitivity, increasing contrast, or promoting development. In particular, it is preferable to add polyethylene glycol or its derivative. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention includes a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration, high contrast). A surfactant may be contained for various purposes such as sensitization and sensitization. Nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants, alkyl carboxylates, alkyl sulfates,
Carboxy group, such as alkyl phosphates,
Anionic surfactants containing amino groups such as sulfo group, phospho group, sulfate group, and phosphate group, amino acids,
Amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium Can be used.

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

In order to obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or a highly alkaline developer having a pH of about 13 as described in US Pat. No. 2,419,975 is used. It is not necessary and a stable developing solution can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing a sufficient amount of sulfite ions as a preservative (in particular, 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Particularly, with a developing solution of 10 to 11.0, a super-high contrast negative image can be sufficiently obtained. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[0042]

【Example】

Example 1 6-Methyl-4-hydroxy-1,3,3a, 7- was added to a monodisperse silver chlorobromide emulsion containing iridium and having an average particle size of 0.25 μm prepared by the control double jet method.
Tetrazaindene (1 g / Ag, 1 mol) was added. Anhydro-5,5'-dichloro-9-ethyl- as a sensitizing dye
3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide pyridinium was added at 300 mg / Ag1mo.
The hydrazine compound and the contrast enhancing agent shown in Table 1 were added as shown in Table 1. The emulsion thus obtained contains 2 g / m ² of a dispersion of polyethylene acrylate and 2.5 g / m ² of gelatin.
^{2. The} coating was carried out on a polyethylene terephthalate film so that the coated silver amount was 3.5 g / m ² . Comparative compounds (1), (2) and (3) were similarly used as comparative samples of the contrast enhancing agent.

[0043]

Embedded image

The sample thus obtained was exposed through a light wedge with a printer using a tungsten lamp as a light source, and then developed with a developer having the following composition at 35 ° C. for 30 seconds, stopped, fixed, washed with water and dried. Their relative photographic speed, contrast and dot quality were evaluated. Contrast is the slope of the straight line part of the characteristic curve (ta of optical density 0.1 to 2.50).
It is represented by nθ), and if it is 10 or less, the hardness is insufficient and it is not practical. The halftone dot quality is a subjective measure and was ranked on a scale of 5 with 1 being extremely poor and 5 being extremely good. Three or more were considered to be practically usable. Further, the black spots in the unexposed area were evaluated on a scale of 5 using a magnifying glass of 100 times, and those having no black spots were set to 5, and 3 or more were practically usable. The results are shown in Table 2.

<Developer (concentrate)> Hydroquinone 65 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.9 g Sodium pyrosulfite 145 g Diethylenetriaminepentaacetic acid pentasodium salt 6.0 g Boric acid 6.9 g Sodium bromide 12g 1-Phenyl-5-mercaptotetrazole 0.05g Sodium hydroxide 23g Benzotriazole 0.4g Potassium hydroxide 80g Potassium carbonate 80g Diethylene glycol 120g Water was added 1 liter The above concentrate was added to 4 parts of water 1 It was diluted at a ratio of 1 part to obtain a developing solution having a pH of 10.5.

[0046]

[Table 1]

[0047]

[Table 2]

Example 2 By the control double jet method, the average particle size of rhodium dichloride of 8.0 × 10 ^-6 mol / Ag of 1 mol was 0.1.
A 13 μm monodisperse silver chloride emulsion was prepared. The emulsion desalted, washed with water and redissolved by the flow curation method was divided, and the exemplified hydrazine compound and the contrast enhancing agent were added as shown in Table 3. 5 × 10 ⁻³ mol / Ag 1 mol of 5-chlorobenzotriazole, polyethyl acrylate latex, 2-hydroxy-4,6-dichloro-1,3,
After adding 5-triazine sodium salt, gelatin was coated on a polyethylene terephthalate film so that gelatin was 3 g / m ² and coated silver amount was 5 g / m ² . On this, as a protective layer, 1 g / m ^{2 of} gelatin, 80 mg / m ² of a yellow dye having an absorption maximum wavelength at 400 to 450 nm (eg, Oxonol Yellow manufactured by Hoechst Co.), a surfactant and a hardener are applied and coated. Then, the samples shown in Table 3 were prepared. As a comparative sample of the contrast enhancing agent, the comparative compound as in Example 1 was used.
(1), (2) and (3) were used.

These films were used in a bright room printer (P-627FM manufactured by Dainippon Screen Mfg. Co., Ltd.).
After imagewise exposure at 35 ° C. with the developer shown in Example-1.
It was developed for 30 seconds, stopped, fixed, washed with water and dried. An automatic processor (Dainippon Screen Mfg. Co., Ltd., LD-221QT) was used for this processing. And Example-1
The same items were evaluated. The results are shown in Table 4.

[0050]

[Table 3]

[0051]

[Table 4]

It can be seen that when the compound of the general formula (1) of the present invention is used, a small amount of addition of the compound exhibits a high effect of promoting a high contrast, and the sensitivity, contrast and halftone dot quality are improved. Higher contrast than that of the comparative compound is maintained, and practically preferable photographic characteristics in which the occurrence of pepper fog is suppressed are provided. Further, it is apparent that the use of the compound of the general formula (1) causes the hydrazine compound to produce a high contrast even in a developer having a low pH.

[0053]

INDUSTRIAL APPLICABILITY The formation of a high-contrast image by a silver halide photographic material containing a hydrazine compound in the presence of a high-contrast accelerator selected from the compounds of the general formula (1) of the present invention is a developer having a pH lower than that of the prior art. However, it is easy, and practically preferable photographic characteristics in which the occurrence of pepper fog is suppressed can be provided. In addition, the contrast enhancing agent described in the present specification is easy to synthesize, low in cost, and very effective.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Kaneko 3-4-2 Marunouchi, Chiyoda-ku, Tokyo Sanryo Paper Co., Ltd. (72) Kenji Hirata 3-4-2 2-3 Marunouchi, Chiyoda-ku, Tokyo Ryohyo Paper Co., Ltd. (72) Inventor Akira Tanaka 3-4-2 Marunouchi, Chiyoda-ku, Tokyo Sanryo Paper Co., Ltd. (72) Inventor Reinhold Rieuger, Federal Republic of Germany 6074 Radermark. Shirashi Shutase 11

Claims (2)

[Claims] 1. A method for processing a silver halide photographic light-sensitive material, which comprises developing the exposed silver halide photographic light-sensitive material in the presence of a compound represented by the following general formula (1). Embedded image In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ¹ , R ² , R 5
³ and R ⁴ , R ⁵ and R ⁶ , and R ¹ and R ³ may be linked to form a ring. L ¹ and L ² represent an alkylene group, an arylene group or at least two repeating alkyleneoxy groups, and A represents an atom or an atom group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. Represents a divalent linking group.
m and n represent 0 or 1. 2. A support having at least one silver halide emulsion layer, and the emulsion layer or another hydrophilic colloid layer containing a compound represented by the general formula (1) and a hydrazine derivative. A silver halide photographic light-sensitive material characterized by the above.