JPH09146208A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain superior quick processability and high process stability by incorporating at least one kind of compound which has a specific structure part in a polymer molecule. SOLUTION: A molecule contains at least one kind of compound having the structure part represented by a formula I. In formula I, Ar represents aroma group, which may be substituted for, R1 is an alkyl group, an aryl group, an alkoxy group, an amino group, or a heterocycle group which may be substituted for, and Z is a bivalent combination group. In the formula I, Ar is the bivalent aroma group which may be substituted for by, for example, a methyl group, an ethyl group, an i-propyl group, a methoxyl group, an ethoxyl group, etc., and a phenylene group is preferable as an aroma cycle. Further, Z is a combination group preferably having formulas II and III. In formulas II and III, R2 is a hydrogen atom and a low-class alkyl group.

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 the field of graphic arts, an image forming system exhibiting photographic characteristics of ultra-high contrast (particularly, gamma of 10 or more) is required in order to improve reproduction of continuous tone images or line images by halftone images. is necessary.
As a method for obtaining high contrast photographic characteristics using a stable developing solution, US Pat. Nos. 4,166,742, 4,168,977, 4,211,857, and 4,224 are known. No. 401, No. 4,311,781,
A method using a hydrazine derivative described in U.S. Pat. No. 4,272,606 is known. According to this method, ultra-high contrast and high-sensitivity photographic characteristics can be obtained, and the addition of a high concentration of sulfite to the developer is allowed. And improve dramatically. However, the conventionally known hydrazine compound has a drawback of processing solution fatigue, which is caused by the fact that the hydrazine compound flows out into the developing solution during the development processing, and the change to other photographic light-sensitive materials becomes large. In addition, the conventional ultra-high contrast system using a hydrazine compound requires a developer having a relatively high pH, for example, 11.5 or 11.8, which increases the handling risk, and the waste solution treatment requires BO.
There are problems such as high D and COD. Also, p of the developing solution
Since it is necessary to use a large amount of a pH buffering agent for keeping H constant, the solid content concentration of the developing solution becomes high, and the solution becomes sticky and is difficult to wipe off when scattered. Therefore, there has been a demand for the development of a hydrazine compound capable of increasing the contrast with a developer having a lower pH. In addition, the contrast enhancement system using hydrazine has a problem that spot-like fog called black spots, which is seen in the unexposed area, which is induced by the infectious development mechanism, occurs, and the development of a hydrazine compound with extremely few black spots has been developed. Has been desired. Japanese Patent Application Laid-Open No. 1-100530 discloses a technique of incorporating a hydrazine compound into a polymer structure for the purpose of providing a high contrast material. However, there is no description about the change of the treatment liquid PH, especially the change of the characteristics at low pH, and the above-mentioned drawbacks are insufficient. Further, the return sensitive material generally handled in a bright room occupies a large field as one of the sensitive materials for plate making, and in this field, high quality of blank characters for reproducing thin Mincho characters is required. Therefore, development of a nucleating agent having higher activity has been desired. In particular, in a low-sensitivity light-sensitive material which can be handled even in a light room, hardening by a nucleating agent hardly occurs, and the development of a more active nucleating agent is desired.

[0003]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide photographic light-sensitive material for plate making which is excellent in rapid processability and has high process stability. A second object of the present invention is to provide a silver halide photographic light-sensitive material for plate making which can be developed at a lower pH.
A third object of the present invention is to provide a silver halide photographic light-sensitive material for plate making, which has little change in photographic performance due to change in developer composition.

[0004]

These objects of the present invention are as follows. First, in a silver halide photographic light-sensitive material, at least one compound having in its molecule a structural part represented by the above chemical formula 1 is used. Achieved by containing. Where A
r represents an optionally substituted aromatic group, R ₁ represents an optionally substituted alkyl group, aryl group, alkoxy group, amino group or heterocyclic group, and Z represents a divalent linking group. Represent Preferably, Z is at least Chemical formula 2 or Chemical formula 3
Is a linking group having.

Secondly, a polymer having at least one silver halide emulsion layer on a support, the polymer having the structural part represented by the above chemical formula 1 in the emulsion layer or the hydrophilic colloid layer, and a tertiary in the molecule. It was made by containing a contrast enhancing compound having an amino group.

Thirdly, a polymer having at least one silver halide emulsion layer on a support and having the structural part represented by the above chemical formula 1 in the emulsion layer or the hydrophilic colloid layer and the above-mentioned molecule in the molecule. It was achieved by containing a polymer having a structural part represented by Chemical formula 4. In the formula, R ₄ and R ₅ represent optionally substituted alkyl groups, which may be the same or different and may form a ring with each other. L is an organic linking group.

The contents will be described below in order. In the formula of Chemical formula 1, Ar is, for example, a methyl group, an ethyl group, i
-A divalent aromatic group which may be substituted with a propyl group, a methoxy group, an ethoxy group or the like, and a phenylene group is preferable as the aromatic ring. R ₁ is an optionally substituted alkyl group, for example, methyl group, ethyl group, propyl group, octyl group, ethylhexyl group, chloroethyl group,
Bromoethyl group, methoxyethyl group, diethylaminoethyl group, benzyl group, phenethyl group, hydroxyethyl group, hydroxypropyl group, 3-diethylaminopropyl group, 3-N, N-dibutylaminopropyl group, cyclohexyl group, pyridin-2-yl -Methyl group, bromo-
1-methylpyridinium-2-yl-methyl group and the like, and the aryl group includes, for example, phenyl group, tolyl group, xylyl group, p-methoxyphenyl group, o-ethoxyphenyl group, naphthyl group and the like, alkoxy. Examples of the group include an ethoxy group, a methoxy group and a phenoxy group, and examples of the amino group include anilino group, toluidino group, anisidyl group, ethylamino group, propylamino group, diethylamino group, dimethylamino group, 2-N, N.
-Diethylaminoethylamino group, 2-N, N-dipropylaminoethylamino group, 3-N, N-diethylaminopropylamino group, 3-hydroxypropylamino group, 2,3-dihydroxypropylamino group, pyridine-2- Yl-methylamino group, pyridin-4-yl-methylamino group, tosyl-1-methylpyridinium-2-
Yl-methylamino group, tosyl-3-methylimidazolium-1-yl-methylamino group, pyridin-2-yl-amino group, pyridin-3-yl-amino group, pyrimidin-2-yl-amino group, pyrrole Examples thereof include a 1-yl-amino group, a 3-N-morpholinopropylamino group, and a 3-N-pipecorinopropylamino group, and examples of the heterocyclic group include a pyrrole ring, a pyrroline ring, a pyrrolidine ring, a pyrazole ring, and a pyrazoline ring. , Ring-forming nitrogen atom-bonding groups such as imidazole rings, tosyl-3-methylimidazolium-1-yl group, etc., and Z is ureido group, thiourea group, sulfonamide group, carbamoyl group, etc. The
Preferred is a divalent linking group having at least Chemical formula 2 or Chemical formula 3.

R ₂ in the formula ₂ represents a hydrogen atom, a lower alkyl group such as a methyl group or an ethyl group, and R ₃ in the formula ₃ also represents R _2.
Is synonymous with and may be the same or different.

Next, the monomers having the structural part represented by Chemical Formula 1 (which will be referred to as hydrazine monomers) used in the present invention will be listed, but the present invention is not limited thereto.

[0010]

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[0011]

[Chemical 6]

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

Embedded image The hydrazine monomer is then used as a homopolymer or a copolymer with other monomers. When used as a copolymer, the monomer copolymerizable with the present monomer may be a commonly used copolymerizable monomer such as acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, Nt-butylacrylamide, N-dimethylaminopropylacrylamide, N-
Acroylmorpholine, N, N-diethylacrylamide, N-hydroxyethylacrylamide, N-dibutylaminoethylacrylamide, N-vinylpyrrolidone, 1-vinylimidazole, (meth) acrylic acid,
(Meth) acrylic alkyl ester (C ¹ -C ²⁰ ), hydroxyethyl acrylate, diacetone acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 3- [methacryloylaminopropyl] trimethylammonium chloride, diallyldimethylammonium chloride, acrylonitrile , Crotonic acid, itaconic acid, styrene, sodium styrene sulfonate, maleic anhydride and the like.

The proportion of the hydrazine monomer in the polymer used in the present invention (referred to as hydrazine polymer) is 20 to 100% by weight, preferably 30.
１００100% by weight. When this ratio is low, the effect of promoting the contrast enhancement becomes weak, and the amount of addition necessary for promoting the contrast enhancement becomes excessive, which is not preferable.

The polymer used in the present invention can be produced according to a usual vinyl polymerization method. That is, a polymerization initiator is added to a solution of a single vinyl monomer or a mixture of several vinyl monomers in a nitrogen gas atmosphere and heated, or a solution containing the polymerization initiator is maintained at a certain temperature, and the monomer mixture is dropped therein. Can be obtained. Solvents used for polymerization are water, methanol, ethanol,
Alcohols such as isopropanol, dioxane, T
HF, DMF, DMSO and the like are used, and water, ethanol, dioxane, DMF and the like are preferable. A mixture of these solvents is also used. As the polymerization initiator, generally known initiators can be used, such as ammonium persulfate, potassium persulfate, benzoyl peroxide, and AIB.
N, 2,2'-azobis (2-amidinopropane) dihydrochloride, cumene hydroperoxide and the like. The average molecular weight of the polymer of the present invention is in the range of about 500 to 300,000, and preferably 1,000 to 200,000.

Specific examples of typical hydrazine polymers relating to the present invention will be given below, but the present invention is not limited thereto.

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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The hydrazine polymers of the present invention are suitable water-miscible organic solvents such as alcohols (methanol,
It can be used by dissolving it in ethanol, propanol etc.), ketones (acetone, methyl ethyl ketone etc.), N, N-dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. Also, by an already well-known emulsification dispersion method, dimethyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl terephthalate, and dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion. It can also be created and used. It can also be used by a method known as a solid dispersion method using a colloid mill, a ball mill or ultrasonic waves.

The silver halide used in the light-sensitive silver halide emulsion layer 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 silver chloride and salt are used as the kind of silver halide. Although silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used, when silver iodobromide or silver chloroiodobromide 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 and the like of the silver halide grains are not particularly limited, but the grain size is 0.7
Submicron ones are preferred. The silver halide emulsion is
Gold compounds such as chloroaurate and gold trichloride, rhodium,
The sensitivity can be increased with a sulfur compound that reacts with a salt of a noble metal such as iridium or a silver salt to form silver sulfide, or a reducing substance such as a stannous salt or amines without coarsening the particles. Further, an iron compound such as a salt of a noble metal such as rhodium or iridium or a red blood salt may be allowed to be present during physical ripening or nucleation of silver halide grains.
In particular, the addition of a rhodium salt or a complex salt thereof is preferable because the effect of the present invention of achieving ultra-high contrast photographic properties in a short development time is further promoted.

In the present invention, the surface latent image type silver halide emulsion means an emulsion composed of silver halide grains having a surface sensitivity higher than the internal sensitivity, and this emulsion is preferably US Pat. No. 4,224,224. It has a difference between the surface sensitivity and the internal sensitivity defined in the specification of No. 401. It is desirable that the silver halide emulsion be monodisperse, and in particular, the above-mentioned US Pat.
An emulsion having the monodispersity defined in No. 224,401 is preferable. 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 from 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 0.5 μm or less, particularly preferably 0.1 to 0.4 μm. The shape of the silver halide grains may be a regular one such as cubic or octahedral, or a mixed crystal, but it is preferably a so-called monodisperse emulsion having a relatively narrow grain size distribution. The term "monodisperse emulsion" as used 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. However, for the purpose 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 particles is particularly preferable. The silver halide emulsion thus prepared may or may not be chemically sensitized. From the viewpoint of improving the handleability in a safelight environment, which can be called a bright room, it is chemically sensitized. It is rather preferable that it is not sensitized. In the case of chemical sensitization, ordinary sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization (eg gold sensitization) and the like are used.

In the light-sensitive material of the present invention, the hydrazine polymer compound is preferably contained in the surface latent image type silver halide emulsion layer, but is contained in the hydrophilic colloid layer adjacent to the surface latent image type silver halide emulsion layer. You may let me. Such a layer may be a layer having any function such as a subbing layer, an intermediate layer, a filter layer, a protective layer and an antihalation layer. The amount of the hydrazine polymer compound added in the layer is
The appropriate addition amount may vary over a wide range, although it varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, but it is preferably 10 ^{−3 to 2} g / m ² .

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
It is a dye belonging to a cyanine dye, a merocyanine dye, and a complex merocyanine dye. 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. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 17643 (1978).
Issued December 2012) Page 23, IV, Section J.

As the binder or protective colloid that can be used in the emulsion layer or the intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyacetal partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and various kinds of synthetic hydrophilic polymer materials such as copolymers such as polyvinylimidazole can be used. . As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, an enzyme-treated gelatin as described in P30 (1966) may be used, or a hydrolyzed product or an enzymatically decomposed product of gelatin may be used.

The photographic emulsion used in the present invention contains various compounds such as nitroimidazoles for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Azoles such as nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo Compounds conventionally known as antifoggants or stabilizers such as compounds, azaindenes and benzothiazolium salts can be contained. Among these, particularly preferable are benzotriazoles (such as 5-methylbenzotriazole) and nitroindazoles (such as 5-nitroindazole). These compounds may be contained in the processing solution.

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.) alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may include 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). A surfactant may be included for various purposes such as acceleration, contrast enhancement, and sensitization. For example, saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl) Amines or amides, polyethylene oxide adducts of silicone, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride,
Alkylphenol polyglycerides), nonionic surfactants such as fatty acid esters of polyhydric alcohols, alkyl esters of sugars, alkyl carboxylate, alkyl sulfate, alkyl benzene sulfonate,
Alkyl phosphates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc., carboxy, sulfo, phospho, sulfate, phosphate Surfactants containing acidic groups such as groups, amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium Cationic surfactants such as heterocyclic quaternary ammonium salts such as 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, olefins, styrene and the like alone or in combination, or acrylic acid,
A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

The light-sensitive material of the present invention may contain an organic desensitizer. Preferred organic desensitizers have at least one water-soluble group or alkali-dissociable group. These preferable organic desensitizers are exemplified in JP-A-63-64039. When an organic desensitizer is used, the silver halide emulsion layer contains 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / m ² ,
Preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻⁵ mol / m ²
It is appropriate to make it exist.

The emulsion layer of the present invention or the other hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further lowering photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and safety against safelight light when handled as a light-sensitive room light material Mainly from 310 nm to 600 n
A dye having substantial light absorption in the m region is used. These dyes may be added to the emulsion layer depending on the purpose, or may be added together with a mordant to the upper portion of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther than the silver halide emulsion layer with respect to the support. It is preferable to use it after fixing.
It depends on the molar extinction coefficient of the dye, but usually 10 ^{-3 to 1} g /
It is added in the range of m ² . Preferably 10-500 mg
/ M ² . The dye is a suitable solvent (for example, water, alcohols such as methanol and ethanol, acetone,
It can be dissolved in methyl cellosolve or the like or a mixed solvent thereof and added to the coating solution. These dyes can be used in combination of two or more. Specific examples of these dyes are described in JP-A-63-64039. In addition, U.S. Pat. Nos. 3,314,794, 3,352,681 and 3,499,762,
No. 3,533,794, No. 3,700,455
No. 3,705,805, No. 3,707,37
5, No. 4,045,229, JP-A-46-278.
No. 4, West German Patent Application Publication No. 1,547,863, and JP-A-2-293839 are also used. Others, US Pat. No. 2,274,78
No. 2, JP-A Nos. 62-185755 and 63-2045.
Pyrazolone oxonol dyes described in US Pat. No. 2,956,879, diarylazo dyes described in US Pat. Nos. 2,956,879, and US Pat. Nos. 3,423,207 and 3,384,48.
No. 7, styryl dyes and butadienyl dyes, US Pat. No. 2,527,583, merocyanine dyes,
U.S. Pat. Nos. 3,486,897 and 3,652,2
No. 84, No. 3,718,472, merocyanine dyes and oxonol dyes described in U.S. Pat.
No. 61, enaminohemioxonol dyes described in British Patent Nos. 584,609 and 1,177,429,
JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, U.S. Pat. No. 2,533,472
No. 3,148,187, No. 3,177,07
No. 8, No. 3,247,127, No. 3,540,8
No. 87, No. 3,575,704, No. 3,653.
905 and JP-A-62-133453 can also be used.

To obtain ultrahigh contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional lith developer or pH 13 described in US Pat. No. 2,419,975 is used.
It is not necessary to use a highly alkaline developer close to the above, and a stable developer can be used. That is, for the silver halide photographic light-sensitive material of the present invention, a developer containing sufficient sulfite ion as a preservative (especially 0.15 mol / l or more) can be used, and a pH of 9.5 or more, Especially 10-11.
With the developing solution of No. 5, a sufficiently high-contrast negative image can be obtained. There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1). -Phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol), etc. can be used alone or in combination. The silver halide light-sensitive material of the present invention is particularly suitable to be processed with a developer containing dihydroxybenzenes as a main developing agent and 3-pyrazolidones or aminophenols as an auxiliary developing agent. Preferably, the developer contains 0.05 to 0.5 of dihydroxybenzenes.
Mol / liter, 3-pyrazolidones or aminophenols are used together in the range of 0.06 mol / liter or less.

Further, as described in US Pat. No. 4,269,929, by adding amines to the developing solution, the developing speed can be increased and the developing time can be shortened. The developer may also include other pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates,
Development inhibitors such as bromides, iodides and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles) or antifoggants can be contained. Further, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), a defoaming agent, a hardener, and a silver stain preventing agent for the film. (For example, 2-mercaptobenzimidazole sulfonic acids, etc.) may be included. The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C. Although it is preferable to use an automatic processor for photographic processing, the total processing time from putting the light-sensitive material into the automatic developing machine until it comes out is 90 to 12 by the method of the present invention.
Even if it is set to 0 second, a photographic characteristic of a super gradation of negative gradation can be obtained. In the developer of the present invention, compounds described in JP-A-56-24347 can be used as a silver stain inhibitor. As a solubilizing agent to be added to a developer, JP-A-61-61
Compounds described in -267759 can be used. Further, as a pH buffer agent used in a developing solution, JP-A-60-
The compound described in Japanese Patent No. 93433 or JP-A-62-18
The compounds described in No. 6259 can be used.

Next, as another means of constituting the present invention, the contrast enhancement promoting compound described in claim 3 will be described. Although the background of the technology for obtaining the high-sensitivity light-sensitive material has been described above, attempts have been proposed to further enhance the higher-tone. For example, JP-A-60-179734, JP-A-62-948, US Pat. No. 4,385,108,
4,269,929, 4,988,604, 4,994,365, 5,1
Although attempts have been made to make the hydrazine compound more active as disclosed in No. 04,769, improvement of only the hydrazine compound has a limit in increasing the contrast at low pH. Therefore, the development of a contrast enhancing agent has been conventionally advanced. JP-A-56-106244, 60-218642,
No. 61-267759, a method of adding a secondary or tertiary amino compound to a developing solution, JP-A-60-1
40340, 62-22241, 63-124045, U.S. Pat.
A method of adding an amino compound as disclosed in Japanese Patent No. 975,354 to a light-sensitive material is known. However, none of them have a satisfactory high contrast property, must be used in a large amount, or have a drawback that the change in photographic performance becomes large when the composition of the developer changes due to running or air oxidation. However, the development of a more effective accelerator has been desired.

In order to improve these points, the present inventors combined the hydrazine polymer described in claim 1 with a compound having a tertiary amino group in the molecule, or described the hydrazine polymer and claim 4. This can be achieved by the combined use of the polymer having the structure of Chemical Formula 4 (which is referred to as a contrast enhancing accelerator polymer for short) as an accelerator polymer.

Next, representative ones of the contrast enhancing accelerators having a tertiary amino group are exemplified, but not limited thereto.

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These accelerators are suitable solvents (water, alcohols such as methanol and ethanol, acetone, N,
It is dissolved in N-dimethylformamide, methyl cellosolve, etc.) and added to the coating solution. You may use these additives together in multiple types. The amount of the high-contrast accelerator having a tertiary amino group added to the light-sensitive material varies depending on the optimum amount, but it is preferably in the range of 10 ^{−3 to 5} g / m ² .

Next, in the formula 4 in the accelerator polymer described in claim 4, R ₄ and R ₅ are alkyl groups which may be substituted, for example, methyl group, ethyl group, propyl group,
Examples thereof include a butyl group, an ethylhexyl group, an octyl group, a cyclohexyl group, a phenethyl group and the like, and a pyrrolidine ring and a piperidine ring in which R ₄ and R ₅ are condensed to form a ring. L
Represents a divalent linking group, for example, an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a phenylene group, an arylene group such as a naphthylene group, an ethyleneoxy chain or a repeating unit of a propyleneoxy chain is 2 to
Examples thereof include polyalkyleneoxy groups having 30 groups.

Representative examples of the accelerator polymer containing these chemical formulas 4 are illustrated, but not limited thereto.

[0051]

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[0053]

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The accelerator polymers listed above are used as homopolymers or copolymers with other monomers. The polymerization form, the kind of the copolymerized monomer, the ratio of the monomer in the copolymer, the molecular weight and the like are the same as those in the case of the hydrazine polymer described above. The amount of these accelerator polymers added to the light-sensitive material varies depending on the optimum amount, but it is preferably in the range of 10 ^{−3 to 5} g / m ² . The active ingredient as an accelerator for these polymers can be obtained by using the following monomer (this is referred to as accelerator contrast monomer for short). Representative examples of this accelerator monomer are exemplified, but not limited to these.

[0055]

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[0056]

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Next, a synthesis example of the hydrazine polymer of the present invention will be shown. Synthetic Example (Exemplified Hydrazine Polymer HP-2) 6.0 g of the hydrochloride salt of the exemplified hydrazine monomer HM-5 and 4.0 g of acrylamide were added to 30 ml of water and 60 m of ethanol.
It was dissolved in 1, and 0.1 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the mixture was stirred under a nitrogen stream at 65 ° C for 4 hours to obtain a viscous polymer solution. The solution is poured into acetone to precipitate a white solid polymer. From the result of GPC measurement, the average molecular weight was about 25,000. Other polymers can be similarly synthesized.

[0058]

[Example 1]

1) Preparation of coating sample 5.0 × / mol of silver was added to an aqueous gelatin solution kept at 40 ° C.
The aqueous solution of silver nitrate and the aqueous solution of sodium chloride were simultaneously mixed in the presence of 10 ⁻⁶ mol of (NH ₄ ) ₃ RhCl ₆ , and then the soluble salt was removed by a method well known in the art, followed by addition of gelatin, followed by chemical treatment. 2-Methyl-4-hydroxy-1,3,3a, 7-tetraazaindene was added as a stabilizer without aging. This emulsion has an average grain size of 0.
It was a monodisperse emulsion having a cubic shape of 2 μm. In this emulsion, the polymer hydrazine compound of the present invention shown in Table 1 and the following chemical formulas 28, 29 and 30 are shown in Table-1.
Then, polyethyl acrylate latex was added in an amount of 30 wt% with respect to gelatin based on solid content, 1,3-divinylsulfonyl-2-propanol was added as a hardening agent, and 3.8 g / m 2 was added on the polyester film. A of ²
It was applied so that the amount would be g. Gelatin was 1.8 g / m ² . 1.5g of gelatin as a protective layer on this
m ² , polymethyl methacrylate 0.3 with particle size 2.5μ
A layer of g / m ² was applied.

[0059]

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[0060]

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[0061]

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2) Evaluation of Photographic Property The coating sample thus obtained was imagewise exposed with a bright room printer P-627GA manufactured by Dainippon Screen Co., Ltd., and developed with a developer-1 having the following composition at 35 ° C. for 30 seconds. It was fixed with a fixing solution PURCF901 from Paper Manufacturing Co., Ltd., washed with water and dried. Table 1 shows the results of evaluating the contrast, Dmax, and the image quality of the extracted characters of each sample. The contrast indicating the degree of contrast of the image is the slope of the linear portion of the characteristic curve (optical density 0.1 to 2.
It is represented by the tan θ of 5), and if it is 10 or less, the hardness is insufficient and it is not practical. Character quality 5 is 50% using halftone originals
Is an image quality in which a character having a width of 30 μm is reproduced when properly exposed so that the halftone dot area is 50% of the halftone dot area on the reversal light-sensitive material. On the other hand, when the appropriate exposure is applied, which is the same as the blank character image quality, 150 μm
It is an uncharacteristic character quality that can not reproduce the image quality that can reproduce only characters over the width, and it is 4 between 5 and 1 by sensory evaluation.
A rank of ~ 2 has been set. Three or more is a practical level. Similarly, Dmax is 50% of the original and halftone dot area is 50%.
Is the maximum density when exposed so that the halftone dot area becomes.

[Developer-1] Hydroquinone 30.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-plaseridine 0.3 g Sodium sulfite 75.0 g EDTA.2Na 1.0 g Tripotassium phosphate 80.0 g Potassium bromide 2.0g Sodium hydroxide 13.0g 5-Methylbenzotriazole 0.3g 1-Diethylamino-2,3-diethylpropoxypropane 17.0g Sodium p-toluenesulfonate 7.0g Water was added 1 liter Hydroxyl Adjust to pH 11.5 with potassium.

[0064]

[Table 1]

From the results shown in Table 1, it can be seen that the polymer hydrazine having the chemical formula 1 has a high contrast even when the contrast enhancing agent is not added, the density of the nuclear image is easily attached, and the quality of the extracted character image is excellent.

Example 2 The amount of the polymer hydrazine compound shown in Table 2 was added to the emulsion of Example 1, and E-5 and E- were added as the contrast enhancing accelerator having a tertiary amino group.
The same procedure as in Example 1 was carried out except that 100 mg of 7 was used, and coating was performed. Then, the following developing solution-2 is used to form Example 1.
It evaluated by the same criteria as. Table 2 shows the results.

[Developer-2] Hydroquinone 65 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-phenolidone 2.9 g Sodium pyrosulfite 145 g EDTA.2Na 6.0 g Boric acid 6.9 g Potassium hydroxide 80 g Water Sodium oxide 23 g 1-Phenyl-5-mercaptotetrazole 0.05 g Sodium bromide 12 g 5-Methylbenzotriazole 0.4 g Potassium carbonate 80 g Diethylene glycol 120 g Water was added to 1 liter The above concentrate was added to 1 part to 4 parts of water. PH diluted with a ratio
The developer was 10.4.

[0068]

[Table 2]

From the results shown in Table 2, when the contrast enhancing accelerator is added to the polymer hydrazine having the chemical formula 1 of the present invention, the contrast and Dmax are higher than those when the contrast enhancing accelerators other than the present invention are added, and It can be seen that the extracted character image quality is still superior.

Example 3 The amount of the polymer hydrazine compound shown in Table 3 was added to the emulsion in Example 1, and the accelerator polymer of the present invention (AP-exemplified as an example) was added to each sample as a contrast increasing accelerator. 3 and 4) were added so that the coating amount was 0.3 g / m ² , and the same preparation and coating as in Example 1 were carried out. And it evaluated by the same criteria as Example 2. Table 3 shows the results.

[0071]

[Table 3]

From the results shown in Table 3, even in the case of adding the contrast enhancing polymer having the chemical formula 2 to the polymer hydrazine having the chemical formula 1 of the present invention, compared with the case of adding the hydrazine other than the present invention, Furthermore, the contrast is high and Dma
It can be seen that x and the extracted character quality are also maintained at a high level.

Example 4 A monodisperse silver chloride emulsion containing iridium and having an average particle size of 0.23 μm was prepared by the double jet method, and 6-methyl-4-hydroxy-1,
1,3 g of 3,3a, 7-tetrazaindene / Ag1 mol
Was added. Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxidepyridinium was added as a sensitizing dye at 300 mg / Ag of 1 mol. Table 4 and 5 into it
The hydrazine polymer of the present invention (HP-
2), 4), 15), and 19)), the coating amount is 0.3 g / m ²
Add so that As comparative samples, hydrazine compound chemical compounds 29 and 30 were added so that the coating amounts would be the same. After that, E-5 and AP-4 were added to each sample as a contrast enhancing agent so that the coating amount was 0.2 g / m ² . Furthermore, 1,
3-divinylsulfonyl-2-propanol was added, and the amount of silver was 3.5 g on the polyethylene terephthalate film.
It was applied so as to be / m ² . A gelatin layer of 1.5 g / m ² was coated thereon as a protective layer. The sample thus obtained was exposed by a printer using a tungsten lamp as a light source through an optical wedge. Then, the following developer [Developer-2] was prepared, and development was carried out at 35 ° C. for 1 minute with a solution in which the pH was adjusted to the values shown in Tables 4 and 5 with an aqueous sodium hydroxide solution and sulfuric acid, I saw changes in contrast, black spots, and halftone dot image quality. The halftone dot image quality is a subjective measure, and is divided into 5 levels, 1 being extremely poor and 5 being extremely good, and 3 or more being a level that can be practically used. Also, the black spots (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 was set to a practically usable level. . The results are shown in Table 4.

[Developer-2] Hydroquinone 65 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-parasidone 2.9 g Sodium pyrosulfite 145 g EDTA.2Na 6.0 g Boric acid 6.9 g Potassium hydroxide 80 g Water Sodium oxide 23 g 1-Phenyl-5-mercaptotetrazole 0.05 g Sodium bromide 12 g 5-Methylbenzotriazole 0.4 g Potassium carbonate 80 g Diethylene glycol 120 g Water was added to 1 liter The above concentrate was added to 1 part to 4 parts of water. PH diluted with a ratio
The developer was 10.4.

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[Table 4]

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[Table 5]

From the results of Tables 4 and 5, when the accelerator polymer was added (No. 79 to 101) in the combined use of the hydrazine polymer of the present invention and the contrast enhancing accelerator,
Compared to the comparisons (Nos. 102 to 113), the fluctuation of the contrast is small with respect to the change of PH, and a stable degree of contrast is shown. Moreover, the number of black spots was smaller than that of the comparative compound, which is favorable. Looking at the halftone dot image quality, the present invention provides stable image quality with respect to PH changes. On the other hand, the comparison shows that the deterioration of the image quality with respect to the PH is deteriorated especially with the low PH processing.

[0078]

INDUSTRIAL APPLICABILITY In a super-high contrast image forming method using a silver halide photographic light-sensitive material, (1)
Polymers having a hydrazine structure represented by: (2) By using these polymers in combination with a contrast enhancing agent, a contrast of high contrast and a high image density are provided, and stable even against changes in the pH of the developer. It is possible to obtain a good light-sensitive material which can obtain the contrast and quality and has little black spots.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one compound having a structural part represented by the following chemical formula 1 in a polymer molecule. Embedded image In the formula, Ar represents an aromatic group which may be substituted, and R
₁ represents an optionally substituted alkyl group, aryl group, alkoxy group, amino group, or heterocyclic group, and Z represents a divalent linking group. 2. In the chemical formula 1, Z is at least the chemical formula 2.
2. The silver halide photographic light-sensitive material according to claim 1, which is a linking group having the chemical formula 3. Embedded image In the formula, R ₂ represents a hydrogen atom or a lower alkyl group. Embedded image In the formula, R ₃ has the same meaning as R ₂ and may be the same or different. 3. A polymer having at least one silver halide emulsion layer on a support, wherein the emulsion layer or the hydrophilic colloid layer has a structural part represented by Chemical formula 1, and a tertiary amino group in the molecule. A silver halide photographic light-sensitive material, comprising: 4. A polymer having at least one silver halide emulsion layer on a support, wherein the emulsion layer or the hydrophilic colloid layer has a structural part represented by the chemical formula 1 and the following chemical formula 4 in the molecule. A silver halide photographic light-sensitive material comprising a polymer having a structure shown. Embedded image In the formula, R ₄ and R ₅ represent optionally substituted alkyl groups, which may be the same or different and may form a ring with each other. L is an organic linking group.