JPH09304858A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sliver halide photographic sensitive material which has characteristics with enough high contrast and suppresses production of black spots even when it is processed with a developer of pH<11.0. SOLUTION: This photosensitive material has at last one photosensitive silver halide emulsion layer on a base body. The silver halide emulsion layer or other hydrophilic colloid layers contain at least one kind of polymer compd. having a structure expressed by formula I and at least one compd. expressed by formula II. In formula I, R<1> , R<2> , R<3> are alkyl groups or the like which may have substitutents, X is an anion, and L is a connecting group. In formula II, both of A1 , A2 are hydrogen atoms or one is a hydrogen atom and the other is a sulfonyl or acyl group, R1 is an aliphatic group, etc., G1 is a carbonyl group, etc., R2 is a substd. Alkyl group having at least one electron withdrawing group substituted for the carbon atom where G1 is substituted.

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 more particularly to a silver halide photographic light-sensitive material used mainly in the printing plate making industry and capable of stably forming a super-high contrast negative image. Is.

[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 a high-contrast photographic property by using a stable developing solution, US Pat. Nos. 4,166,742, 4,168,977, 4,211,857, and 4, No. 224,401, 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.

JP-A-56-106244 further improves a high contrast image forming method using the hydrazine compound.
It has been proposed to add an amine compound to the developer in order to obtain a negative image with a high gamma value in a lower pH developer. Further, JP-A-61-167939 and JP-A-4-62544 disclose that the addition of a quaternary phosphonium salt compound to a developing solution improves the contrast. However, when these are added to a developing solution and used, there are problems such as odor of the solution and stains due to adherence to equipment used, or environmental pollution due to waste solution.

JP-A-60-140340 discloses that the addition of amines to a silver halide photographic light-sensitive material improves the tonality, but when developing with a developer having a pH of less than 11.0. In the above, sufficient contrast cannot be expressed. JP-A-62-250439, and JP-A-62-250439
No. 280733 discloses that a hydrazine derivative and a quaternary onium salt compound are used for processing with a developer having a pH of 11 or more to form a high contrast image. Further, in JP-A-61-47945, JP-A-1-179930 and JP-A-2-2542, an emulsion containing 50 mol% or more of silver bromide, a specific hydrazine derivative and a quaternary onium salt compound are used to adjust the pH to 11 It is disclosed that the above-mentioned developing solution is used to form a high-contrast image. However, in order to fully exhibit the high-contrast effect of the hydrazine compound, it is necessary to adjust the pH to 1
Since a developing solution having a high pH of 1.0 or more is required, the developing solution is susceptible to air oxidation, and stable ultra-high contrast photographic characteristics cannot be obtained, which is a more effective image forming system. Was required.

Therefore, development of a light-sensitive material has been carried out for realizing high-contrast development with a developing solution having a lower pH. In JP-A-4-511143, JP-A-4-56949 and JP-A-4-62544, a photosensitive material containing a specific hydrazine derivative, an amine, a hydrazine and a quaternary onium compound is treated with a developer having a pH of 10.4 to 10.8. Is disclosed. The specification describes that a high-contrast image with a gamma of 10 or more can be obtained by using a specific hydrazine derivative and a specific accelerator in a silver iodobromide emulsion system. JP 6
No. 313937, a sensitizer containing a hydrazine derivative and a phosphonium salt in an emulsion system having a silver chloride content of 50 mol% or more, and in JP-A No. 7-36139, a hemicyanine dye having an acidic group-substituted alkyl group is spectrally sensitized. To a silver halide emulsion system containing a hydrazine derivative and a bispyridinium compound or a phosphonium compound.
Processing with a H10.5 developer is disclosed.
However, the contrast enhancement system using hydrazine
The problem is the generation of spots of fog called black spots that occur in the unexposed areas that are induced by the infectious development mechanism. It has been desired to develop a more effective contrast enhancer which retains photographic properties such as excellent halftone dot reproducibility even when the composition or pH changes.

On the other hand, in recent years, in the printing field, there has been a demand for improving the efficiency of the returning work process due to the complexity of printed materials and the development of scanners. For this reason, a photographic film with a low sensitivity of about 10 ^-4 to 10 ^-5 has been developed as compared with a return film conventionally used, and a return film that can be handled in a bright room (under a white fluorescent lamp excluding ultraviolet rays). It is practically used as a film, that is, a light-sensitive material for a bright room. The performance required of such a light-room photosensitive material is that it can be handled for a long time in a bright room, has high sensitivity to a printer light source, and also has the conventional dark-room photosensitive material. To have a sufficient maximum density at a moderate or higher contrast.

However, when an attempt is made to obtain a low-sensitivity light-sensitive material for a bright room having a high contrast and a sufficient maximum density by using a hydrazine compound, for example, JP-A-60-830.
No. 28 and No. 60-162246 disclose silver halide light-sensitive materials containing a water-soluble rhodium salt.
Addition of a rhodium salt in an amount sufficient to reduce the sensitivity hinders the contrast enhancement by the hydrazine compound. Fine graining of silver halide is also effective for obtaining a sufficient maximum concentration with low coating amount of silver with low sensitivity, but fine graining of silver halide also hinders high contrast due to hydrazine compound. It has the drawback that pH is 1
There is a demand for an image forming system for a light-sensitive material for a bright room, which is capable of obtaining stable ultra-high contrast photographic characteristics when processed with a stable developing solution of 1.0 or less.

[0008]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a halogenated compound having sufficiently high photographic characteristics even when processed with a developer having a pH of less than 11.0 and suppressing the generation of black spots. It is to provide a silver photographic light-sensitive material.

Secondly, an object of the present invention is to provide a light-sensitive photographic light-sensitive material for a bright room, which has a photographic characteristic of sufficiently high contrast even when processed with a developer having a pH of less than 11.0 and which can be handled in a bright room for a long time. Is to provide.

A third object of the present invention is to provide a silver halide photographic light-sensitive material having a small change in photographic characteristics such as gamma and sensitivity even when treated with a fatigued developer.

[0011]

The above objects of the present invention are to provide at least one photosensitive silver halide emulsion layer on a support, the silver halide emulsion layer or another hydrophilic colloid layer. A silver halide photographic light-sensitive material characterized by containing at least one polymer compound having a structural part represented by the following general formula (1) and at least one compound represented by the following general formula (2) To be achieved.

[0012]

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[In the general formula (1), R ¹ , R ² and R ³ represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group which may have a substituent. X represents an anion and L represents a linking group. ]

[0014]

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[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 heterocyclic group. And 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 substitution in which the carbon atom substituted with G ₁ is substituted with at least one electron withdrawing group. Represents an alkyl group. ]

The polymer having the structure of the general formula (1) used in the present invention will be described in detail below. In the general formula (1), R ₁ , R ₂ , and R ₃ may be the same or different, and the alkyl group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, or hexyl. Examples thereof include linear or branched ones such as group, heptyl group, 2-ethylhexyl group, octyl group, dodecyl group, benzyl group and phenethyl group, and cyclic alkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group. Examples of the alkenyl group include allyl group, methallyl group and cinnamyl group. As the aryl group, in addition to phenyl group, naphthyl group, etc., alkyl-substituted phenyl group (eg, methylphenyl group, ethylphenyl group, xylyl group, etc.), halogen-substituted phenyl group (eg, fluorophenyl group, chlorophenyl group, bromophenyl group, etc.) , Alkoxy-substituted phenyl groups (eg, methoxyphenyl group, ethoxyphenyl group, etc.), acyl-substituted phenyl groups (acetophenyl group, propiophenyl group, etc.),
Examples thereof include substituted aryl groups such as amino-substituted phenyl groups (aminophenyl group, methylaminophenyl group, dimethylaminophenyl group, etc.), hydroxyphenyl group, nitrophenyl group, methylquinolyl group, methoxyquinolyl group and the like. The heterocyclic group is, for example, a 5- or 6-membered monocyclic or condensed ring containing an oxygen, nitrogen or sulfur atom, and is a furan ring, a thiophene ring, a pyridine ring, a pyrroline ring, a quinoline ring, an oxazole ring, a thiazole ring or an imidazole ring. ring,
Examples thereof include a benzothiazole ring. L is a divalent linking group, for example, a linear or branched or cyclic alkylene group, an oxyalkylene group such as an ethyleneoxy group and a propyleneoxy group, an arylene group such as a phenylene group and a naphthylene group, a carbonyl group, a sulfonyl group. , An oxycarbonyl group, a sulfonyloxy group, a carboxamide group,
Examples thereof include a sulfonamide group and the like, or an organic residue formed by bonding them to each other, preferably a divalent residue containing an oxycarbonyl group, a carboxamide group, a sulfonamide group, a phenylene group, or the like.

Next, specific examples of the structural portion represented by the general formula (1) of the present invention will be shown, but the present invention is not limited thereto.

[0018]

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[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

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[0022]

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Next, the polymer having the general formula (1) used in the present invention is a homopolymer or copolymer of a monomer having a polymerizable unsaturated group, and various (meth) acrylic acid-based monomer units are used. It is preferably composed of
The polymerizable unsaturated monomer containing the general formula (1) in the structural formula can be supplied as a (meth) acrylic acid ester derivative, a (meth) acrylamide derivative, a styrene derivative, an alkene derivative, or the like. Examples of monomers that can be copolymerized with these monomers include those that are hydrophobic (meth).
Acrylic acid alkyl ester (C ₁ ~C _20), (meth)
Benzyl acrylate, acrylonitrile, N-isopropylacrylamide, Nt-butylacrylamide,
For hydrophilic substances such as N-dimethylaminopropyl acrylamide, vinyl acetate, styrene, and chloromethylated styrene, acrylamide, methacrylamide, N, N-
Dimethylacrylamide, N, N-diethylacrylamide, hydroxyethyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, N-acroylmorpholine, crotonic acid, itaconic acid, (meth) acrylic acid, sodium styrenesulfonate,
Examples include commonly used monomers such as vinylimidazole, maleic anhydride, N-vinylpyrrolidone, and derivatives thereof.

The polymer of the present invention can be produced by a conventional vinyl polymerization method. That is, a polymerization initiator is added to a solution of a monomer having the general formula (1) or a mixture of the monomer and a monomer copolymerizable with the monomer under a nitrogen atmosphere, and the mixture is heated or contains a polymerization initiator. It can be obtained by keeping the liquid at a high temperature and dropping the monomer mixture therein. As the solvent used for the polymerization, water, alcohols such as methanol, ethanol and isopropanol, dioxane, THF, DMF and DMSO are used, and water and ethanol are preferable. A mixture of these solvents is also used. As the polymerization initiator, generally known potassium persulfate, benzoyl peroxide, azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (2,4-Dimethylvaleronitrile), cumene hydroperoxide and the like can be used. As another method, a polymer having a reactive group may be synthesized in advance, and a compound having a reactive group containing the general formula (1) in the structural formula may be reacted therewith to obtain the target polymer. The average molecular weight of the polymers of the present invention is between about 500 and 300,000, preferably about 1000 to 200,000. If the molecular weight is too high, the solubility will be reduced and the viscosity will be increased, the amount used will be restricted, and the permeation into the surface of the photosensitive material will be delayed, and it will be difficult to obtain a sufficient effect.

The polymer containing the general formula (1) of the present invention, in comparison with the low molecular weight compound, may be diffused in the light-sensitive material by being polymerized. The tendency is to prevent thickening of the image, crushing of halftone dots, and the like, and there is a feature that the deterioration of image quality is small even when the PH during development is too high. Further, if the PH is too low, there is an advantage that the PH is lower than that of the corresponding low molecular weight compound, in which the contrast is lost probably because the local concentration is high.

It is generally desirable for the polymers of this invention to be hydrophilic in use, and thus it is more desirable that the other monomers in the copolymer be hydrophilic as well. The component ratio of the monomer containing the general formula (1) in the copolymer is 5 to 10
It is 0% by weight, preferably 10 to 100% by weight.
If the component ratio of the monomer is high, the addition amount of the polymer may be small, but it is used in an appropriate range in consideration of easiness of copolymerization with other monomer and solubilization of the polymer.

Next, representative polymers of the present invention will be exemplified, but the present invention is not limited thereto. The value of each monomer unit is% by weight
Represents

[0028]

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[0029]

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[0030]

[Chemical 12]

[0031]

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[0032]

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Next, synthetic examples of the polymer of the present invention will be shown. Synthesis Example (Exemplified Polymer P-7) 6 g of dimethylacrylamide and 4 g of 5-methacryloyloxypentyltriphenylphosphonium-p-toluenesulfonate were mixed with 30 ml of pure water and 4 parts of ethanol.
It is dissolved in 0 ml and stirred and heated under a nitrogen gas stream at an internal temperature of 65 ° C. An initiator 2,2'-azobis (2-amidinopropane) dihydrochloride (45 mg) was added thereto and reacted for 4 hours to obtain a viscous polymer solution. The average molecular weight of this solution was about 30,000. Other polymers can be similarly synthesized.

The polymer compound having the structure represented by the general formula (1) in the light-sensitive material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in any other hydrophilic colloid layer. Good. 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. Content of the polymer compound of the invention in the layer, characteristics of the silver halide emulsion used, since different by chemical structure and development conditions of the compound, a suitable content is can vary over a wide range, 10 ^- A range of ^{2 to 2} g / m ² is practically useful, and more preferably 4 × 10 ⁻² to
A range of 1 g / m ² is preferred.

Next, the general formula (2) will be described in detail below. In the general formula (2), A ₁ and A ₂ are hydrogen atoms, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group, or the sum of σ _p of Hammett is −0.5 or more). Thus substituted phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or the sum of Hammett's σ _p is −
A benzoyl group substituted to be 0.5 or more), or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (substituents include, for example, halogen atom, ether group, sulfonamide group, amide) Group, hydroxy group,
Examples thereof include a carboxy group and a sulfo group. ), And
Most preferably, A ₁ and A ₂ are hydrogen atoms.
The aliphatic group represented by R ₁ is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group. The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.
The heterocyclic group represented by R ₁ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O, and S atoms, which may be a monocyclic ring, May form a condensed ring with an aromatic ring or a heterocyclic ring. The heterocycle is preferably a 5- to 6-membered aromatic heterocyclic group, and includes, for example, a pyridyl group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, a benzthiazolyl group. Those are preferable. R ₁ may be substituted with a substituent, and examples of the substituent include the following. These groups may be further substituted. For example, 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, Examples thereof include a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxy group, an ammonium group, a pyridinium group, a thiuronium group and an isothioureido group. When possible, these groups may be linked to each other to form a ring. Also, R ₁
The compound 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 8 or more carbon atoms and is relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. be able to.

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. R ₂ represents a substituted alkyl group in which a carbon atom substituted with G is substituted with at least one electron withdrawing group, and preferably a substituted alkyl group with two electron withdrawing groups. The electron withdrawing group for substituting the carbon atom substituted with G of R ₂ is halogen, nitro, cyano, nitrosopolyhaloalkyl, polyhaloaryl, alkyl or arylcarbonyl group, formyl group, alkyl or aryloxycarbonyl group, alkylcarbonyl group. Oxy group, carbamoyl group, alkyl or arylsulfinyl group, alkyl or aryl sulfonyl group, alkyl or aryl sulfonyloxy group, sulfamoyl group, phosphino group, phosphine oxide group, phosphonic acid ester group, phosphonic acid amide group, arylazo group, amidino group , An ammonio group, a sulfonio group, an electron-deficient heterocyclic group, and the like. Particularly preferably R ₂ represents a trifluoromethyl group.

Next, 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.

[0038]

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[0039]

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[0040]

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The hydrazine compound of the present invention is described in, for example, JP-A-61-213847, JP-A-62-178246, JP-A-62-180361, JP-A-62-1260153, and JP-A-62-126053.
No. 3-253357, U.S. Pat. No. 4,684,604
No. 3,379,529 and 4,377,63
No. 4, No. 4,332,878, No. 4,937,1
No. 60, Japanese Patent Application No. 63-98803, and the like.

The compound represented by the general formula (2) in the light-sensitive material of the present invention is preferably contained in the silver halide emulsion layer, but may be contained in other hydrophilic colloid layers. The content of the compound represented by the general formula (2) of the present invention in the layer varies depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the developing conditions. About 5 × 10 ^-6 to 8 × 10 ^-2 per mole of silver in the silver halide emulsion.
A molar range is practically useful, more preferably 5x
The range of 10 ⁻⁵ to 1 × 10 ⁻² mol is preferable.

In order to realize high-contrast development with a developing solution having a lower pH, nucleation development accelerators have been conventionally developed. A method of adding a secondary to tertiary amino compound to a developing solution as described in the above-mentioned publicly known documents, JP-A-60-140340, 62-222241 and 63-124045. Method of adding an amino compound as disclosed to a photosensitive layer, JP-A-2-1701
A method of adding an amino compound as disclosed in No. 55 to a photosensitive layer is known. Japanese Patent Application Laid-Open No. 61-1
No. 67939, JP-A-6-313937, etc., a method of adding a quaternary phosphonium salt compound to a developer or a light-sensitive material is disclosed, but all of them are preferred embodiments of the present invention. 90 mol% is silver chloride, and 1 × 10 ⁻⁶ to 1 mol per mol of silver halide.
For a silver halide emulsion containing 2 × 10 ⁻⁴ mol of a water-soluble rhodium salt and having an average silver halide grain size of 0.1 μm or less, a large amount of rhodium salt and a hydrazine compound for fine grain formation are used. Therefore, it becomes more difficult to obtain high-quality photographic characteristics, and a more effective image forming system has been desired. By combining the hydrazine compound of the present invention and a nucleation accelerator, not only in a general emulsion system but also in a system in which such a contrast increase is apt to be inhibited, a strong contrast increasing action is brought about, and a developer which is fatigued is used. The present inventors have found that there is little variation in photographic characteristics such as gamma and sensitivity even after processing.

The silver halide emulsion used in the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide, silver chloride and the like can be used. When silver bromide or silver chloroiodobromide is used, the content of silver iodide is preferably 5 mol% or less. Further, the morphology, crystal habit, size distribution, etc. of the silver halide grains used in the present invention are not particularly limited, but those having an average grain size of 0.7 micron or less, particularly 0.5 micron or less are preferable, and ,
It is preferable that 90% or more of all particles have a particle diameter within a range of ± 10% of the average particle diameter. The silver halide emulsion may be prepared by any known method such as forward mixing, reverse mixing and simultaneous mixing.

In a preferred embodiment, the silver halide used in the photosensitive silver halide emulsion layer of the light-sensitive material of the present invention is silver chloride or silver chlorobromide or silver chlorobromoiodide in which at least 90 mol% is silver chloride. , Silver chloroiodide and the like can be used. More preferably, silver chloride, silver chlorobromide having a silver bromide content of 5 mol% or less, or silver chloroiodide having a silver iodide content of 1 mol% or less is preferred. As the water-soluble rhodium salt used in this photosensitive silver halide emulsion layer, conventionally known ones are used, but typically, rhodium monochloride, rhodium dichloride, rhodium trichloride, rhodium ammonium chloride, etc. are used. To be In general, the water-soluble rhodium salt is preferably used at the time of silver halide precipitation or physical ripening, but may be at any time thereafter. The water-soluble rhodium salt is effective in the range of 1 × 10 ⁻⁶ to 2 × 10 ⁻⁴ mol per mol of silver halide.
Preferably 2 × 10 ⁻⁶ to 1 × per mol of silver halide
A range of 10 ^-4 mol is preferred. Also, with rhodium salt,
An iron compound such as a salt of a noble metal such as an iridium salt or a red blood salt may be allowed to be present during physical ripening or nucleation of silver halide grains.

Further, the preferable average grain size of silver halide used in the light-sensitive silver halide emulsion layer of the above embodiment is 0.1 micron or less. With silver halide grains of 0.1 micron or more, the color tone of the image deteriorates, and it is difficult to obtain a hard tone image having a cold black tone, or when it is used as a light-sensitive material, it is safe. The safety with respect to light is a problem. Here, the particle size can be determined by an ordinary method using an electron microscope, and the average value of the particle size is determined by number average.

The fine graining of the silver halide emulsion grains used in the photosensitive silver halide emulsion layer of the light-sensitive material of the present invention is carried out at 30 ° C. as a mixing condition in the emulsion mixing in the production process.
Mixing at the following temperatures, adding a physical inhibitor, shortening the mixing time, accelerating the addition rate of the silver salt solution and the halogen salt solution, using a continuous mixer, diluting the reaction solution concentration, etc. Although a conventionally known method can be used for producing fine silver halide grains,
A method of mixing at a mixing temperature of ℃ or less is preferable.

The emulsion that has been physically ripened is desalted and then
It is preferable that the coating is performed by adding a necessary additive, but the desalting treatment can be omitted.

The silver halide emulsion used in the present invention is:
Chemical sensitization can be performed by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allyl isothiocyanate, cystine, and rhodanine, U.S. Pat. Nos. 1,574,944, 2,278,947, and 2,410,689, Sulfur-containing compounds as described in Nos. 2,440,206, 3,187,458, 3,415,649, 3,501,313 and the like can be used. Along with sulfur sensitization, US Pat. Nos. 2,448,060 and 2,540,086
Nos. 2,556,245 and 2,566,263 can be used in combination with a sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium or ruthenium. Further, a sensitization method using various gold compounds such as potassium chloroaurate and auric trichloride and a palladium compound such as palladium chloride can be used in combination.

The silver halide emulsion of the present invention can be spectrally sensitized with a dye known as a sensitizing dye in the photographic industry. These dyes include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holo-holer cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxanol 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. The light-sensitive material of the present invention includes
In addition to the photosensitive emulsion layer, an overcoat layer, an intermediate layer, a back coat layer, an undercoat layer and other hydrophilic colloid layers can be provided. These layers may also contain a matting agent.

As the binder or protective colloid that can be used in the emulsion layer, overcoat layer, intermediate layer, backcoat layer and the like of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic substances are used. A sex colloid 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 and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Partial acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric substances such as polyvinyl imidazole and other homopolymers or copolymers can be used.
As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.16, P30 (1
The enzyme-treated gelatin as described in 966) may be used, or a hydrolyzate or an enzymatic hydrolyzate of gelatin may be used.

The photographic emulsion used in the present invention includes known stabilizers such as mercaptotetrazole, mercaptotriazole, benzotriazole and benzimidazole, antifoggants, polyalkylene oxides, thioether compounds and quaternary ammonium salt compounds. Various development accelerators can be contained.

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, storage or photographic processing, or stabilizing photographic performance. . 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.

The photographic emulsion used in the present invention includes an emulsion layer, an overcoat layer, a backing layer, etc. for the purpose of enhancing the image quality due to irradiation, halation and the like, the character removal performance and other performances required in the printing plate making industry. Other hydrophilic colloid layers of can include filter dyes known to those skilled in the art.

Further, in a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (eg , Development acceleration, contrast enhancement, and sensitization) may be included for various purposes. Non-ionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic surface active agent containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group, a phosphoric acid ester group, such as an alkylcarboxylic acid salt, an alkyl sulfuric acid ester, an alkyl phosphoric acid ester, etc. Agents; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters; aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium It can be used cationic surface active agents such as.

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 and other hydrophilic colloid layers 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, methacrylic acid, α A polymer having a monomer component of a combination of β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, and styrenesulfonic acid can be used.

For the photographic light-sensitive material used in the present invention, any support known in the art can be used. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin (for example, polyethylene and polypropylene) laminated paper, polystyrene film, polycarbonate film, and metal plate such as aluminum. These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating by a known method as necessary.

In order to obtain super-high 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, the silver halide photographic light-sensitive material of the present invention can use a developer sufficiently containing (especially, 0.15 mol / l or more) a sulfite ion as a preservative, and has a pH of 9.5 or more. Especially 10.5-1
With the developer of 2.3, a negative image having a sufficiently high contrast can be obtained. There is no particular limitation on the developing agent, and dihydroxybenzenes, 3-pyrazolidones, aminophenols and the like can be used alone or in combination. Other developers include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides, iodides, and organic antifoggants (particularly preferably
Development inhibitors or antifoggants such as nitroindazoles or benzotriazoles). In addition, if necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant, a defoaming agent, a film hardener, a silver stain preventing agent for the film (for example, 2-mercaptobenzimidazoles), etc. May be included. Specific examples of these additives are Research Disclosure 17
No. 6, 17643, etc.

Further, in order to obtain ultrahigh contrast photographic characteristics, the developing solution is disclosed in JP-A-56-106244 and 61-61.
No. 267759, No. 61-230145, No. 62-2
No. 11647, JP-A-2-50150, JP-A-2-208
The amine compounds described in No. 652 and the like can also be added. The representative ones are listed below.

A-1) Nn-butyldiethanolamine a-2) 3-diethylamino-1,2-propanediol a-3) 2-diethylamino-1-ethanol a-4) 2-diethylamino-1-butanol a -5) 3-Diethylamino-1-propanol a-6) Triethanolamine a-7) 3-Dipropylamino-1,2-propanediol a-8) 2-Dioctylamino-1-ethanol a-9) 3 -Amino-1,2-propanediol a-10) 1-diethylamino-2-propanol a-11) n-propyldiethanolamine a-12) 2-di-isopropylaminoethanol a-13) N, N-di-n -Butylethanolamine a-14) 2-methylamino-1-ethanol a-15) 3-dimethylamino-1,2-propanedi A-16) 4-dimethylamino-1-butanol a-17) 1-dimethylamino-2-butanol a-18) 1-dimethylamino-2-hexanol a-19) 5-dimethylamino-1-pen Tanol a-20) 6-Dimethylamino-1-hexanol a-21) 1-Dimethylamino-2-octanol a-22) 6-Dimethylamino-1,2-hexanediol The added amount may be a contrast enhancing amount. Yes, but generally 0.
An amount of 005 to 1.0 mol / l can be added.

In the present invention, a system in which a developing agent is incorporated in a light-sensitive material and processing is carried out with an alkaline activator solution may be adopted. (Japanese Unexamined Patent Publication Nos. 57-129436, 57-129433, 57-129434, and 5)
7-129435, U.S. Pat. No. 4,323,643). The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. It is preferable to use an automatic developing machine for photographic processing. In the present invention, the total processing time from when the photosensitive material is put into the automatic developing machine to when it comes out is from 60 seconds to 120 seconds.
Even if it is set to seconds, a photographic characteristic of a negative tone of a super-high contrast can be sufficiently obtained.

[0062]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the description.

Example 1 <Preparation of emulsion> 5 g of sodium chloride in 600 ml of water,
An aqueous solution containing 40 g of gelatin was used at 40 ° C. to control the pAg to 8.5 by the double jet method, an aqueous solution of silver nitrate, a water-soluble iridium salt of 3.25 × 10 ⁻⁶ mol / mol Ag, and 1.8 × 10 ⁻⁷ mol / mol Ag. A halogen solution containing a water-soluble rhodium salt is mixed to prepare a silver chlorobromide (silver bromide 30 mol%) emulsion having an average particle size of 0.25 μm, which is 0.2 mol% with respect to 1 mol of silver. After adding the potassium iodide aqueous solution as described above, the precipitate was washed with water and redissolved. Sodium thiosulfate (2 mg) and chloroauric acid (4 mg) were added to this emulsion per mol of silver, and the mixture was heated at 55 ° C. for 60 minutes for chemical sensitization.
4-hydroxy-6-methyl-1,3,3 as stabilizer
150 mg of a, 7-tetrazaindene was added. To this emulsion, the compound of Chemical formula 18 was added as a sensitizing dye in an amount of 2.5 × 10 ⁻⁵ mol / mol Ag, and the mixture was divided into the compounds of general formula (2) shown in Table 1 and comparative compounds. 19 was added to 2.5 × 10 ⁻⁴ mol / mol Ag, the polymer compound of the present invention shown in Table 1 was added to 10 ⁻¹ g / m ² , or the compound 20 of the comparative compound was added to 5 × 10 ⁻⁴ mol / mol Ag. , 2-
After adding hydroxy-4,6-dichloro-1,3,5-triazine sodium salt and the surfactant of Chemical formula 21,
5g with silver nitrate on polyethylene terephthalate film
/ M ² and gelatin were coated at 3 g / m ² . <Protective layer> On top of this, as a protective layer, 1 g of gelatin /
m ² , a surfactant, a matting agent and a film hardener were added and coated to prepare the samples shown in Table 1.

[0064]

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[0065]

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[0066]

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[0067]

[Chemical 21]

The sample thus obtained was exposed to xenon flash light through an interference filter of 670 nm and a wedge for sensitometry, and then developed with a developer having the following composition at 35 ° C. for 30 seconds, fixed, washed with water, After drying, gamma was determined. For this processing, an automatic processor (Dainippon Screen Mfg. Co., Ltd., LD-221Q
T) was used. Gamma was measured at tan θ of a linear portion having an optical density of 1.0 to 2.5.

Further, as a black spot test, each sample was developed with the same developer at 35 ° C. for 60 seconds, and the occurrence thereof was examined.
The results are shown in Table 1. Black spots are observed with a magnifying glass of 100 times, and the number of occurrences is visually evaluated on a scale of 5, and those without black spots are set to 5, and 1 represents the worst quality. 5 and 4 are practical, 3 is poor but practically practical, and 2 and 1 are impractical.

<Developer> 1-Phenyl-4-Hydroxymethyl-4-methyl-3-Plasoridone 2.3 g Hydroquinone 85.0 g Sodium hydroxide 26.0 g Sodium carbonate 50.0 g Potassium sulfite 220.0 g Diethylenetriaminepentaacetic acid 9 1 g potassium bromide 12.5 g benzotriazole 0.6 g diethylene glycol 110.0 g water was added 1 l This concentrate was diluted at a ratio of 1 part concentrate to 2 parts water and used at pH 10.5 Adjust strength developer.

[0071]

[Table 1]

From the results shown in Table 1, the photographic light-sensitive material to which the polymer compound of the present invention and the compound of the general formula (2) are added has a pH of 11. It can be seen that a high-contrast image can be obtained even when processed with a developing solution of less than 0.

Example 2 <Preparation of Emulsion> [Emulsion I] While maintaining the mixing temperature at 40 ° C., an average particle size of 0.
A 16-micron cubic monodisperse silver chloride emulsion containing 8 × 10 ^-6 mol / mol Ag of rhodium dichloride was prepared, desalted, washed with water and redissolved by the flocculation method. [Emulsion II] The average particle size was 0.2 by the pAg controlled double jet method while maintaining the mixing temperature at 23 ° C.
Prepare a silver chloride emulsion containing 09 micron cubic monodisperse and containing 8 × 10 ⁻⁶ mol / mol Ag of rhodium dichloride, and desalting, washing and redissolving by the flocculation method as in the case of Emulsion I. did.

5-Chlorobenzotriazole was added to these emulsions, and the emulsion was divided into the compounds of the general formula (2) shown in Table 2 and the compound 19 of the comparative compound.
0 ^-3 mol / mol Ag, 10 ^-1 g / m ² of the polymer compound of the present invention shown in Table 2 or 2 × 10 ^-4 mol / mol Ag of the compound 20 of the comparative compound was added, and 2-hydroxy- 4,6-dichloro-1,3,5-triazine sodium salt and, after addition of surfactant of 21, 5 g / m ² with silver nitrate in a polyethylene terephthalate film, as gelatin is 3 g / m ² Applied.

<Protective layer> As a protective layer, 1 g / m ^{2 of} gelatin, a surfactant, a matting agent and a hardener were added and coated thereon to prepare samples shown in Table 2.

These films were exposed to a bright room printer (P-627FM, manufactured by Dainippon Screen Mfg. Co., Ltd.) through a sensitometric wedge, and then developed with the developer used in Example 1 at 35 ° C. for 30 seconds. Then, it was fixed, washed with water and dried. In this processing, an automatic developing machine (LD-221QT, manufactured by Dainippon Screen Mfg. Co., Ltd.) was used.
Gamma is the tan θ of the linear part where the optical density is 1.0 to 2.5
It was measured at. Table 2 shows the results.

Further, in order to test the safety against safelight light, the following two kinds of tests were conducted. First, 5
Exposure and development were performed so that the 0% halftone dot document became 50%, and this was used as a standard sample. On the other hand, after leaving for 20 minutes under bright room light from which 300 Lux of ultraviolet light has been removed, that is, under the fluorescent light of Toshiba FL40SWNU, the sample is exposed and developed with the same exposure amount as the standard sample, and the change amount of halftone dot (safelight is If it becomes x% when irradiated, ΔDot1 = x−5
0) was measured. In addition, the same safelight from the film surface 6
After exposure for 0 minutes, development was carried out and the change in Dmin was measured as safe light fog. Table 2 shows the results.

[0078]

[Table 2]

From the results shown in Table 2, the photographic light-sensitive material containing the polymer compound of the present invention and the compound of the general formula (2) was treated with a developer having a pH of less than 11.0 as compared with the photographic light-sensitive material of Comparative Example. However, it can be seen that a high contrast image can be obtained.
The emulsion II photographic light-sensitive material has a pH of 11.0 while suppressing safelight fog, as compared with the emulsion I photographic light-sensitive material.
It can be seen that a high-contrast image can be obtained even when treated with a developing solution of less than less than. Further, the photographic light-sensitive material to which the polymer compound and the compound of the general formula (2) were added showed no increase in safelight fog compared to the photographic light-sensitive material to which the hydrazine compound of Comparative Example and the nucleation accelerator of Comparative Example were added. It can be seen that an even harder image can be obtained.

Example 3 The samples Nos. 19 to 28 produced in Example 2 were used to examine changes in photographic characteristics in a fatigued developer. Similar to the safety test for safelight light in Example 2, exposure was performed so that 50% halftone dot document became 50%,
It was developed and used as a standard sample. The sample is exposed with the same exposure amount, and this sample is developed with a fatigue developing solution, and the change amount of halftone dot% (developing with the fatigue developing solution is performed by y%).
Then, ΔDot2 = y−50) was measured. Further, the gamma when developed with a fatigue developer was measured.
The fatigue developing solution was prepared by continuously processing the developing solution used in Examples 1 and 2 to 1 m ² of a photosensitive material having a blackening rate of 50% without replenishment. The results are shown in Table 3.

[0081]

[Table 3]

From the results shown in Table 3, the photographic light-sensitive material to which the polymer compound of the present invention and the compound of the general formula (2) were added, was compared with the photographic light-sensitive material of Comparative Example even when treated with a fatigued developer. The ultra-high contrast is maintained, and only a decrease in halftone dots of up to 1% is shown, which is practically no problem. Therefore, it can be seen that a silver halide photographic light-sensitive material having less variation in photographic characteristics is obtained.

[0083]

According to the present invention, even if it is rapidly processed with a stable developing solution containing no amino compound in a solution having a pH of less than 11.0, it has sufficiently hard photographic characteristics and black spots are generated. And a negative-type silver halide photographic light-sensitive material having less variation in photographic characteristics such as gamma and sensitivity even when treated with a developing solution that is tired.

Claims (2)

[Claims] 1. A structure having at least one photosensitive silver halide emulsion layer on a support, and the structure represented by the following general formula (1) in the silver halide emulsion layer or another hydrophilic colloid layer. Compound having a moiety, and the following general formula (2)
A silver halide photographic light-sensitive material comprising at least one compound represented by Embedded image [In the general formula (1), R ¹ , R ² and R ³ represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group which may have a substituent. X represents an anion and L represents a linking group. ] [Chemical 2] [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, R ₁ is an aliphatic group, an aromatic group or a heterocyclic 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 substituted alkyl group in which a carbon atom substituted with G ₁ is substituted with at least one electron withdrawing group. Represent ] 2. A silver halide emulsion comprising at least 90 mol% of silver chloride and 1 × 1 per mol of silver halide.
2. The silver halide photographic light-sensitive material according to claim 1, which contains 0 ^{-6 to} 2 × 10 ^-4 mol of a water-soluble rhodium salt, and the average size of silver halide grains is 0.1 μm or less.