JPH0764226A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PURPOSE:To obtain good photographic performance without deteriorating physical film properties even in the case of a small amount of replenishing solution by incorporating a specified hydrazine derivative in a hydrophilic colloidal layer and a polymer hardening agent in the hydrophilic colloidal layer on its outer side. CONSTITUTION:At least one hydrophilic colloidal layer on the side of a silver halide emulsion layer with respect to a support contains the hydrazine derivative represented by the formula in which A is an aliphatic group having, preferably, 1-30C, especially, 1-20C straight or branched or cyclic alkyl, such as methyl, ethyl, or t-butyl. optionally substituted by proper group, and B is embodied by acyl, arylsulfonyl, alkyl-sulfinyl, arylsulfinyl, or the like. At least one hydrophilic colloidal layer on the outer side of this hydrophilic colloidal layer contains at least one kind of polymer hardening agent.

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 having a silver halide light-sensitive layer on a support and a method for developing the same, and more specifically to a silver halide photographic light-sensitive material for printing plate making which provides a high contrast image. A material and a processing method thereof

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this step, a technique by infectious development has been used as a method for reproducing an ultrahigh contrast image.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle size of about 0.2 μm or less and a narrow grain distribution and a well-shaped silver chloride content of at least 50 mol% or more. The silver chlorobromide emulsion of is generally used.

Such a lith-type silver halide photographic light-sensitive material can be processed with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type infectious developer, to obtain a high-contrast and high-resolution image.

However, these lith-type developers have a drawback that they are susceptible to air oxidation and have extremely poor preservability, so that it is difficult to keep the quality constant during continuous development processing. Therefore, as a method for obtaining a high-contrast image quickly without using such a developing solution, for example, a silver halide photographic light-sensitive material containing a hydrazine derivative as described in JP-A-56-106244 is used. A method of processing with a developer is disclosed. According to this method, the preservability of the developing solution is good, rapid processing is possible, and an ultrahigh contrast image can be easily obtained. However, in this method, in order to fully exhibit the high contrast of the hydrazine derivative,
It had to be processed with a developer having a pH of 11.2 or higher.

In a strongly alkaline developing solution having a pH of 11.2 or more, the oxidation of the developing agent becomes remarkable when the developing solution comes into contact with air. Although more stable than the lith developer described above, there are many cases in which a super-high contrast image cannot often be obtained due to the oxidation of the developing agent.

In order to compensate for such drawbacks, JP-A-63-29751
No. 1, JP-A-1-179939, the same 1-179940, U.S. Pat.
No. 354 discloses a silver halide photographic light-sensitive material containing a hydrazine derivative capable of increasing the tone even with a developer having a relatively low pH of less than 11.2 and accelerating nucleation.

On the other hand, in order to rapidly process a silver halide photographic light-sensitive material, a silver halide photographic light-sensitive material using silver halide grains containing 50 mol% or more of silver chloride is used. The photosensitive material is likely to cause a failure of so-called pressure fog, which is a fog due to a pressure when it touches a machine such as a camera or a scanner during handling.
In particular, it is a serious problem in the silver halide photographic light-sensitive material using the above-mentioned contrast enhancement technique. As a method of improving this problem, it is known that the outermost layer on the emulsion layer side contains a matting agent having a relatively large particle size. At present, there is a problem that pinholes easily occur when the amount is increased. Further, in the silver halide photographic light-sensitive material using the above-mentioned contrast enhancement technique, there is a problem that a so-called black spot, which is a sandy fog-like defect occurring in an unexposed area after development, which is peculiar to a light-sensitive material using a hydrazine derivative, is inferior. .

On the other hand, in recent years, the development replenishment amount has been reduced for the purpose of resource saving, environmental protection, and the like. However, generally, reducing the replenishment amount of the developer causes an increase in silver sludge and deterioration of developability. In the development method using a hydrazine derivative (hereinafter referred to as hydrazine development), the influence of the deterioration of the developability is particularly large and the high contrast is lost, which has been an obstacle to the reduction of the replenishment amount.

As a means for improving the developability, it is known to reduce the amount of gelatin, but increase of silver sludge, deterioration of film physical properties, etc. occur. Further, in the hydrazine development, the amount of gelatin being unnecessarily reduced leads to an increase in black spots and is accompanied by deterioration of image quality.

[0011]

In contrast to the above problems, an object of the present invention is to provide a silver halide light-sensitive material capable of giving good photographic performance even if the replenishing amount is low without deteriorating the physical properties of the film and the silver halide light-sensitive material. It is to provide a processing method.

[0012]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer being provided on the support. At least one layer containing a hydrazine derivative represented by the general formula [H] (Chemical formula 1) in at least one hydrophilic colloid layer on the containing side and existing outside the silver halide emulsion layer A silver halide photographic light-sensitive material characterized by containing at least one polymer hardener in a hydrophilic colloid layer, and a replenishing amount of development is 250 ml or less per 1 m ² of the light-sensitive material. This can be achieved by the processing method of the above silver halide photographic light-sensitive material.

The silver halide grains contained in the silver halide emulsion layer preferably contain silver chloride in an amount of 50 mol% or more.

The present invention will be specifically described below.

In the present invention, the hydrazine derivative may be contained in at least one of the hydrophilic colloid layers existing on the side containing the silver halide emulsion layer with respect to the support, and in two or more different layers. It may be contained. Particularly preferable addition positions are a silver halide emulsion layer and / or
Alternatively, it is contained in at least one of the hydrophilic colloid layers adjacent to the silver halide emulsion layer.

The general formula [H] (Formula 1) will be described in detail below.

In the formula, the aliphatic group represented by A is preferably one having 1 to 30 carbon atoms, particularly a straight chain having 1 to 20 carbon atoms,
It is a branched or cyclic alkyl group. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group,
Examples thereof include a benzyl group and the like, which further include suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfoxy group,
Sulfonamide group, acylamino group, ureido group, etc.).

The aromatic group represented by A in the general formula [H] is preferably a monocyclic or condensed ring aryl group, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by A in the general formula [H] is preferably a monocycle or a condensed ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, such as a pyrrolidine ring, Examples thereof include an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring and a furan ring.

Particularly preferred as A is an aryl group and a heterocyclic group.

The aryl group and heterocyclic group of A may have a substituent. Representative substituents are an alkyl group (preferably having a carbon number of 1 to 20), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl portion having a carbon number of 1 to 3), an alkoxy group (preferably Alkyl moiety having 1 to 20 carbon atoms, substituted amino group (preferably amino group substituted with alkyl group having 1 to 20 carbon atoms or alkylidene group), acylamino group (preferably having 1 to 40 carbon atoms) ), Sulfonamide group (preferably having 1 to 40 carbon atoms), ureido group (preferably having 1 to 40 carbon atoms)
Group), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms), a hydroxyl group, a phosphoamide group (preferably having 1 to 40 carbon atoms), and the like.

Further, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. The diffusion resistant group is preferably a ballast group commonly used in non-moving photographic additives such as couplers, and the ballast group has 8 carbon atoms.
Examples thereof include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group, an alkylphenoxy group and the like, which are relatively inactive to the above photographic properties.

As the silver halide adsorption promoting group, thiourea, thiourethane group, mercapto group, thioether group,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorbing group described in JP-A No. 64-90439.

B is specifically an acyl group (eg formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc.), alkylsulfonyl groups (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl groups (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (eg methanesulfinyl etc.), an arylsulfinyl group (benzenesulfinyl etc.), a carbamoyl group (eg methylcarbamoyl, phenylcarbamoyl etc.), an alkoxycarbonyl group (eg methoxycarbonyl, methoxyethoxycarbonyl etc.), an aryloxycarbonyl Groups (eg phenoxycarbonyl etc.), sulfamoyl groups (eg dimethylsulfamoyl etc.), sulfinamoyl groups (eg methylsulfur) Finamoyl etc.), an alkoxysulfonyl group (eg methoxysulfonyl etc.), a thioacyl group (eg methylthiocarbonyl etc.), a thiocarbamoyl group (eg methylthiocarbamoyl etc.), an oxalyl group (the general formula [Ha] will be described later) or a heterocyclic group. (Eg, pyridine ring, pyridinium ring, etc.).

B in the general formula [H] represents A ₂ and the nitrogen atom to which they are attached.

[0026]

[Chemical 2]

May be formed.

R ₉ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

As B, an acyl group or an oxalyl group is particularly preferable.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (methanesulfonyl, toluenesulfonyl, etc.), or an oxalyl group ( Etoxaryl etc.)

Among the hydrazine compounds used in the present invention, particularly preferred are compounds represented by the following general formula [Ha].

[0032]

[Chemical 3]

In the formula, R ₄ represents an aryl group or a heterocyclic group, and R ₅ represents

[0034]

[Chemical 4]

Represents

R ₆ and R ₇ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Alternatively, it represents a heterocyclic oxy group, and R ₆ and R ₇ may form a ring together with an N atom. R ₈ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. A ₁ and A ₂ represent the same meanings groups as A ₁ and A ₂ in formula (H).

The general formula [Ha] will be described in more detail.

The aryl group represented by R ₄ is preferably a monocyclic ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring.

The heterocyclic group represented by R ₄ is preferably a 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen, which is a monocyclic ring or a condensed ring. Examples thereof include a ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

Preferred as R ₄ is a substituted or unsubstituted aryl group. Examples of the substituent include those having the same meaning as the substituent of A in the general formula [H].
When the contrast is increased with a developing solution of 1.2 or less, it is preferable to have at least one sulfamide group.

[0041] A ₁ and A _2, A ₁ and A ₂ of the formula H
And a hydrogen atom are the most preferable.

R ₅ is

[0043]

[Chemical 5]

Wherein R ₆ and R ₇ are each a hydrogen atom, an alkyl group (methyl, ethyl, benzyl, etc.),
Alkenyl groups (allyl, butenyl, etc.), alkynyl groups (propargyl, butynyl, etc.), aryl groups (phenyl, naphthyl, etc.), heterocyclic groups (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidinyl) Nyl, quinolidinyl, N, N'-diethylpyrazolidinyl, N-benzylpyrrolidinyl, pyridyl, etc.), amino group (amino, methylamino, dimethylamino, dibenzylamino, etc.), hydroxyl group, alkoxy group (methoxy , Ethoxy, etc.), alkenyloxy group (allyloxy etc.), alkynyloxy group (propargyloxy etc.), aryloxy group (phenoxy etc.), or heterocyclic oxy group (pyridyloxy etc.), and R ₆ and R ₇ are nitrogen. A ring (piperidine, morpholine, etc.) may be formed together with the atom. R ₈ is a hydrogen atom, an alkyl group (methyl, ethyl, methoxyethyl, hydroxyethyl, etc.), an alkenyl group (allyl, butenyl, etc.), an alkynyl group (propargyl, butynyl, etc.), an aryl group (phenyl, naphthyl, etc.), a heterocycle Group (2,2,
6,6-tetramethylpiperidinyl, N-methylpiperidinyl, pyridyl and the like).

Specific examples of the compounds represented by the general formulas [H] and [Ha] are shown below. However, the present invention is not limited to these.

[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

[Chemical 8]

[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

The method for synthesizing the compound represented by the general formula [H] used in the present invention is described in JP-A Nos. 62-180361 and 62-178246.
No. 63-234245, No. 63-234246, No. 64-90439, JP-A No. 2-37, No. 2-841, No. 2-947, No. 2-120736, No.
2-230233, 3-125134, U.S. Patent 4,686,167,
4,988,604, 4,994,365, European patent 253,665
No. 333,435, etc. can be referred to.

The amount of the compound represented by the general formula [H] used in the present invention is 5 × 10 ^{−7 to} 5 × 10 5 per mol of silver halide.
^-1 mol is preferable, and particularly 5 × 10 ^{-6 to} 5 × 10 ^-2
It is preferably in the molar range.

In the present invention, when the compound represented by the general formula [H] is contained in the photographic light-sensitive material, it is contained in the silver halide emulsion layer or a hydrophilic colloid layer adjacent to the silver halide emulsion layer.

Next, as the nucleation accelerator, the following general formula [N
Examples thereof include those shown in a] or [Nb].

[0058]

[Chemical 14]

In the general formula [Na], R ₁ , R ₂ , R ₃
Represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group or a substituted aryl group. A ring can be formed by R ₁ , R ₂ and R ₃ . Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a molecular weight of 300 or more is more preferable. Further, preferable adsorption groups include heterocycle, mercapto group, thioether group, thione group, thiourea group and the like.

Specific compounds include those shown below.

[0061]

[Chemical 15]

[0062]

[Chemical 16]

[0063]

[Chemical 17]

[0064]

[Chemical 18]

In the general formula [Nb], Ar represents a substituted or unsubstituted aryl group or a heteroaromatic ring. R represents an optionally substituted alkyl group, alkenyl group, alkynyl group, or aryl group. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. In order to have a preferable diffusion resistant group, the molecular weight is preferably 120 or more, particularly preferably 300 or more.

Specific compounds include those shown below.

[0067]

[Chemical 19]

[0068]

[Chemical 20]

Next, the polymer hardener according to the present invention will be described.

The polymer hardener of the present invention means a compound having at least two electrophilic groups for reacting with gelatin in the same molecule and having a molecular weight (number average molecular weight) of 10,000 or more.

Here, examples of the electrophilic group for reacting with gelatin or the like include an aldehyde group, an epoxy group, an active halide group (such as cyclolotriazine), an active vinyl group and an active ester group.

The number of these groups may be at least two in the polymer hardener, but is preferably 10 to 5,000.
Further, those having a molecular weight of about 1 to 500,000 are preferably used.

The polymer portion having an electrophilic group for reacting with gelatin is preferably hydrophilic in general, but even if it is not hydrophilic, it is emulsified and dispersed in a hydrophilic colloid (eg gelatin). It can also be used by (dispersing in an organic solvent if necessary).

Examples of the polymer hardener used in the present invention include dialdehyde starch, polyacrolein, US Pat.
Polymers having aldehyde groups such as acrolein copolymers described in 3,396,029, polymers having epoxy groups described in US Pat. No. 3,623,878, US Pat.
No. 5, Research Disclosure 17333 (1978) and the like, polymers having dichlorotriazine groups, JP-A-56-66841, polymers having active ester groups, JP-A-56-142524, US Pat. Patent No. 4,161,4
07, JP-A-54-65033, Research Disclosure Magazine
16725 (1978) and the like, and polymers having an active vinyl group or a group serving as a precursor thereof, and the like. Polymers having an active vinyl group or a group serving as a precursor thereof are preferable, and among them, JP-A- Particularly preferred are polymers in which the active vinyl group or its precursor group is bonded to the polymer main chain by a long spacer, as described in 56-142524. That is,
A polymer having a repeating uniqueness represented by the following general formula [p] is particularly preferable.

[0075]

[Chemical 21]

In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer.

Examples of the ethylenically unsaturated monomer in the general formula [p] are styrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, N, N, N-trimethyl-N-vinylbenzylammonium chloride, α-methylstyrene. , 4-vinylpyridine, N-vinylpyrrolidone,
Monoethylenically unsaturated esters of aliphatic acids (eg vinyl acetate), ethylenically unsaturated monocarboxylic or dicarboxylic acids and their salts (eg acrylic acid, methacrylic acid), maleic anhydride, ethylenically unsaturated monocarboxylic acids Acid or dicarboxylic acid ester (eg, n-butyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-diethyl-N-methyl-N-methacryloyloxytyl ammonium p-toluene sulfonate, ethylenically saturated monocarboxylic acid Alternatively, an amide of a dicarboxylic acid (eg, acrylamide, sodium 2-acrylamido-2-methylpropanesulfonic acid, N, N-dimethyl-N′-methacryloylpropanediamineacetate betaine).

R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a butyl group n-hexyl group), of which a hydrogen atom or a methyl group is particularly preferable.

[0079]

[Chemical formula 22]

[0080]

[Chemical formula 23]

[0081] R ₂ represents a functional group which is a vinyl group or a precursor thereof, -CH = CH _2, is either -CH ₂ CH ₂ X. X is replaced by a nucleophilic group or HX by a base
Represents a removable group in the form of.

R ₂ includes the following groups.

-CH = CH ₂ , -CH ₂ CH ₂ Br, -CH ₂ CH ₂ Cl

[0084]

[Chemical formula 24]

Is particularly preferable.

X and y represent mole percentages, and x has a value of 0 to 99 and y has a value of 1 to 100.

Preferably, x has a value of 0 to 75 and y has a value of 25 to 100.

Specific examples of the polymer hardener of the present invention are shown below.

[0089]

[Chemical 25]

[0090]

[Chemical formula 26]

[0091]

[Chemical 27]

[0092]

[Chemical 28]

[0093]

[Chemical 29]

As the polymer hardener of the present invention, a polymer having at least two electrophilic molecules in the same molecule for reacting with gelatin from the beginning, such as the polymer described above, is used. In a silver halide emulsion layer coated using a gelatin hardener and a polymer which reacts with it to give a polymer having at least two electrophilic groups in the same molecule. A polymeric hardener can be made, thereby achieving the objects of the invention.

Thus, as a gelatin hardener used to make a polymeric hardener in an emulsion layer, eg T.
`` The Theory to the Photographic Proc by H. James
Low molecular hardeners such as those described in "Ess", 4th Edition, pp. 77-84 are used. Among them, a low molecular hardener having a vinyl sulfone group is preferable, and particularly, JP-A-53-412.
The hardeners described in 21 are preferred.

Specific examples of the gelatin hardener of the present invention which gives the polymer hardener are shown below.

[0097]

[Chemical 30]

Further, the polymer used for preparing the polymeric hardener in the emulsion layer must have at least two nucleophilic groups which react with the gelatin hardener in the same molecule. And a polymer having a primary amino group described in British Patent No. 2,011,912, a polymer having a sulfinic acid group described in JP-A-56-4141, a U.S. Patent
Polymers having a phenolic hydroxyl group described in 4,207,109, polymers having an active methylene group described in U.S. Pat.No. 4,215,195 and the like, a sulfinic acid group described in JP-A-56-4141 Polymers having are particularly preferred.

Specific examples of the polymer which provides the polymeric hardener of the present invention are shown below.

[0100]

[Chemical 31]

[0101]

[Chemical 32]

[0102]

[Chemical 33]

Regarding the method for synthesizing the polymer hardener of the present invention, the description in JP-A-60-61742 can be referred to.

When the polymer hardener of the present invention is used, the amount used can be arbitrarily selected according to the purpose. Usually 10
A polymeric hardener having a functional group capable of reacting with gelatin in the range of 5 × 10 ⁻³ equivalent to 5 × 10 ⁻² equivalent to 0 g of dry gelatin is used. Particularly preferably 0.5 x 10
The range is from ^-3 equivalent to 2 x 10 ^-2 equivalent.

The polymer of the present invention may be used alone as a hardener or may be used in combination with other low molecular weight hardeners or polymer hardeners. As a hardening agent that can be used in combination, a compound having a reactive halogen atom such as 2-hydroxy-4,6-dichloro-1,3,5-triazine,
Examples thereof include compounds having a reactive olefin such as divinyl sulfone, isocyanates, aziridine compounds, epoxy compounds, mucochloric acid, chrome vanane, and aldehydes.

With respect to the amount of gelatin, when the total amount of gelatin on the emulsion surface side is 4 g / m ² or less, particularly preferably 2.5 g / m ² or less, the effect of the present invention is particularly great.

In the light-sensitive material of the present invention, at least one conductive layer is preferably provided on the support. As a typical method for forming the conductive layer, a water-soluble conductive polymer,
There are a method of forming using a hydrophobic polymer and a curing agent and a method of forming using a metal oxide. For these methods, see, for example, JP-A-3-265842, page 5, lower right column, line 1 to line 15.
The method described in the upper left column of the page and the sixth line can be used. The silver halide emulsion used in the present invention (hereinafter referred to as a silver halide emulsion or simply an emulsion) includes, for example, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, And any of those used for ordinary silver halide emulsions such as silver chloride can be used, but silver chlorobromide, silver bromide, or iodobromide containing 4 mol% or less of silver iodide is preferable. It is silver or silver chloroiodobromide.

[(Standard deviation of particle size)] / (average value of particle size)
Monodisperse particles represented by × 100 and having a coefficient of variation of 15% or less are preferable.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention. For example,
The silver halide photographic emulsion and backing layer used in the present invention include various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, and ultraviolet absorbers. , An anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion of the present invention and the backing layer.

These additives are described in more detail in Research Disclosure Vol. 176, Item / 7643 (December 1978) and Vol. 187, Item / 8716 (November 1979). It is summarized below.

Additive type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic Agent Page 27 As above As a support which can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate,
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass and metal. These supports are subjected to a surface treatment if necessary.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by various methods such as a commonly used method after exposure.

Examples of the developing agent that can be used in the present invention include dihydroxybenzenes (eg, hydroquinone, chlorohydroquinone, bromohydroquinone, 2,3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidones (eg 1-phenyl-3
-Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-
3-pyrazolidone, etc.), aminophenols (eg, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), pyrogallol, Ascorbic acid, 1-aryl-3-pyrazolines (eg 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl)
-3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-N-methylphenyl) -3-aminopyrazoline, etc.) alone or in combination However, it is preferable to use a combination of 3-pyrazolidones and dihydroxybenzenes or a combination of aminophenols and dihydroxybenzenes. The developing agent is usually preferably used in an amount of 0.01 to 1.4 mol / liter.

In developing the light-sensitive material of the present invention, the effect of the present invention is exhibited when the replenishing amount of the developing solution is 250 cc / m ² or less. The replenishment amount in the present invention is defined when the mother liquor and the replenisher are the same liquid. When the concentrations of the mother nucleus and the replenishing solution are different, the developer concentration of the replenishing solution is defined by the number converted into the replenishing amount when the concentration is changed so as to be the same as the mother solution.

In the light-sensitive material of the present invention, it is preferable that the light-sensitive material is replenished depending on the treated area of the light-sensitive material to be replenished. In these cases, it is defined as a value obtained by dividing the total replenishment amount by all the methods by the total area of the photosensitive material processed during that period.

The light-sensitive material of the present invention can obtain good photographic performance even when the replenishing amount exceeds 250 cc / m ² , but it is also good when the replenishing amount is 250 cc / m ² or less. Provides photographic performance and physical properties. Particularly preferred replenishment amount is 250c
It is c / m ² .

In the present invention, as a silver sludge inhibitor, JP-B-62-4702, JP-A-3-51844, JP-A-4-26838,
4-362942 and 1-319031, more preferably compounds represented by the following general formula [Pa] or [Pb] can be used.

[0118]

[Chemical 34]

In the formula, R ₁₁ and R ₁₂ are hydrogen atom, alkyl group, aryl group, aralkyl group, hydroxy group, mercapto group, carboxy group, sulfo group, phosphono group, amino group, nitro group, cyano group, halogen atom. , An alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and an alkoxy group. Also R
₁₁ and R ₁₂ may combine to form a ring structure.

Further, in the general formula [Pb], M ₁ and M ₂ are hydrogen atoms,
It represents Na, K or NH ₄ , and X ₁ represents a hydrogen atom or a halogen atom.

Typical examples of the compounds represented by the general formulas [Pa] and [Pb] are shown below.

[0122]

[Chemical 35]

[0123]

[Chemical 36]

[0124]

[Chemical 37]

Examples of sulfites and metabisulfites used as preservatives in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite. The sulfite is preferably 0.25 mol / liter or more. It is particularly preferably 0.4 mol / liter or more.

In the developing solution, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) , Solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.),
Surfactants, antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (For example, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), development accelerator (for example, US Pat. No. 2,304,025)
Nos. 5,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg glutaraldehyde or its bisulfite adduct), an antifoaming agent and the like can be added. The pH of the developer is preferably adjusted to 9.5-12.0.

The compounds of the present invention, as a special form of development processing, include a developing agent in a light-sensitive material, for example, an emulsion layer,
You may use it for the activator processing liquid which makes a photosensitive material process in alkaline aqueous solution and develops. Such a developing treatment is often used as one of the rapid processing methods for a light-sensitive material in combination with a silver salt stabilizing treatment with a thiocyanate, and can be applied to such a processing solution.
In the case of such rapid processing, the effect of the present invention is particularly great.

As the fixing liquid, those having a generally used composition can be used. The fixer is generally an aqueous solution containing a fixer and others, and the pH is usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur capable of forming a soluble stable silver complex salt. A compound known as a fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, etc. can be added to the fixing solution.

If desired, the fixer may contain preservatives (eg sulfite, bisulfite), pH buffers (eg acetic acid), pH.
A compound such as a modifier (for example, sulfuric acid), a chelating agent having the ability to soften water, or the like can be included.

The developing solution may be a mixture of fixed components, an organic aqueous solution containing glycol or amine, or a viscous liquid having a high viscosity and in a semi-kneaded state. Further, it may be diluted before use, or may be used as it is.

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C.

The black-and-white light-sensitive material according to the present invention is preferably processed by using an automatic processor. At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The development replenishment amount is 1 in order to reduce the amount of waste liquid.
250cc or less per m ² . Preferably 75 to ² per m ²
It is 00cc. If the developer replenishment rate is less than 75 cc per m ^2, desensitization, softening, etc. cannot be obtained and satisfactory photographic performance cannot be obtained.

In the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone is 20 when processing is performed using the automatic developing machine in order to shorten the developing time. It is preferably -60 seconds. The total processing time referred to here includes all process times required for processing the black-and-white light-sensitive material, and specifically, for processing, for example, developing, fixing, bleaching, washing, stabilizing, drying, etc. It is the time that includes all the process time, that is, the time to Dry to Dry. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dr
y to Dry) is 30 to 60 seconds.

[0135]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (Preparation of Silver Halide Emulsion A) A silver chloroiodobromide emulsion consisting of 70 mol% of silver chloride, 0.2 mol% of silver iodide and the rest of silver bromide was prepared by the simultaneous mixing method. . At the time of simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ^-8 mol per mol of silver. The resulting emulsion was a cubic, monodisperse grain with a mean grain size of 0.20 μm (variation coefficient 9
%) Emulsion. Then, the emulsion was desalted with a modified gelatin described in JP-A-2-280139 (wherein the amino group in gelatin was replaced with henylcarbamyl, for example, G-8 in JP-A-2-280139). The EAg after desalting was 190 mv at 50 ° C.

The emulsion thus obtained was adjusted to pH 5.58 and EAg123 mV, and the temperature was adjusted to 60 ° C., and chloroauric acid was added per mol of silver.
After 2.2 × 10 ^-5 mol was added and stirred for 2 minutes, 2.9 × 10 ^-6 mol of S ₈ was added per 1 mol of silver, and chemical ripening was further performed for 78 minutes. At the end of ripening, the following was added per mol of silver.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g An emulsion liquid was added.

(Preparation of silver halide photographic light-sensitive material) The following formulation was prepared on one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm and subjected to the antistatic treatment described in Example 1 of JP-A-3-92175. The silver halide emulsion of No. 1 was coated so that the silver amount was 3.3 g / m ² and the gelatin amount was 2.6 g / m ² .

Further, the following formulation 2 was used as a protective layer on the upper layer.
Was coated so that the amount of gelatin would be 1 g / m ² .
On the undercoat layer on the opposite side, a backing layer of the following formulation 3 is applied so that the amount of gelatin is 2.7 g / m ^2, and a protective layer of the following formulation 4 is 1 g / m ^{2 of} gelatin on the upper layer. Thus, 9 kinds of samples shown in Table 1 were prepared.

Formulation 1 (composition of silver halide emulsion layers)

[0142]

[Chemical 38]

S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.64 mg / m ² 2-mercapto-6-hydroxypurine 1.7 g / m ² EDTA 50 mg / m ² Formulation 2 (emulsion protective layer composition) ) S-1 12 mg / m ² matting agent: monodisperse silica 22 mg / m ^{2 with an} average particle size of 3.5 μm 1,3-vinylsulfonyl-2-propanol 40 mg / m ²

[0144]

[Chemical Formula 39]

[0145] polymeric hardener 10 mg / m ² Formulation 3 (backing layer composition) saponin ^{133mg / m 2 S-1 6mg} / m 2 Colloidal silica 100 mg / m ²

[0146]

[Chemical 40]

Formulation 4 (Backing protective layer composition) Matting agent: Monodisperse polymethylmethacrylate 50 mg / m ^{2 having an} average particle size of 5.0 μm Sodium-di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² Samples obtained Was exposed to light having a wavelength of 633 nm as a substitute characteristic of He-Ne laser light by closely contacting with a step wedge, and then an automatic developing machine for rapid processing (GR-26SR Konica Corporation) using the developing solution and fixing solution having the following composition ) Under the following conditions.

However, the processing in a new solution (mother solution) after the preparation of the developing solution and the processing with the developing solution after the forced running test using the developing solution having the same concentration as the mother solution as a replenishing solution are performed. Running conditions are 300ml / m ² , 250ml / m ² , 150m
It was l / m ² and 50 ml / m ² , respectively, and the process was repeated until the amount of the developing tank of the automatic processor was doubled. At this time, the replenishment of the fixing solution is 150 ml / m ² .

(Developer Solution Formulation) Sodium sulfite 55 g / liter Potassium carbonate 40 g / liter Hydroquinone 24 g / liter 4-Methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (Dimeson S) 0.9 g / liter Potassium bromide 5 g / Liter 5-methyl-benzotriazole 0.13 g / liter boric acid 2.2 g / liter diethylene glycol 40 g / liter Exemplified P-1 60 mg / liter Add water and potassium hydroxide to make 1 liter / pH 10.5.

(Fixing Solution Formulation) (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g The composition A and the composition B were melted in this order and finished to 1 liter before use. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development 35 ° C. 30 seconds Fixing 33 ° C. 20 seconds Washing at room temperature 20 seconds Drying 40 ° C. 40 seconds The developed sample obtained was used for PDA-65 (Konica Digital Density). (Total)
It was measured at. The sensitivities in the table are relative sensitivities when the sensitivity of Sample No. 1 at a concentration of 3.0 is 100. Further, gamma is represented by tangents of densities of 0.1 and 3.0. When the gamma value in the table is less than 6, it is a photosensitive material that cannot be used, and even if it is 6 or more and less than 10, the contrast is still insufficient. A gamma value of 10 or more means that a super-high contrast image can be obtained for the first time, indicating that the material is a sufficiently practical photosensitive material.

Regarding the film strength, the scratch strength of the developer under the above-mentioned developing conditions was measured by the scratch meter HEIDON.
-18 for fresh solution and 250 ml replenishing running.

If the scratch strength is less than 50 g, problems such as scratches will occur in practical use.

The results obtained are shown below.

[0155]

[Table 1]

As is apparent from Table 1, the photographic material of the present invention can obtain good photographic performance even when it is run with a replenishing amount of 250 ml / m ² or less. In addition, there was no problem in dryness during running.

Example 2 Samples 1 and 3 prepared in Example 1 were prepared by changing the total amount of gelatin in the emulsion layer and the emulsion protective layer without changing the ratio, and a new solution and 250 ml / m ² were prepared. The same evaluation as in Example 1 and the evaluation of black spots were performed for running by supplementation with 50 ml / m ² . Evaluation of black spots is based on the black spots in the unexposed area.
It was evaluated using a 40x loupe. The highest rank 5 was one in which no black spots were generated, and the rank was lowered to 4, 3, 2, 1 according to the degree of occurrence of black spots. Rank 1
And 2 are practically unfavorable levels. The results are shown in Table 2.
Shown in.

[0158]

[Table 2]

As is clear from Table 2, the light-sensitive material of the present invention gives good photographic performance and film strength even when it is run with a replenishing amount of 250 ml / m ² or less. It can be seen that especially when the amount of gelatin on the emulsion side is 2.5 g / m ² or less, the photographic performance after running is excellent and the black spots are also good.

[0160]

According to the present invention, it is possible to provide a silver halide light-sensitive material capable of giving good photographic performance even with a low replenishment amount without deteriorating the physical properties of the film, and a processing method thereof.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one hydrophilic colloid layer on the side containing the silver halide emulsion layer with respect to the support contains a hydrazine derivative represented by the following general formula [H], and is outside the silver halide emulsion layer. A silver halide photographic light-sensitive material, characterized in that at least one kind of polymer hardener is contained in at least one hydrophilic colloid layer present in 1. [Chemical 1] [In the formula, the aliphatic group represented by A preferably has 1 to 1 carbon atoms.
It is a straight chain, branched or cyclic alkyl group having a carbon number of 1 to 20, particularly 30. For example, methyl group, ethyl group, t-
Examples thereof include a butyl group, an octyl group, a cyclohexyl group and a benzyl group, which may be further substituted with a suitable substituent. B is specifically an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, It represents a thiocarbamoyl group, an oxalyl group, or a heterocyclic group. ] 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains contained in the silver halide emulsion layer contain 50 mol% or more of silver chloride. 3. The replenishment amount for development is 250 ml per 1 m ² of light-sensitive material.
3. Replenishing at the following ratios: 1.
A method for processing a silver halide photographic light-sensitive material.