JPH08254787A - Silver halide photographic sensitive material and method for processing same - Google Patents

Abstract

PURPOSE: To provide the photosensitive material prevented from occurrence of trouble due to microorganisms and attachment of stains during the time from manufacture of the photosensitive material to its development processing. CONSTITUTION: This silver halide photographic sensitive material having a silver halide emulsion layer on a support contains a hydrazine derivative or a tetrazolium compound as a contrast-enhancing agent in the emulsion layer and a hydrophilic colloidal layer, and the photosensitive material is processed in the presence of at least one kind of aminoglycoside selected from gentamycins, amikacins, toplamycins, dibecamycins, albecacins, micronomycins, isebamycins, silimycins, netylmycins, and astromycins.

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 for printing plate making and a processing method thereof.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material), particularly a light-sensitive material for printing plate making, generally has a developing section, a fixing section, a washing section or a stabilizing bath section and a drying section after exposure. It is processed by an automatic processor.

Since the light-sensitive material contains a large amount of gelatin and other organic substances, it always has a problem of microbial contamination such as bacteria and mold. In particular, when microbial contamination occurs during the production of a light-sensitive material or before processing, troubles such as pinholes in which fungi agglomerate and dirt adhere to the surface occur. In particular, when mold develops in a light-sensitive material containing a contrast-increasing agent, it significantly inhibits contrast-increasing, and when a more safe ascorbic acid is used as a developing agent in a developing solution, stains often occur. ing.

For this reason, conventionally, a mildew-proofing agent has been contained in a light-sensitive material, but it becomes insufficient due to the generation of resistant bacteria. Further, the replenishment of the processing liquid and washing water has been reduced, and stains on the light-sensitive material are increasing.

[0005]

SUMMARY OF THE INVENTION In response to the above problems, an object of the present invention is to provide a light-sensitive material and a light-sensitive material capable of preventing damages and adhesion of stains by microorganisms during the production of the light-sensitive material and before processing. It is to provide a processing method.

[0006]

The above object of the present invention can be achieved by the following means.

In a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support and containing a hydrazine derivative or a tetrazolium compound as a contrast adjusting agent in the silver halide emulsion layer and the hydrophilic colloid layer, the halogen Presence of at least one kind of aminoglycoside selected from gentamicin, amikacin, topramycin, dibekacin, arbekacin, micronomycin, isebamycin, silymycin, netilmycin and astromycin in a silver halide photographic light-sensitive material A method for processing a silver halide photographic light-sensitive material, which comprises performing the processing below.

A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support and containing a hydrazine derivative or a tetrazolium compound as a contrast adjusting agent in the silver halide emulsion layer and the hydrophilic colloid layer is a gentamicin compound. , Amikacins, topramycins, dibekacins, arbekacins, micronomycins, isebamycins, silymycins, netilmycins, and halogenated products containing at least one aminoglycoside selected from astromycins Silver photographic light-sensitive material.

In a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, the silver halide photographic light-sensitive material is prepared using gentamicin, amikacin, topramycin, dibekacin, arbekacin, micronomycin. In the presence of at least one aminoglycoside selected from isebamycins, silymycins, netilmycins and astromycins, the compound represented by the general formula [1] is substantially free of a dihydroxybenzene compound. A method of processing a silver halide photographic light-sensitive material, which comprises processing with a developer containing the same.

In a silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, gentamicin, amikacin, topramycin, dibekacin,
A silver halide photographic light-sensitive material containing at least one kind of aminoglycoside selected from arbekacins, micronomycins, isebamycins, sirimycins, netilmycins and astromycins,
A silver halide photographic light-sensitive material, characterized by being treated with a developer containing substantially no dihydroxybenzene compound and containing the compound represented by the general formula [1].

The present invention will be specifically described below.

In the present invention, the hydrazine derivative is preferably a compound represented by the following general formula [H].

[0013]

Embedded image

In the formula, A represents an aryl group or a heterocycle containing at least one sulfur atom or oxygen atom, and G represents a-(CO) _n- group, a sulfonyl group, a sulfoxy group, -P (= O). R
Represents a ₂ -group or an iminomethylene group, n represents an integer of 1 or 2, and A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or Represents an unsubstituted acyl group, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group,
It represents an amino group, a carbamoyl group, or an oxycarbonyl group. R ₂ is a substituted or unsubstituted alkyl group,
An alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an amino group and the like.

Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0016]

Embedded image

In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or heterocyclic group (eg, pyridyl group, cenyl group, Represents a furyl group),
Those groups which are further substituted with an appropriate substituent are preferably used. Further, R ¹ preferably contains at least one ballast 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 having 8 or more carbon atoms is relatively inert to photographic properties, such as an alkyl group. , Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

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.

In the general formula [Ha], X represents a group capable of substituting for a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, X may be the same or different. .

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and both are preferably hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ³ group and a —CON (R ⁴ ) (R ⁵ ) group (R ³ represents an alkynyl group or a saturated heterocyclic group,
R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 4]

[0026]

Embedded image

[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

Embedded image

Specific examples of other preferable hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by the method as described in No. 248, columns 59 to 80.

The amount of addition may be any amount that causes a high contrast (a high contrast amount), and the optimum amount varies depending on the grain size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of inhibitor, etc. Generally, it is in the range of 10 ^-6 to 10 ^-1 mol, and preferably in the range of 10 ^-5 to 10 ^-2 mol, per mol of silver halide.

The hydrazine derivative used in the present invention is
It is added to the silver halide emulsion layer or its adjacent layer.

In order to effectively promote the contrast increase by the hydrazine derivative, it is preferable to use a nucleation accelerator represented by the following general formula [Na] or [Nb].

[0035]

[Chemical 9]

In the general formula [Na], R ₁₁ , R ₁₂ , and R ₁₃
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 ₁₁ , R ₁₂ , and R ₁₃ . 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, as preferable adsorption groups, heterocycle, mercapto group, thioether group,
Examples thereof include thione group and thiourea group. General formula (N
Particularly preferred as a] is a compound having at least one thioether group as a silver halide adsorbing group in the molecule.

Specific examples of these nucleation accelerators [Na] will be given below.

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic group or heterocyclic group. R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group or an aryl group, and Ar and R ₁₄
May be linked by a linking group to form a ring. These compounds preferably have a diffusion resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Further, as a preferable silver halide adsorbing group, a group having the same meaning as the silver halide adsorbing group of the compound represented by the general formula [H] can be mentioned.

Specific examples of the compound of the general formula [Nb] include those shown below.

[0044]

Embedded image

[0045]

[Chemical 15]

Specific examples of other preferable nucleation promoting compounds are described in JP-A-6-258751 (13), page (0062) to (15), page 006.
(2-1) to (2-20) described in "5" and 3-1 described in No. 6-258751 (15), page "0067" to (16), "0068" ~ 3-6.

These nucleation promoting compounds can be used in any layer on the silver halide emulsion layer side, but are preferably used in the silver halide emulsion layer or a layer adjacent thereto.

In the present invention, the tetrazolium compound is preferably a compound represented by the following general formula [T].

[0049]

Embedded image

In the present invention, the substituents R ₁ , R ₂ and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T] are hydrogen atoms or Hammett's sigma value (σ Those in which _P ) is negative are preferred.

Hammett's sigma value for phenyl substitution is well documented, eg, Journal of Medical Chemistry, Vol. 20,
See, for example, C. Hansch et al., P. 304, 1977, and a particularly preferred group having a negative sigma value is, for example, a methyl group (σ _P = −0.17 or less. Σ _P value) ethyl group (−0.15), cyclopropyl group (−0.21), n-propyl group (−0.13), isopropyl group (−0.15), cyclobutyl group (−0.15), n-butyl group (−
0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-0.66),
Acetylamino group (-0.15), hydroxyl group (-0.3
7), a methoxy group (-0.27), an ethoxy group (-0.24), a propoxy group (-0.25), a butoxy group (-0.32), a pentoxy group (-0.34) and the like. Useful as a substituent of the compound of the formula [T].

N _T represents 1 or 2, and ^examples of the anion represented by X _T ^nT- include halogen ions such as chloride ion, bromide ion and iodide ion, and inorganic materials such as nitric acid, sulfuric acid and perchloric acid. Acid radical of acid, acid radical of organic acid such as sulfonic acid and carboxylic acid, anionic activator, specifically
Lower alkylbenzene sulfonate anion such as p-toluene sulfonate anion, higher alkylbenzene sulfonate anion such as p-dodecylbenzene sulfonate anion, higher alkyl sulfate ester anion such as lauryl sulfate anion, boric acid anion such as tetraphenylboron, For dialkyl sulfosuccinate anion such as di-2-ethylhexyl sulfosuccinate anion, polyether alcohol sulfate anion such as cetyl polyethenoxysulfate anion, higher aliphatic anion such as stearate anion, and polymer such as polyacrylate anion The thing with an acid radical etc. can be mentioned.

Specific examples of the compound represented by the general formula [T] are shown below, but the tetrazolium compound is not limited thereto.

[0054]

[Chemical 17]

The above-mentioned tetrazolium compound can be used, for example, in Chemical Reviews, Vol. 55, pp. 335-4.
It can be easily synthesized according to the method described on page 83.

The aminoglycosides used in the present invention will be described. The aminoglycosides of the present invention are compounds known as antibiotics. For example, regarding gentamicins, US Pat. No. 3,091,572,
U.S. Pat. No. 3,136,704, U.S. Pat. No. 3,781,268 for amikacins; U.S. Pat. No. 4,107,424, German patents 2,35 for arbekacins.
0,169; German Patent 2, for dibekacins
135,191; U.S. Pat. No. 4,002,742 for isebacomycins; U.S. Pat. No. 4,045,298 for micronomycins;
No. 6,781; US Pat. Nos. 4,002,742 and 4,029,882 for netilmycins; German Patent 2,437,160; US Pat. No. 3,832,286 for silymycins. can do. In the present invention, the use of gentamicin is particularly preferable among these aminoglycosides. Representative specific examples of gentamicin are listed below.

[0057] Compound No. B-1 (gentamicin A _{2) B-2} (Gentamycin A) B-3 (gentamicin A _l) B-4 (gentamicin B) B-5 (gentamicin X ₂₎ B-6 (anti-biotic JI-20A) B-7 (gentamicin B ₁₎ B-8 (anti-biotic G418) B-9 (anti-biotic JI-20B) B-10 (gentamycin C _l) B-11 (gentamicin C1a) B-12 (Gentamicin C ₂ ) B-13 (Gentamicin C ₂ a) B-14 (Gentamicin C ₂ b) The method for producing the aminoglycosides used in the present invention is described in the above-mentioned patent, but commercially available ones are used. can do. Also, regarding these properties,
THE MERCK INDEX AN ENCYCLO
PEDIA OF CHEMICALS, DRUGS, AND BIOLOGICALS) No. 11
Edition (1989) MERCK & CO., INC.

The aminoglycosides used in the present invention are contained in at least one of the silver halide emulsion layer coated on the support and the hydrophilic colloid layer of the auxiliary layer as exemplified above, preferably in all layers. Can be made. The aminoglycosides are preferably dissolved in water and added to a coating solution containing a hydrophilic colloid for use. The amount of aminoglycoside used is preferably about 0.01 to 20 mg / m ^{2, and} more preferably 0.1 to 5 mg / m ² .

The developer used in the present invention contains substantially no dihydroxybenzene compound, but contains the compound represented by the above general formula [1].

In the compound represented by the general formula [1], a compound represented by the following general formula [1-a] in which R ₁ and R ₂ are bonded to each other to form a ring is preferable.

[0061]

Embedded image

In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, Represents an amide group or a sulfonamide group, Y ₁ represents O or S, Y ₂ represents O, S or NR ₄
Represents

The alkyl group in the general formula [1] or the general formula [1-a] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, a lower alkoxy group is preferable as the alkoxy group, a phenyl group or a naphthyl group is preferable as the aryl group, and these groups may have a substituent. Often, the substitutable group includes a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like as a preferable substituent.

Specific examples of the compound represented by the general formula [1] or the general formula [1-a] according to the present invention are shown below.
The present invention is not limited to these.

[0065]

[Chemical 19]

[0066]

Embedded image

These compounds are typically ascorbic acid, erythorbic acid or derivatives derived from them, and they are available as commercial products or can be easily synthesized by known synthetic methods.

As another method for achieving the object of the present invention, the developing solution used may contain substantially no dihydroxybenzene compound but a developing agent composed of a transition metal complex salt.

Examples of the developing agent composed of a transition metal complex salt that can be used in the present invention include Ti, V, Cr, Mn and F.
It is a complex salt of a transition metal such as e, Co, Ni and Cu, preferably T
It is a complex salt of i, V, Cr and Fe. These may be in a form having a reducing power for use as a developing solution, for example, T
It is known that i ³⁺ , V ²⁺ , Cr ²⁺ , Fe ^{2+ and the} like take the form of complex salts. Specific ligands include ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA)
Examples thereof include aminopolycarboxylic acids and salts thereof, and phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid and salts thereof. Among these, transition metal complex salts having a ligand such as EDTA and DTPA are particularly preferably used.

Specific examples of preferable ligands are shown below, but the ligands are not limited to these.

(1) Ethylenediaminetetraacetic acid (EDTA) (2) Diethylenetriaminepentaacetic acid (DTPA) (3) Triethylenetetraminehexaacetic acid (TTHA) (4) Hydroxyethylethylenediaminetriacetic acid (HEDT)
A) (5) Nitrilotriacetic acid (NTA) (6) 1,2-Diaminocyclohexanetetraacetic acid (7) 1,3-Diamino-2-propanoltetraacetic acid (8) Hexametapolyphosphoric acid (9) Tetrapolyphosphoric acid and others Examples of preferred compounds are described in JP-B-54-41899, P.128.
(2) to P.129 (3).

The complex used in the present invention can be formed in a developing solution by adding a transition metal salt and a ligand compound. The preferred content of these compounds in the developer is 1 to 100 g per liter of the developer.

In the present invention, substantially hydroquinones (eg, hydroquinone, chlorohydroquinone,
Brom hydroquinone, methyl hydroquinone, hydroquinone monosulfonate, etc.) is preferably not contained. The term "substantially free" means an amount of less than 0.01 mol per liter of the developing solution.

In the present invention, a developing agent consisting of a transition metal complex salt and 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-3-pyrazolidone
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4
-Ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (eg o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p) -Aminophenol, 2,4-diaminophenol, etc.) developing agents can be used in combination. When used in combination, the developing agent for 3-pyrazolidones and aminophenols is usually the developer 1.
It is preferably used in an amount of 0.01 to 1.4 mol per liter.

The halogen composition of silver halide in the silver halide emulsion used in the present invention is not particularly limited, but preferably silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride,
It is a silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is preferably 1.2 μ or less, and particularly preferably 0.8 to 0.1 μ.
The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or particles which can be approximated to a sphere. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size. For more information on determining the average particle size, see: Themes of the Photographic Process (CEMees & T.H.James)
Author: The theory of the photographic process), No. 3
Edition, pp. 36-43 (1966 (published by McMillan "Mcmillan")).

The shape of the silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape or the like may be used. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within a grain size range of ± 40% of the average grain size is particularly preferable.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any one-side mixing method, simultaneous mixing method, a combination thereof and the like may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Gives a silver halide emulsion having a substantially uniform grain size.

During physical aging or chemical aging, metal salts such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. Iridium 10 ^-9 to obtain high illuminance characteristics
Doping in the range from 10 to 10 ^-3 mol is often customary in silver halide emulsions. In the present invention, in order to obtain a high-contrast emulsion, it is preferable to dope rhodium, ruthenium, osmium and / or rhenium in the range of 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide.

Rhodium, ruthenium, osmium and /
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. As the addition position, there are a method of uniformly distributing in the particles, and a method of forming a core-shell structure and localizing a large amount in the core part or the shell part.

It is often the case that better results are obtained when the shell is present in a larger amount. Further, in addition to localizing in a discontinuous phase constitution, a method of increasing the existing amount may be used as it continuously becomes outside the particles. Addition amount is 10 per mol of silver halide
The range of ^-9 to 10 ^-3 mol can be appropriately selected.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Resear).
ch Disclosure) No. 176, 17643, pages 22-23 (December 1978)
It is described in the literature described or cited.

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used, but as the preferable sulfur sensitizer, other than the sulfur compound contained in gelatin, various sulfur compounds, for example, thiosulfates, thioureas, Rhodanines, polysulfide compounds and the like can be used. A known selenium sensitizer can be used as the selenium sensitizer. For example, U.S. Pat.No. 1,623,499, JP-A-50-71325, JP-A-60-15
The compounds described in JP-A No. 1994-154, etc. can be preferably used.

As the tellurium sensitizer, known tellurium sensitizers can be used. For example U.S. Patent 1,623,499
Nos. 3,772,031 and 3,320,069 can be preferably used.

The gold sensitization method is a typical one of the noble metal sensitization methods, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained.

Examples of reduction sensitizers include stannous salts, amines,
Formamidine sulfinic acid, a silane compound, etc. can be used.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon ring fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole , Quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. As a nucleus having a ketomethylene structure in the merocyanine dye or the composite merocyanine dye,
5-6 such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus
A member ring can be applied. Specifically, those described in Research Disclosure Vol. 176, RD-17643 (December, 1978), pages 2-3, US Pat. Nos. 4,425,425 and 4,425,426 can be used. The sensitizing dye may be dissolved using ultrasonic vibration described in US Pat. No. 3,485,634. In addition, dissolve sensitizing dyes,
Alternatively, as a method of dispersing and adding to the emulsion, U.S. Patent Nos. 3,482,981, 3,585,195, 3,469,987, and 3,4
25,835, 3,342,605, British Patent 1,271,329, 1,
038,029, 1,121,174, U.S. Patent 3,660,101,
The method described in 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Useful combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure Vol. 176. 17
643 (issued in December 1978), page 23, IV, section J.

In the case of being applied to the photosensitive material for printing plate making of the present invention, a desensitizing dye can be used for controlling the sensitivity and the safelight property. It is especially useful to use a desensitizing dye in the preparation of a bright room light-sensitive material. The organic desensitizers that can be used in the present invention are shown below.

(DS-1) Phenosafranine (DS-2) Pinacryptol Green (DS-3) 2,3-Dimethyl-6-nitro-benzothiazolium
Paratoluenesulfonate (DS-4) 2- (paranitrostyryl) quinoline / paratoluenesulfonate (DS-5) 1,3-Diethyl-1'-methyl-2'-phenylimidazo [4,5-b] quinoxaline- 3'-Indolocarbocyanine iodide (DS-6) Pinacryptol yellow (DS-7) 1,1,3,3'-hexamethyl-5,5'-dinitroindocarbocyanine paratoluenesulfonate (DS- 8) 5,5'-dichloro-3,3'-diethyl-6,6'-dinitrocarbocyanine iodide (DS-9) 1,1'-dimethyl-2,2'-diphenyl-3,3'- Indolocarbocyanine bromide (DS-10) 1,1'3,3'-tetretylimidazo [4,5-b] quinoxalinocarbocyanine chloride (DS-11) 5-meta-nitrobenzylidene rhodanine (DS-12) 6-chloro-4-nitro-nitrobenzotriazole (DS-13) 1,1′-dibutyl-4,4′-bipyridinium dibromide (DS-14) 1,1'-Ethylene-2,2'-bipyridinium dibromide (DS-15) 2-Mercapto-4-methyl-5-nitrothiazole (DS-16) 2- (Ortho-nitrostyryl ) -3-Ethyl-thiazolium paratoluene sulfonate (DS-17) 2- (paranitrostyryl) quinoline paratoluene sulfonate The amount of organic desensitizer used is 10 to 5 g, preferably 1 to 5 g per mol of silver halide. It is in the range of 50 g to 3 g. As an addition method, the solution may be added as an aqueous solution or as a solution in an organic solvent. Further, it can be added in the form of fine particles by a sand mill, a ball mill, or an impeller dispersion.
The size of the fine particles is suitably 0.001 μ to 20 μ, but particularly preferable condition is 0.01 μ to 1 μ. Organic desensitizers are characterized by a polarographic half-edge potential. That is, the sum of the polarographic anode potential and the cathode potential is positive. Regarding this measuring method, U.S. Pat.
No. 307.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3, 3a, 7-Tetrazaindenes), pentazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. may be added. it can.

As the binder or protective colloid of the photographic emulsion according to the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (eg vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination,
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

Regarding these additives, the above-mentioned additives and other known additives, for example, Research Disclosure No. 17643 (December 1978), No. 18716 (19).
(November 1979) and No. 308119 (December 1989). The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII The various photographic additives used in the present invention may be dissolved in an aqueous solution or an organic solvent, but when they are poorly soluble in water, they are made into a fine particle crystal state to give water, gelatin, hydrophilicity. Alternatively, it can be used by dispersing it in a hydrophobic polymer. In order to disperse the dye, dye, desensitizing dye, hydrazine, redox compound, antifoggant, ultraviolet absorber and the like of the present invention, they can be dispersed by a known disperser. Specific examples thereof include a ball mill, a sand mill, a colloid mill, an ultrasonic disperser, and a high speed impeller disperser. These dispersed photographic additives are fine particles having an average particle size of 100 μm or less, and are usually used in an average particle size of 0.02 to 10 μm. A mechanically high-speed stirring method as a dispersion method (Japanese Patent Laid-Open No. 58-10514)
No. 1), a method in which the organic solvent is removed by heating and dissolving it in an organic solvent and dispersing this while adding the gelatin containing a surfactant or defoaming agent and the hydrophilic polymer described above (JP-A-44).
-22948), a method of dissolving crystals dissolved in an acid such as citric acid, acetic acid, sulfuric acid, hydrochloric acid, malic acid in a polymer having a pH of 4.5 to 7.5 (JP-A-50-80119), and hydroxylation. A method in which crystals are precipitated and dispersed in a polymer such as gelatin having a pH of 4.5 to 7.5 by dissolving in an alkali such as sodium, sodium hydrogen carbonate or sodium carbonate (Japanese Patent Laid-Open No. 22525-2) can be applied. For example, hydrazine, which is poorly soluble in water, can be dissolved by referring to JP-A No. 2-3033, and this method can be applied to other additives. Further, a dye having a carboxyl, a sensitizing dye, an inhibitor and the like can increase the immobilization rate of fine particle crystals by utilizing the chelating ability of the carboxyl group. That is, it is preferable to add a calcium ion or a magnesium ion to the hydrophilic colloid layer in an amount of 200 to 4000 ppm to form a sparingly soluble salt. The use of another salt is not limited as long as it is possible to form a poorly soluble salt. The method for dispersing fine particles of a photographic additive can be arbitrarily applied to a sensitizer, a dye, an inhibitor, an accelerator, a contrast-increasing agent, a contrast-increasing aid, etc. according to its chemical and physical properties.

A plurality of constituent layers from 2 layers to 10 layers of the present invention
For simultaneous coating at a high speed of 30 to 1000 meters per minute, the known slide hopper method or curtain coating method described in US Pat. Nos. 3,636,374 and 3,508,947 can be used. In order to reduce unevenness during coating, it is preferable to use the hydrophilic polymer which can reduce the surface tension of the coating liquid and can impart thixotropic property in which viscosity is reduced by shearing force.

The light-sensitive material of the present invention may be provided with a crossover cut layer, an antistatic layer, an antihalation layer and a back coat layer.

A known method can be used for packaging the photographic light-sensitive material of the present invention.

Since the silver halide photographic light-sensitive material is sensitive to heat and humidity, it is preferable to avoid storing it under severe conditions. Generally, it is better to store at 5 ° C to 30 ° C. Humidity should be between 35% and 60% relative humidity. In order to protect it from humidity, it is generally packaged in polyethylene of 1 to 2000 µ. Polyethylene can suppress the permeation of water by improving the regularity of crystals by using a metallocene catalyst. Also,
Moisture permeation can be suppressed by coating the surface of polyethylene by vapor deposition with silica to a thickness of 0.1 to 1000 μm.

If necessary, the developer contains an alkaline agent (sodium hydroxide, potassium hydroxide, etc.), a pH buffering agent (eg, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.), Dissolution aids (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoamers, Antifoggants (eg halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali) Metal salts, nitrilotriacetic acid salts, polyphosphates, etc., development accelerators (eg For example, compounds described in U.S. Pat. No. 2,304,025 and Japanese Patent Publication No. 47-45541), hardeners (eg glutaraldehyde or bisulfite adduct thereof), antifoaming agents and the like can be added. PH of developer
Is preferably adjusted to 7.5 or more and less than 10.5. The pH is more preferably 8.5 or more and 10.4 or less.

The waste developer can be regenerated by energizing it. Specifically, an anion exchange is performed by putting a cathode (for example, an electric conductor or semiconductor such as stainless steel wool) in the developing waste solution and an anode (for example, an insoluble electric conductor such as carbon, gold, platinum, or titanium) in the electrolyte solution. The waste developer tank and the electrolyte solution tank are in contact with each other through the film, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material according to the present invention while energizing. At that time, various additives added to the developer,
For example, preservatives, alkaline agents, pH buffers, sensitizers, antifoggants, silver sludge inhibitors, etc., which can be added to the developing solution, can be additionally added. Further, there is a method of processing the light-sensitive material while energizing the developing solution, and at that time, an additive which can be added to the developing solution as described above can be additionally added. When the waste developer is regenerated and used, transition metal complex salts are preferable as the developing agent of the developer used.

As a special form of development processing, a developing agent is contained in a light-sensitive material, for example, in an emulsion layer or in a layer adjacent to the light-sensitive material, and the light-sensitive material is processed in an alkaline aqueous solution to be used in an activator processing solution for development. Good. Further, a light-sensitive material containing a developing agent in a light-sensitive material, for example, an emulsion layer or an adjacent layer thereof may be processed with a developer. 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.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent 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.

The fixing solution contains a water-soluble aluminum salt which acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may contain preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, citric acid), pH adjusters (eg, sulfuric acid), and chelates capable of softening water. Compounds such as agents may be included.

In the present invention, the ammonium ion concentration in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution.

The ammonium ion concentration is particularly preferably in the range of 0 to 0.05 mol per liter of fixing solution. As the fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

In the present invention, the concentration of acetate ion in the fixing solution is preferably less than 0.33 mol / liter. The type of the acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates the acetate ion in the fixing solution. However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used, and particularly sodium salt. Salts and ammonium salts are preferred. The acetate ion concentration is more preferably 0.22 mol or less, and particularly preferably 0.13 mol or less, per liter of the fixing solution, whereby the acetic acid gas generation amount can be highly reduced. Most preferably, it is substantially free of acetate ions.

The fixing solution used in the present invention preferably contains thiosulfate. Examples of the thiosulfate include lithium, potassium, sodium and ammonium salts, preferably sodium salt or ammonium salt. The amount of thiosulfate added is 0.1 per 1 liter of fixer.
-5 mol, more preferably 0.5-2.0 mol, still more preferably 0.7-1.8 mol. Most preferred 0.8-1.5
Is a mole.

The fixer used in the present invention includes citric acid,
Salts such as tartaric acid, malic acid, succinic acid, and optical isomers thereof are included. Citric acid, tartaric acid, malic acid,
As the salt of succinic acid, lithium salt, potassium salt, sodium salt, ammonium salt, etc., such as lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, tartaric acid ammonium potassium, tartaric acid sodium potassium, etc. may be used. Good. Of these, more preferred are citric acid, isocitric acid, malic acid, succinic acid and salts thereof. Most preferably, malic acid and its salt.

In the present invention, the fixing treatment is followed by washing with water and / or treatment with a stabilizing bath. As a stabilizing bath, adjust the film pH for the purpose of stabilizing the image (pH of the film surface after processing)
3 to 8) and inorganic and organic acids and salts thereof,
Or an alkaline agent and its salt (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide,
Used in combination with sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc.), aldehydes (eg formalin, glyoxal, glutaraldehyde, etc.), chelating agent ( For example, ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphates, etc., antifungal agents (eg phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, P- Hydroxybenzoate, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-
2'-hydroxy diphenyl ether, etc.), color tone adjusting agent and / or residual color improving agent (eg nitrogen-containing heterocyclic compound having mercapto group as a substituent; specifically, 2-mercapto-5-sodium sulfonate-benzimidazole) , 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,
4-triazole, 2-mercaptohypoxanthine, etc.). Among them, it is preferable that the stabilizing bath contains an antifungal agent. These may be replenished in liquid or solid form.

In the present invention, in order to reduce the amount of waste liquid, it is preferable that the processing is performed while replenishing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. The developer replenishing amount and the fixer replenishing amount are each 330 m per 1 m ^2.
l or less. Preferably 30 to 200 ml per 1 m ²
Is. The developer replenishing amount and the fixer replenishing amount herein refer to the amount of replenishing liquid. Specifically, it is the replenishing amount of each liquid when replenishing the same liquid as the developing mother liquid and the fixing mother liquid, and each concentrating liquid when replenishing with the liquid obtained by diluting the developing concentrated liquid and the fixing concentrated liquid with water. And the total amount of water, the total amount of each solid processing agent and the volume of water when the solid development processing agent and the solid fixing processing agent are replenished with a liquid dissolved in water, and the solid development processing agent. And the total amount of each solid processing agent volume and water volume when the solid fixing processing agent and water are separately replenished. When the solid processing agent is replenished, it is preferable to represent the total amount of the volume of the solid processing agent directly added to the processing tank of the automatic processor and the volume of replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as or different from the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine. In particular, when the developer replenishing amount is 120 ml or less per 1 m ² , it is preferable that the developer replenishing liquid is a liquid or a solid processing agent different from the developing mother liquid in the tank of the automatic developing machine. The amount of the silver sludge inhibitor having the formula (I) is preferably larger than the amount contained in the developing mother liquor, and is contained in the developing replenisher.
The amount of the compound represented by or the transition metal complex salt is preferably 1.2 to 4 times the amount contained in the developing mother liquor. Also, especially when the replenishing amount of the fixer is 150 ml or less per 1 m ² ,
The fixer / developer replenisher is preferably a liquid or a solid processing agent different from the fixer mother liquor in the tank of the automatic processor, and the amount of thiosulfate contained in the fixer replenisher is larger than the amount contained in the fixer mother liquor. preferable.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

In the present invention, the total processing time (Dry to Dry) from when the film front end is inserted into the automatic developing machine to when it exits from the drying zone when processing is performed using the automatic developing machine from the demand for shortening the developing time is It is preferably 50 seconds or less and 10 seconds or more. 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. Time including all process time, that is, Dry
It's time to dry. Desensitization when the total processing time is less than 10 seconds,
Satisfactory photographic performance cannot be obtained due to softening. More preferably, the total processing time (Dry to Dry) is 15 to 44 seconds. Also,
The development time is preferably 18 seconds or less and 2 seconds or more for stable running processing of a large amount of light-sensitive material of 10 m ² or more.

In order to bring out the effect of the present invention remarkably, a heat transfer material at a temperature of 60 ° C. or higher (for example, 60 ° C. to 13 ° C.) is used in an automatic processor.
A heat roller at 0 ° C or a radiant object at 150 ° C or higher (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide / yttrium oxide / thorium oxide, silicon carbide, etc., can be used to generate heat and radiate heat from a resistance heating element. Energy of copper, stainless steel, nickel,
It is preferable to use one having a drying zone by emitting infrared rays by transmitting it to a radiator such as various ceramics to generate heat.

A heat roller is used as an example of the heat transfer material having a temperature of 60 ° C. or higher. As for the heat roller, it is preferable that the outer circumference of the hollow roller made of aluminum is covered with silicone rubber, polyurethane, or Teflon. It is preferable that both ends of the heat roller are disposed inside the vicinity of the conveying port of the drying section by bearings of a heat-resistant resin (for example, product name: Rulon) and rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller, and the gear is rotated in the carrying direction by the drive means and the drive transmission means. A halogen heater is inserted in the roller of the heat roller, and this halogen heater is preferably connected to a temperature controller arranged in the automatic developing machine.

A thermistor placed in contact with the outer peripheral surface of the heat roller is connected to the temperature controller. The temperature controller detects the temperature from the thermistor at 60 ° C to 150 ° C, preferably 70 ° C to 130 ° C. Therefore, it is preferable to control the halogen heater on and off.

The following examples can be given as examples of the radiation object that emits a radiation temperature of 150 ° C. or higher. (Preferably 250 ° C or higher) Tungsten, carbon, tantalum, nichrome, zirconium oxide / yttrium oxide / thorium oxide mixture, silicon carbide, molybdenum disilicide, lanthanum chromate There is a method of controlling or transferring the heat energy from the resistance heating element to the radiator to control, and examples of the radiator include copper, stainless steel, nickel and various ceramics.

[0120]

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

Example 1 (Preparation of Silver Halide Emulsion A) A silver chlorobromide core grain having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which is composed of 70 mol% of silver chloride and the rest of which is silver bromide, is prepared by using a simultaneous mixing method. Prepared. When mixing the core particles, K ₃ RuCl ₆ was added at 8 × 10 ^-8 mol per mol of silver. The core particles were shelled using the double jet method. At this time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ^-7 mol per mol of silver. The resulting emulsion had a core / shell type monodisperse (variation coefficient of 10%) with an average thickness of 0.10 μ and an average diameter of 0.25 μ, and had silver chloroiodobromide (90 mol% silver chloride, 0.2 mol% silver iodobromide, and the rest odor). It was a tabular grain emulsion (comprising silver halide). Then, JP-A-2-28
Denatured gelatin described in JP-A No. 2-139, which is obtained by substituting amino groups in gelatin with phenylcarbamyl.
[0139] Desalination was performed using Exemplified Compound G-8) on page 287 (3).
The EAg after desalting was 190 mv at 50 ° C.

The resulting emulsion was treated with 4-hydroxy-6-methyl-1,
Add 3,3a7-tetrazaindene at 1 × 10 ^-3 mol per mol of silver, and add potassium bromide and citric acid to give a pH of 5.
6. After adjusting to EAg123mv, 2 × 10 ^-5 mol of chloroauric acid was added, then 3 × 10 ^-6 mol of inorganic sulfur was added, and chemical aging was performed at a temperature of 60 ° C. until the maximum sensitivity was obtained. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol and gelatin. Was added.

(Preparation of silver halide photographic light-sensitive material for printing plate-making scanner for HeNe laser light source) On one undercoat layer of a polyethylene terephthalate (PET) support, a gelatin undercoat layer of the following Formulation 1 was used. 0.5 g / m ² of silver halide emulsion layer 1 of Formulation 2 thereon, so that the silver amount was 2.9 g / m ² and the gelatin amount was 0.5 g / m ² .
Further, as an intermediate protective layer on the upper layer thereof, a coating solution of the following Formulation 3 was used so that the amount of gelatin was 0.3 g / m ² , and on the upper layer thereof, a silver halide emulsion layer 2 of Formulation 4 was silver amount of 0.2 g / m ² ,
Simultaneous multilayer coating was performed so that the amount of gelatin was 0.4 g / m ² and the coating solution of the following formulation 5 was 0.6 g / m ² . On the other side of the undercoat layer, a backing layer of the following Formulation 6 was prepared so that the amount of gelatin was 0.6 g / m ^2, and a hydrophobic polymer layer of the following Formulation 7 was further formed thereon and the following Formulation 8 The backing protective layer of 0.4g gelatin amount
A sample was obtained by performing simultaneous multilayer coating on the emulsion layer side so that it would be / m ² .

The coating solution for protective film was stagnated at 38 ° C. for the time shown in Table 1 before coating on the PET support.

Formulation 1 (gelatin undercoat layer composition) Gelatin 0.5 g / m ² Dye AD-11 solid dispersion fine particles (average particle size 0.1 μm) 25 mg / m ² Dye AD-8 solid dispersion fine particles (average particle size 0.1 μm) 20 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (silver halide emulsion layer 1 composition) Silver halide Emulsion A Silver amount 2.9 g / m ² equivalent amount Cyclodextrin (hydrophilic polymer) 0.5 g / m ² Sensitizing dye d-1 6 mg / m ² Sensitizing dye d-2 3 mg / m ² Hydrazine derivative: Exemplified compound (Table 30 mg / m ² Nucleation accelerator: Exemplified compound Na-3 40 mg / m ² Compound e 100 mg / m ² Latex polymer f 1.0 g / m ² Hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxy purine ^{10mg / m 2 EDTA 50mg / m} 2 colloidal silica (average particle size 0.05 .mu.m) 10 mg m ² Formulation 3 (intermediate layer composition) Gelatin ^{0.3g / m 2 S-1 2mg} / m 2 Formulation 4 (silver halide emulsion layer 2 composition) Silver halide emulsion B silver amount 0.2 g / m ² corresponding amount Sensitizing dye d-1 0.5 mg / m ² redox compound and comparative compound Amount shown in Table 1 S-1 1.7 mg / m ² Formulation 5 (emulsion protective layer composition) Gelatin 0.6 g / m ² Additive species (shown in Table 1) 50 mg / M ² Dye AD-5 solid dispersion (average particle size 0.1 μm) 40 mg / m ² S-1 12 mg / m ² Matting agent: Monodisperse silica with average particle size 3.5 μm 25 mg / m ² 1,3-vinyl Sulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener: Exemplified compound K-2 30 mg / m ² Formulation 6 (backing layer composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² Dye k 20 mg / m ² Polystyrene sulfo Sodium acid salt 20mg / m ² Compound i 100mg / m
² prescription 7 (hydrophobic polymer layer composition) latex (methyl methacrylate: acrylic acid = 97: 3) 1.0 g / m
² Hardener g 6 mg / m ² Formulation 8 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethylmethacrylate 50 mg / m ^{2 with an} average particle size of 5 μm Sodium-di- (2-ethylhexyl) sulfosuccin 10 mg / m ² surfactant h 1 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener: Compound K-2 20 mg / m
²

[0126]

[Chemical 21]

[0127]

[Chemical formula 22]

[0128]

[Chemical formula 23]

The obtained sample was evaluated by the following development processing and method.

(Evaluation method) Gamma: PDA6 after wedge exposure of the sample and development processing
Density of 0.5 when measured with a densitometer (manufactured by Konica Corporation).
The gamma has a tangent of 3 and 3.0.

Pinhole: The sample was exposed to a concentration of 4.0, and the number of pinholes due to bacteria per 1 m ² was counted.

(Processing) Developer composition (per liter) Diethyltriamine pentaacetic acid 5 sodium
1.0 g sodium sulfite
42.5 g potassium sulfite 17.5 g potassium carbonate 55.0 g hydroquinone 20.0 g 1-phenyl-5-mercaptotetrazole 0.03 g 4-methyl-5-hydroxymethyl-1-phenyl-3-hydrazine 0.85 g potassium bromide 4.0 g benzotriazole 0.21 g Boric acid 8.0g Diethylene glycol 40.0g 8-Mercaptoadenine 0.07g Add water and potassium hydroxide to make 1 liter and adjust the pH to 10.4.

Fixer composition (per liter) Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 gg Aluminum sulfate (27% aqueous solution) ) 25 ml water was added to make 1 liter, and the pH was 4.9.

Processing Conditions Step Temperature (° C.) Time (sec) Development 38 12 Fixing 35 10 Washing with water 20 10 Drying 50 12 Total 44 The results are shown in Table 1.

[0135]

[Table 1]

Compound A: HOCH ₂ C (Br) (NO ₂ ) CH ₂ OH,
Compound B: Phenol As is clear from the results shown in Table 1, the sample according to the present invention has the effect of maintaining the high contrast even when the solution is stagnant and reducing the pinholes caused by bacteria.

Example 2 (Synthesis of Latex La) 40 ml of water was mixed with 0.125 kg of various industrial KMDS (dextran sulfate sodium salt) and 0.05 kg of ammonium persulfate while stirring at a liquid temperature of 80 ° C.
Under a nitrogen atmosphere, a mixture of (a) to (c) as shown below is added over 1 hour, and after stirring for 1.5 hours, K
MDS (1.25 kg) and ammonium persulfate (0.005 kg) were added, and the mixture was stirred for 1.5 hours. After completion of the reaction, steam distillation was carried out for another hour to remove residual monomers, and after cooling to room temperature, the pH was adjusted to 6.0 with ammonia. The obtained latex liquid was adjusted to 50.5 Kg with water.

(A) n-Butyl acrylate 4.51 Kg (a) Styrene 5.49 Kg (c) Acrylic acid 0.1 Kg As described above, a monodisperse latex having an average particle size of 0.25 μm and a Tg of about 0 ° C. was obtained.

(Emulsion preparation) A silver nitrate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × of a rhodium hexachloride complex.
The solution added to 10 ^-5 mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate.
A cubic crystal, monodisperse, silver chlorobromide emulsion containing μ, 1 mol% of silver bromide was obtained.

This emulsion was sulfur-sensitized by a conventional method, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer to give gelatin of 1.2 g / m ^2. After adding gelatin, add the following additives to prepare emulsion coating solution E-
No. 0 was prepared, and then emulsion protective layer coating solution P-0, backing layer coating solution B-0 and backing protective layer coating solution BP-0 were prepared with the following compositions.

(Preparation of Emulsion Coating Solution) Adjusted to NaOH (0.5N) pH 5.6 Tetrazolium compound (shown in Table 2) 30 mg / m ² saponin (20%) 0.5 cc / m ² sodium dodecylbenzenesulfonate 20 mg /
m ² 5-methylbenzotriazole 10 mg / m ² compound (b) 2 mg / m ² compound (c) 6 mg / m ² latex La 1.0 g / m ² styrene-maleic acid copolymer polymer (thickener) 90 mg / m ²

[0142]

[Chemical formula 24]

(Emulsion Protective Layer Coating Solution P-0) Gelatin 1.1 g / m ² compound (d) (1%) 25 cc / m ² compound (e) Amount shown in Table 4 p-perfluoro-4-nonenyl-benzenesulfone Acid soda 2 mg / m ² Spherical monodisperse silica (8 μm) 20 mg / m ² 〃 (3 μm) 10 mg / m ² Compound (f) 100 mg / m ² Citric acid Adjusted to pH 6.0 Styrene-maleic acid copolymer polymer (increased Sticky agent) 100 mg / m ² (backing layer coating solution B-0) Gelatin 1.0 g / m ² compound (g) 100 mg / m ² compound (h) 18 mg / m ² compound (i) 100 mg / m ² saponin (20% ) 0.6 cc / m ² latex (j) 300 mg / m ² 5-nitroindazole 20 mg / m ² styrene-maleic acid copolymer polymer (thickener) 45 mg / m ² glyoxal 4 mg / m ² compound (k) 10 mg / m ² compound (l) 10mg / m ² 5- methyl benzotriazole 20 mg / m ² (backing protective layer coating solution BP-0) Keratin 0.5 g / m ² Compound (d) (1%) 2cc / m 2 Spherical polymethylmethacrylate (4μ) 25mg / m ² Sodium chloride 70 mg / m ² Glyoxal 22 mg / ^{m 2}

[0144]

[Chemical 25]

[0145]

[Chemical formula 26]

[0146]

[Chemical 27]

On the PET support provided with the undercoat layer in Example 1, first, as the emulsion side, the emulsion layer and the emulsion protective layer were kept in order from the side closer to the support at 35 ° C. by a slide hopper system to form a hardener solution. As formalin solution was added at 30 mg per g of gelatin, and simultaneous multilayer coating was performed. A backing layer and a backing protective layer were applied in multiple layers on the opposite surface of the support while adding a hardener with a slide hopper.

The sample thus obtained was subjected to the following treatments to obtain Example 1
Was evaluated in the same way as

(Standard processing conditions) Development 28 ° C. 30 seconds Fixing 28 ° C. 20 seconds Washing with water 15 seconds at room temperature Drying 40 ° C. 35 seconds [Developer formulation] (Composition A) Pure water (ion exchange water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to make the pH of the solution 10.4 or 11.0 Bromide Potassium 4.5g (Composition B) Pure water (ion exchanged water) 3ml Diethylene glycol 50mg Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3ml 5-Nitroindazole 110mg 1-Phenyl-3-pyrazolidone 500mg When using the developer The above-mentioned composition A and composition B were dissolved in 500 ml of water in this order, and the solution was made into 1 liter and used.

[Fixer Formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 5.6 g Sodium acetate trihydrate 27.8 g Boric acid 9.8 g Sodium citrate dihydrate 2.0 g Acetic acid (90 % W / V aqueous solution) 6.4
ml (Composition B) Pure water (ion exchanged water) 28m
l Sulfuric acid (50% W / V aqueous solution) 6.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 25.31 g When using the fixer, dissolve the above composition A and composition B in 500 ml of water in this order. It was used after finishing to 1 liter. The fixer pH was about 4.4.

The results are shown in Table 2.

[0152]

[Table 2]

From the results in Table 2, it is clear that the present invention maintains the high contrast even when the solution is stagnant and further reduces the pinholes caused by bacteria.

Example 3 The same procedure as in Example 1 was carried out except that the following developing solution was used. The sample used was that prepared in Example 1.

(Developer) Pure water (ion exchanged water) 800 ml Potassium carbonate 70 g Compound of general formula [I] A-17 25 g Dimezone S 1.0 g DTPA · 5N _a 1.45 g Potassium bromide 5 g 5-methylbenzotriazole 0.2 g 1-Phenyl-5-mercaptotetotrazole 0.03 g Compound [S] 0.09 g Sodium sulfite 40 g Diethylene glycol 40 g pH adjustment with potassium hydroxide 9.8 g Finally, 1 L was added with pure water.

Dimezone S 1-phenyl-4-hydroxymethyl-4-methylpyrazolidone 1.0 g

[0157]

[Chemical 28]

Fixing solution Sodium thiosulfate 250 g Pure water (ion-exchanged water) 20 ml Sodium sulfite 15 g Boric acid 6 g Tartaric acid 2 g Malic acid 10 g Aluminum sulfate (aqueous solution having an Al ₂ O ₃ conversion content of 8.1% W / W) 20 ml Finally, pure Make up to 1 liter with water. The pH was adjusted to 4.5 with a 50% W / W sulfuric acid aqueous solution.

The results are shown in Table 3.

[0160]

[Table 3]

From the results shown in Table 3, the same procedure as in Example 1 was carried out even when a photosensitive material containing a hydrazine derivative was used without using hydroquinone and a developing solution containing a compound represented by the general formula [I] of the present invention. It can be seen that various effects can be obtained.

Example 4 The developer formulation and the fixer formulation were the same as in Example 3, and the other conditions were the same as in Example 2. The sample used in Example 2 was used.

The results are shown in Table 4.

[0164]

[Table 4]

From the results shown in Table 4, even when the photosensitive material containing tetrazolium as a preferred material was used without using hydroquinone and using the developing solution containing the compound represented by the general formula [I] of the present invention, It can be seen that the same effect can be obtained.

Example 5 The developer used in Example 1 is DHH, and the developer used in Example 3 is DAA. The developing solution was DHH, DAA (replenishing amount was 12.5 ml per sheet for cutting 4 sheets), the fixing solution was that used in Example 1 (replenishing amount was 22 sheets for 4 sheets, and the washing water was for water temperature). Well water heated to 20 ° C. (4 pieces, 100 ml per sheet) was used.

Automatic processor GR-26SR (Konica Corporation)
Example 1 shown below using a partially modified
The size of the sample prepared in Step 5 was blackened under a fluorescent lamp.
After being treated for 00 sheets and left for 72 hours, one piece of unblackened large size of scanner film RSP-III (manufactured by Konica [Co.]) was treated.

With this sample, the degree of stain was visually evaluated. It was evaluated on a scale of 10 from 10 which was not soiled at all, 10 which was a practically acceptable lower limit, and 1 which was unusable. Similar experiments were conducted on the DAA developer and other samples, and the results are shown below. The treatment process time was the same as in Example 1.

Developer Solution Sample (Example 1 NO) Contamination DHH 9 6 DHH 13 9 DAA 9 4 DAA 13 9 As is clear from the above results, the present invention produces less stains even in a developer containing no hydroquinone. You can see that there are few.

Example 6 To the developers DHH and DAA, 50 mg / liter of gentamicin C1 was added, respectively. No. 3 of Example 3 and Example 2. An experiment similar to that of Example 5 was performed using the sample of No. 3. When the compound of the present invention was added to the developing solution, the generation of stain was small as in Example 5.

[0171]

Industrial Applicability According to the present invention, it is possible to provide a light-sensitive material and a method for processing the light-sensitive material, which prevent damages and adhesion of stains by microorganisms during the production of the light-sensitive material and before the processing.

Claims (4)

[Claims] 1. A support having a silver halide emulsion layer,
In a silver halide photographic light-sensitive material containing a hydrazine derivative or a tetrazolium compound as a contrast-increasing agent in the silver halide emulsion layer and the hydrophilic colloid layer, the silver halide photographic light-sensitive material is replaced with gentamicin, amikacin,
A silver halide characterized by being processed in the presence of at least one aminoglycoside selected from topramycins, dibekacins, arbekacins, micronomycins, isevamycins, silymycins, netilmycins and astromycins. Processing method of photographic light-sensitive material. 2. A silver halide emulsion layer is provided on a support,
In a silver halide photographic light-sensitive material containing a hydrazine derivative or a tetrazolium compound as a contrast-increasing agent in the silver halide emulsion layer and the hydrophilic colloid layer, gentamicins, amikacins, topramycins, dibekacins, arbekacins, micronos A silver halide photographic light-sensitive material containing at least one aminoglycoside selected from mycins, isebamycins, sirimycins, netilmycins and astromycins. 3. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, the silver halide photographic light-sensitive material being gentamicin, amikacin, topramycin, dibekacin, arbekacin, microno. In the presence of at least one aminoglycoside selected from mycins, isebamycins, silymycins, netilmycins and astromycins, the compound is substantially free of a dihydroxybenzene compound and is represented by the following general formula [1] A method for processing a silver halide photographic light-sensitive material, which comprises processing with a developer containing a compound. Embedded image [Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or R ₁ and R _{2 s} may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. ] 4. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support, which comprises gentamicin, amikacin, topramycin, dibekacin,
A silver halide photographic light-sensitive material containing at least one kind of aminoglycoside selected from arbekacins, micronomycins, isebamycins, sirimycins, netilmycins and astromycins,
A silver halide photographic light-sensitive material, characterized by being treated with a developer containing substantially no dihydroxybenzene compound and containing the compound represented by the general formula [1].