JPH1124212A - Method for processing black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method for processing the black-and-white silver halide photographic sensitive material free from drop of maximum density and rise of fog and deterioration of reversed letter quality even in the case of using a single agent type developer or such a fixing agent. SOLUTION: The developer comprises part granules containing a compound represented by the formula and part granules containing an alkaline compound having an acid dissociation constant (pKa) of >=9, or a fixing agent comprising part granules containing at least one of a thiosulfate or thiocyanate and part granules containing a water-soluble aluminum salt and gluconic acid, and in each of the developer and the fixing agent, each of the part granules are covered with sugars or water-soluble polymers into one unit to form the single agent type developer and fixing agent. In the formula, each of R11 and R12 is an optionally substituted alkyl group or the like and each may combine with each other to form a ring; (k) is 0 or 1, and when k=1, X is a -CO- or -CS- group; and each of M1 and M2 is an H or alkali metal atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a black-and-white silver halide photographic material, and more particularly to a method for processing a black-and-white silver halide photographic material using a solidified processing agent.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter also simply referred to as a "light-sensitive material") is subjected to processing such as development, fixing, washing and stabilization after exposure. Processing is usually performed by an automatic developing machine, and a method of replenishing a replenisher in order to keep the activity of the processing solution constant is generally widely used. The replenishment of the replenisher is intended to dilute the eluate from the light-sensitive material, correct the amount of evaporation, and replenish the consumed components. Each processing solution and replenisher used in these automatic processors is supplied as a concentrated solution, and is usually diluted at the time of use.

In recent years, it has become common to prepare and replenish processing solutions by using a solid processing agent formed as a kind of molded product by previously mixing a required amount of a solid component of the processing agent.

However, at present, the solid processing agent is generally divided into two or more parts for both the developer and the fixing agent. When two agents are used for production, there is a problem in that it takes a lot of time and effort in packaging, and there is always a risk that the number of tablets in each part is wrong. In addition, having to make two types for manufacturing is very costly.

[0005] Conventionally, treatment with a single tablet has been tried. However, the treatment with one tablet greatly reduces the maximum density, and when processing with a recent hydrazine sensitizing material, fogging occurs. And the linearity greatly deteriorates. Furthermore, in the case of a light-sensitive room return photographic material or the like, a serious problem that a predetermined performance such that characters are crushed at the time of return cannot be exhibited, and a solution has been strongly desired.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a black-and-white silver halide photographic light-sensitive material in which the maximum density is not reduced even when a single processing agent is used, and the fog is not increased and the quality of a blank character is not deteriorated. It is an object of the present invention to provide a processing method using a solid developer for use and a solid fixing agent.

[0007]

The above object of the present invention is attained by the following constitutions.

(1) At least two part granules comprising a part granule containing a compound represented by the following general formula (A) and a part granule containing at least one alkaline compound having an acid dissociation constant (pKa) of 9 or more. Wherein the part granules are coated with at least one selected from saccharides or water-soluble polymer compounds, and wherein the part granules are used as a kind of molded product without localization using a solid developer. For processing black-and-white silver halide photographic light-sensitive materials.

[0009]

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In the formula, R ₁₁ and R ₁₂ each represent an alkyl group, an amino group, an alkoxy group, or an alkylthio group;
These may have a substituent and may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

(2) In the above-mentioned processing method, a dihydroxybenzene-based developing agent (HQ mole) and the above-mentioned general formula (A)
The method for processing a black-and-white silver halide photographic material according to (1), wherein the molar ratio (HQ / A) to the compound (A mole) represented by the formula (A) is from 0 to 1,000.

(3) The black-and-white silver halide photographic material as described in (1) or (2), wherein the silver halide photographic material contains a compound represented by the following formula (H). Processing method.

[0013]

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In the formula, A represents an aliphatic group, an aromatic group or a heterocyclic group, and B represents an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group, Represents an aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group, or a heterocyclic group. A ₁ and A _{2 each} represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group.

(4) The black-and-white silver halide photographic material as described in (1) or (2), wherein the silver halide photographic material contains a compound represented by the following formula (C). Processing method.

[0016]

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In the formula, R _c1 , R _c2 and R _c3 represent a hydrogen atom or a substituent, and X ⁻ represents an anion.

(5) At least two part granules comprising part granules containing at least one thiosulfate or thiocyanate and part granules containing at least one water-soluble aluminum salt and gluconic acid. A black-and-white silver halide photograph, wherein a solid fixing agent coated with at least one selected from saccharides or a water-soluble polymer compound and formed as a type of molded product without localization of the part granules is used. Processing method of photosensitive material.

Hereinafter, the present invention will be described in detail.

The compound represented by the general formula (A) is ascorbic acid or a derivative thereof. Among the compounds represented by the general formula (A), R ₁₁ and R ₁₂ are bonded to each other to form a ring. It is preferable to use a developing agent represented by -a).

[0021]

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[0022] In the formula, R ₁₃ is a hydrogen atom, each substituted or unsubstituted alkyl group, an aryl group, an amino group, an alkoxy group, or a sulfo group, a carboxyl group, an amide group, a sulfonamide group, Y ₁₁ is O or S is represented, and Y ₁₂ represents O, S or NR ₁₄ . R ₁₄ represents a substituted or unsubstituted alkyl group or aryl group.

The formula (A) or the formula (Aa)
Specific examples of preferred compounds represented by are shown below, but are not limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

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The developer according to the present invention can be used in combination with a hydroxybenzene-based developer in addition to the developing agent represented by the general formula (A). The hydroxybenzene-based developer referred to herein is a compound represented by the following general formula (I):
(III).

[0029]

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In the formula, R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, a carboxyl group, a halogen atom or a sulfo group.

Examples of the dihydroxybenzene-based developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, methylhydroquinone, and hydroquinonesulfonic acid, with hydroquinone being particularly preferred.

The molar ratio (HQ / A) of the dihydroxybenzene-based developing agent (HQ mole) to the compound represented by formula (A) (A mole) is from 0 to 1,000, preferably from 0 to 100. And more preferably 0 or more and 3
0 or less.

Next, the general formula (H) used in the present invention
The hydrazine compound represented by the formula will be described.

The aliphatic group represented by A preferably has 1 to 30 carbon atoms, and particularly preferably is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, a benzyl group, and the like, and these are further suitable substituents (for example, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, A sulfoxy group, a sulfonamide group, an acylamino group, a ureido group, etc.). The aromatic group represented by A is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring. As the heterocyclic group represented by A, at least nitrogen of a monocyclic or condensed ring,
Sulfur, a hetero ring containing one hetero atom selected from oxygen is preferable, for example, a pyrrolidine ring, an imidazole ring,
Examples include 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. A
Are particularly preferably an aryl group and a heterocyclic group. The aryl group and heterocyclic group of A may have a substituent. Representative substituents in this case are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or condensed ring having an alkyl moiety having 1 to 3 carbon atoms), an alkoxy group (Preferably, the alkyl moiety has 1 to 20 carbon atoms), a substituted amino group (preferably, an amino group substituted with an alkyl group or an alkylidene group having 1 to 20 carbon atoms), an acylamino group (preferably, 1 to 20 carbon atoms) 40), a sulfonamide group (preferably having 1 to 40 carbon atoms), a ureido group (preferably having 1 to 40 carbon atoms), a hydrazinocarbonylamino group (preferably having 1 to 40 carbon atoms) , A hydroxyl group and a phosphoamide group (preferably having 1 to 40 carbon atoms). A preferably contains at least one diffusion-resistant group or silver halide adsorption promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group or an alkenyl group which is relatively inert to photographic properties having 8 or more carbon atoms is preferable. Alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether, thione, heterocyclic, thioamide heterocyclic,
Examples thereof include a mercapto heterocyclic group and an adsorptive group described in JP-A-64-90439.

B is specifically an acyl group (for example, formyl, acetyl, propionyl, trifluoroacetyl,
Methoxyacetyl, phenoxyacetyl, methylthioacetyl, chloroacetyl, benzoyl, 2-hydroxymethylbenzoyl, 4-chlorobenzoyl, etc., alkylsulfonyl group (eg, methanesulfonyl, 2-chloroethanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.) ), An alkylsulfinyl group (eg, methanesulfinyl), an arylsulfinyl group (eg, benzenesulfinyl), a carbamoyl group (eg, methylcarbamoyl, phenylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl, methoxyethoxycarbonyl, etc.), aryloxycarbonyl Group (eg, phenoxycarbonyl, etc.), sulfamoyl group (eg, dimethylsulfamoyl, etc.), sulfinamoyl group (eg, Thiosulfinyl group (eg, methoxysulfonyl), thioacyl group (eg, methylthiocarbonyl), thiocarbamoyl group (eg, methylthiocarbamoyl), oxalyl group (general formula (Ha) will be described later), or hetero Represents a ring group (for example, a pyridine ring, a pyridinium ring, etc.). B together with A ₂ and the nitrogen atom to which they are attached

[0036]

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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 preferred.

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 ( Ethoxalyl).

Particularly preferred among the hydrazine compounds used in the present invention are hydrazine compounds represented by the following formula (Ha).

[0040]

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In the general formula (Ha), R ₁ represents an aryl group or a heterocyclic group, and R ₂ represents

[0042]

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Represents R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group,
Represents a heterocyclic group, an amino group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group, and R ₃ and R ₄ may form a ring together with an N atom. R ₅ is a hydrogen atom,
Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group. A ₁ and A ₂ have the general formula (H)
A ₁ and A ₂ in the above have the same meanings.

The general formula (Ha) will be described in more detail. The aryl group represented by R ₁ is preferably a single ring or a condensed ring, and examples thereof include a benzene ring and a naphthalene ring. The heterocyclic group represented by R ₁ is preferably a 5- or 6-membered unsaturated heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur and oxygen in a single ring or a condensed ring. Ring, pyrimidine ring, thiophene ring, furan ring, thiazole ring, benzothiazole ring and the like. Preferred as R ₁ 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). In the case where the contrast is increased with a developer having a pH of 11.2 or less, it preferably has at least one sulfoamide group. A ₁ and A ₂ represent A ₁ and A ₂ group having the same meaning as in formula (H), in the most preferably both hydrogen atoms. R ₂ is

[0045]

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Wherein R ₃ and R ₄ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, benzyl),
Alkenyl group (allyl, butenyl, etc.), alkynyl group (propargyl, butynyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (2,2,6,6-tetramethylpiperidinyl, N-benzylpiperidyl) 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 ( R ₃ and R ₄ may form a ring (piperidine, morpholine, etc.) together with a nitrogen atom, representing a propargyloxy group, an aryloxy group (eg, phenoxy group), or a heterocyclic oxy group (eg, pyridyloxy group). R
₅ 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 heterocyclic group (2,2,6,6-tetramethylpiperidinyl,
N-methylpiperidinyl, pyridyl, etc.).

Specific examples of the hydrazine compound represented by the general formula (Ha) are shown below. However, the present invention is not limited to these. Besides, specific examples of the hydrazine compound represented by the general formula (Ha) are described in JP-A-5-2412.
No. 64.

[0048]

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The method for synthesizing the hydrazine compound represented by the general formula (H) used in the present invention is described in JP-A-62-1803.
No. 61, No. 62-178246, No. 63-23424
No. 5, 63-234246, and 64-90439
JP-A-2-37, JP-A-2-841, JP-A-2-947
No. 2-120736, No. 2-230233, No. 3-125134, US Pat. No. 4,686,167,
The methods described in JP-A-4,988,604, JP-A-4,994,365, EP-A-253,665, JP-A-333,435 and the like can be referred to.

The amount of the hydrazine compound represented by the general formula (H) of the present invention is 5 × 1 per mol of silver halide.
It is preferably 0 ^{-7 to} 5 × 10 ^-1 mol, particularly 5 × 10 ^-1 mol.
It is preferable to be in the range of 10 ^{-6 to} 5 × 10 ^-2 mol.

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

Next, examples of the nucleation accelerator include nucleation accelerators represented by the following general formula [Na] or [Nb].

[0053]

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In the general formula [Na], R ₇₁ , R ₇₂ , R
₇₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₇₁ , R ₇₂ and R ₇₃ can form a ring. 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 compound having a molecular weight of 300 or more is more preferable. Preferred examples of the adsorptive group include a heterocyclic ring, a mercapto group, a thioether group, a thione group, and a thiourea group.

Specific compounds include the following.

[0056]

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[0057]

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[0058]

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In the general formula [Nb], Ar represents a substituted or unsubstituted aryl group or a heteroaromatic ring. R ₈₁ 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 preferred diffusion-resistant group, a molecular weight of 12
It is preferably 0 or more, particularly preferably 300 or more.

Specific examples of the compound represented by the general formula [Nb] include the following.

[0061]

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[0062]

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The silver halide photographic light-sensitive material of the present invention preferably contains a tetrazolium compound. Such a tetrazolium compound is represented by the general formula (C)
The tetrazolium compound represented by these is mentioned.

In the general formula (C), preferred examples of the substituent represented by R _c1 , R _c2 to R _c3 include an alkyl group (for example, methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl) ), Amino group, acylamino group (eg, acetylamino), hydroxyl group, alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.), acyloxy group (eg, acetyloxy), halogen atom (eg, fluorine, chlorine, bromine) Carbamoyl, acylthio (eg, acetylthio), alkoxycarbonyl (eg, ethoxycarbonyl), carboxyl, acyl (eg, acetyl), cyano, nitro, mercapto, sulfoxy, aminosulfoxy It includes groups such as.

[0065] by X ^- as the anion represented, for example, chloride, bromide, halide ions such as iodide ions, nitric acid, sulfuric acid, acid roots of inorganic acids such as perchloric acid,
Acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically lower alkylbenzene sulfonic acid anions such as p-toluene sulfonic acid anion and higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion , Polyalkyl alcohols such as dialkylsulfosuccinate anions such as di-2-ethylhexylsulfosuccinate anions, higher alkyl sulfate anions such as lauryl sulfate anions, boric acid anions such as tetraphenylboron, etc. Higher aliphatic anions such as sulfate ester anions and stearic acid anions, and polymers having acid radicals such as polyacrylic acid anions can be given.

Hereinafter, specific examples of the tetrazolium compound represented by the general formula (C) used in the present invention will be described.

[0067]

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Specific examples of the tetrazolium compound represented by the general formula (C) are described in JP-A-1-287557, [Chem. 8], [Chem. 9], [Chem. 10], [Chem. 11], and [Chem. 12]
And a tetrazolium compound represented by However, the tetrazolium compound represented by the general formula (C) used in the present invention is not limited to these compounds.

The tetrazolium compound used in the present invention is, for example, a chemical review (Chemical R).
views), vol. 55, pages 335 to 483, and can be easily synthesized.

The tetrazolium compound represented by the general formula (C) of the present invention is used in an amount of about 1 mg to 10 mg per mol of the silver halide contained in the silver halide photographic light-sensitive material of the present invention.
g, in particular, in the range of about 10 mg to about 2 g.

The alkali having an acid dissociation constant of 9 or more used in the developer of the present invention specifically includes potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, lithium hydroxide, potassium phosphate and sodium phosphate. And the like. Particularly preferred among these are potassium carbonate, sodium carbonate and lithium hydroxide.

The acid dissociation constant is an equilibrium constant of a chemical equilibrium (called ionization equilibrium) established between an ionized portion and an unionized portion in an aqueous solution of an electrolyte. Taking carbonate as an example, carbonic acid is in the following equilibrium state in an aqueous solution.

[0073]

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At this time, the acid dissociation constant is defined by the following equation.
Here [H ^{+], -} representing each concentration etc. [HCO _3].

[0075] ^{_{Ka 1 = [H +] [}} HCO 3 -] / [H 2 CO 3] Ka 2 = [H +] [CO 3 2-] / [HCO 3 -] pKa 1 = log (Ka 1) pKa ₂ = log (Ka ₂ ) A polybasic acid such as carbonic acid is considered to be a compound of the present invention when the largest pKa value among the dissociation steps is 9 or more.

Thiosulfate used in the fixing agent of the present invention,
Examples of the thiocyanate include potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate. Among these, ammonium thiosulfate and sodium thiosulfate are particularly preferred from the viewpoint of the effects of the present invention.

Examples of the water-soluble aluminum salt used in the fixing agent according to the present invention include aluminum sulfate, aluminum oxide, potassium alum, and ammonium alum. Among these, aluminum sulfate is particularly preferable from the viewpoint of the effects of the present invention.

As the gluconic acid used together with at least one of the water-soluble aluminum salts used in the fixing agent according to the present invention, D, L and DL derivatives are known. Those salts can be used.

Examples of the saccharide or water-soluble high molecular compound used for coating each part granule of the developer and the fixing agent according to the present invention include sugar alcohols, monosaccharides (eg, glucose and galactose), and disaccharides (eg, maltose). ,
Sucrose, lactose, etc.), polysaccharides, polyalkylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyvinyl acetate, aminoalkyl methacrylate copolymer, methacrylic acid-methacrylic acid ester copolymer, methacrylic acid-
An acrylate copolymer, a vinyl polymer having a betaine structure, and the like are included. Of these, preferred
Sugar alcohols, polysaccharides and polyalkylene glycols represented by the general formula G.

General formula G HO- (CH ₂ CH ₂ O) _1- (CH ₂ CH ₂ CH ₂ O) _m-
(CH ₂ (CH ₃ ) CHO) _n -H (wherein l, m and n each represent an integer of 0 to 1000;
+ M + n is 10 or more. Preferred sugar alcohols include threitol, erythritol, arabitol, ribitol, xylitol, sorbitol, mannitol, iditol, talitol, galactitol, and allozlicitol.

Preferred polysaccharides are pullulan, methylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose,
Examples include cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose succinate, carboxymethylethylcellulose, dextrins, cyclodextrins, and starch degradation products. Particularly preferred starch decomposed products include Pine Flow and Paindex manufactured by Matsutani Chemical.

The compounds represented by the general formula G are preferably the following compounds (1) to (6).

[0083]

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In the above formula, l, m, and n have the same meanings as l, m, and n in the general formula G, respectively.

Among them, particularly preferred is polyethylene glycol represented by the compound example (1). Further, the average molecular weight is preferably from 1,000 to 10,000. Specific examples include polyethylene glycol # 2000, # 4000, and # 6000 manufactured by Kanto Chemical.

The granulation method used in the present invention includes:
Methods such as tumbling granulation, extrusion granulation, spouted bed granulation, fluidized bed granulation, crushing granulation, stirring granulation, and compression granulation can be applied. In addition, as a method of coating the saccharide or the water-soluble polymer compound on the granules in the present invention, the granules granulated by any method can be coated with pan coating, tumbling coating, fluid coating and the like.

Further, by using a fluidized bed granulator, a tumbling fluidized bed granulator or the like, granulation and coating can be continuously performed in the same container. This method is preferable in terms of high production efficiency and the effect of the present invention. Hereinafter, a method using a fluidized-bed granulator will be described.

FIG. 1 is a schematic view of an example of a fluidized bed granulator, and the production method of the present invention will be described with reference to FIG. The air sucked by the blower fan F is purified through an air supply filter E made of chemical fiber or the like, then heated to a predetermined temperature by a heat exchanger D, and passed through a rectifying plate 4 to form a fluidized bed granulator main body 1. Sent to This hot air keeps the powder in a suspended state, makes it uniformly contact with the droplets atomized by the compressed air B, the liquid sending device C and the spray device 3, and evaporates and dries the fluidized bed humidified by spraying. Acts as a heat source. The fine powder scattered to the upper part is collected by the dust collecting filter 2 and blown off into the fluidized bed. The air filtered here is exhausted out of the system by the exhaust fan A.

As the liquid to be sprayed, a solution in which the saccharide or the water-soluble polymer compound of the present invention is dissolved in a solvent is used. The solvent is preferably water from the viewpoint of the effects of the present invention, safety and environmental suitability.
The concentration of the saccharide or water-soluble polymer compound dissolved in the solvent is preferably 1% by weight to 70% by weight.

As a method of spraying the solution onto the flowing powder, a pressure nozzle, a rotating disk, a two-fluid nozzle, or the like can be used. The pressurizing nozzle is a method of applying pressure to a solution and ejecting the solution as a high-speed liquid stream into the atmosphere to obtain fine droplets based on a difference between the solution and a relative speed with respect to the atmosphere. The rotating disk is a method in which a liquid is poured into the center of a disk rotating at high speed, and the liquid is atomized into droplets around the disk by centrifugal force. The two-fluid nozzle is a method of breaking down a liquid and obtaining fine droplets by using a compressible gas such as air, nitrogen gas, or water vapor to obtain a high-speed gas stream at a relatively low pressure.

Among them, the method of spraying a trace component solution with a two-fluid nozzle is preferable in terms of the effect of the present invention because the drying of the droplets is fast. In this case, the ratio of the volume of the atomized air discharged from the nozzle per unit time to the volume of the solution (gas / liquid ratio) is preferably 100 or more and 10,000 or less, particularly preferably 1,000 or more and 5000 or less.

A commercially available fluidized bed granulator can be used.
More specifically, Powrex multiplex series,
Examples include the GPCG series, WST / WSG series, Fujimaru's New Malmerizer series, Ogawara's Mixgrade series, Freund's Spiral flow series, and flow coater series.

Part granules containing the compound represented by the general formula (A) of the present invention and an alkaline compound having an acid dissociation constant (pKa) of 9 or more, or at least one of thiosulfates and thiocyanates, At least one of these containing at least one of the conductive aluminum salts and gluconic acid.
One part granule is present in one molding without localization. In order to uniformly mix the part granules without localization, a commercially available mixer is used, but a cross rotary mixer or a V-type mixer is preferable in view of the effects of the present invention. The term “molded product” as used in the present invention refers to a product obtained by solidifying granules, powders, crystals and a mixture thereof into a predetermined shape, and is preferably a so-called tablet characterized by being molded by compression. For the production of tablets, commercially available single-shot tablet presses, single-shot double tablet presses, rotary tablet presses and the like are used. The compression pressure at the time of compression is preferably 0.5 to ³ ton / cm ² . If it is less than 0.5 ton / cm ² , fine powder is likely to be generated at the time of transportation and the like, and if it exceeds 3 ton / cm ² , the effects of preservability and solubility are reduced.

In the present invention, the saccharide or the water-soluble polymer compound is
0.2% by weight or more based on the weight of the part granules to be coated 2
It is preferably 0% by weight or less. The particle size distribution of each part granule is such that granules having a particle size of 149 μm or less are 20% by weight or less based on the weight of each part granule, and
Granules having a particle size of 000 μm or more
It is preferably 0% by weight or less. The measurement of the particle size in the present invention is based on a sieving method using a JIS standard sieve. That is, 149 μm (100 mesh) or 100
It is determined by measuring the weight of the powder that has passed through a 0 μm (16 mesh) sieve and the powder that has not passed.

The solid fixing agent of the present invention preferably contains a compound represented by the formula D in view of the effects of the present invention.

Formula R-(O) _n --SO ₃ M (wherein R represents a linear or branched alkyl group, alkenyl group, or alkynyl group, n represents 0 or 1, and M represents a hydrogen atom The following are examples of the compound represented by the formula D, which is preferably used in the present invention.

[0097]

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Particularly preferred compounds among these are (1)
In (5), R is an alkyl group having 4 to 10 carbon atoms, and n is preferably 0.

In the processing of the photosensitive material, the processing is performed while replenishing a fixed amount of processing solution in proportion to the area of the photosensitive material in order to reduce the amount of waste liquid. The replenishing amount of the developing solution is 200 ml or less per m ² , and the replenishing amount of the fixing solution is 250 ml.
/ L or less. Preferably 50 per m ² each
１９０190 ml.

The starting developer and the starting fixer may be liquid processing agents or solid processing agents dissolved therein. However, in order to produce a large amount of processing solution at once in a short time, the liquid processing agent is used. It is more convenient to have

The replenishing amount of the developing solution and the replenishing amount of the fixing solution indicate the amount of the replenishing solution. Specifically, it is the replenishment amount of each of the developing mother liquor and the fixing mother liquor when replenishing the same liquor, and the respective concentrated liquor when the developing concentrated liquor and the fixing concentrated liquor are replenished with a solution diluted with water. And the total amount of water, and the total amount of each solid processing agent volume and water volume when the solid processing agent is replenished with a solution prepared by dissolving in water, and the solid processing agent and water are separately replenished. It is the sum of the volume of each solid treatment agent and the volume of water in each case. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing and fixing replenishers may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, or different liquids or solid processing agents.

In the case of a solid processing agent, the amount of the processing agent fed at one time is preferably 0.1 to 50 g, and the amount of the processing agent is
0 g is preferably 5 to 50 g in the case of the fixing solution. Even if the solid processing agent in this range is directly charged into a processing tank of a general small-sized automatic processor and processed while slowly dissolving, it does not affect the photographic state. . This is because the solid processing agent does not dissolve rapidly but dissolves slowly, so even if the amount added at a time is large, the composition is balanced to the amount consumed during processing and shows stable photographic performance. . It was found that the photographic performance could be kept constant by injecting the replenishing water along with the dissolution. The temperature of the processing liquid is always adjusted to the processing temperature, and is maintained at a substantially constant temperature.
That is, since the dissolution speed is almost constant, the calculated addition of the solid processing agent and the balance of the components are achieved.

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

From the viewpoint of rapid processing, when processing is performed using an automatic developing machine, the total processing time (Dr) from when the leading end of the photosensitive material is inserted into the automatic developing machine to when it comes out of the drying zone is obtained.
yto dry) is preferably from 10 to 60 seconds, more preferably from 15 to 50 seconds. Also, 100m
^In order to stably run a large amount of ^two or more photosensitive materials, the development time is preferably 2 to 18 seconds.

As an automatic developing machine, a heat transfer material of 60 ° C. or more (heat roller of 60 ° C. to 130 ° C. or the like) or 150 ° C.
The above radiating objects (tungsten, carbon, nichrome, zirconium oxide, a mixture of yttrium oxide, thorium oxide, silicon carbide, etc.) are directly heated to radiate heat, and heat energy from a resistance heating body is made of copper, stainless steel, nickel, various ceramics, etc. (Which emit infrared rays by transmitting to a radiator) and have a drying zone.

As the automatic developing machine, those employing the following method or function can be preferably used.

Deodorizing device: JP-A-64-37560, page 544 (2), upper left column to page 545 (3), upper left column Washing water regeneration purifying agent and device: JP-A-6-25035
No. 2, page (3) paragraph “0011” to page (8) paragraph “0”
058 ”Waste liquid treatment method: JP-A-2-64638, No. 388
(2) Bottom left column to page 391 (5) Bottom left column Rinse bath between developing bath and fixing bath: JP-A-4-313
No. 749, page (18), paragraph "0054" to page (21), paragraph "0065" Replenishing water replenishment method: JP-A-1-281446, No. 25
0 (2) lower left column to lower right column Detect dry air temperature and humidity to control drying air: JP-A-1-315745, page 496 (2), lower right column to 50th
1 (7) lower right column and JP-A-2-108051-58
8 (2) lower left column to 589 (3) lower left column Silver recovery from fixing waste solution: JP-A-6-27623, page (4), paragraph "0012" to page (7), "0071".

The silver halide of the black-and-white silver halide photographic light-sensitive material subjected to the processing of the present invention is silver chloride, a silver chloride content of 60.
It is preferable to use silver bromochloride or silver chloroiodobromide in an amount of at least mol% for reducing the replenishment amount and for rapid processing.

The average grain size of the silver halide grains is preferably 1.2 μm or less, particularly preferably 0.1 to 0.8 μm. Further, it is preferable that the particle size distribution is narrow, and it is preferable to use a so-called monodispersed emulsion. Further, an emulsion composed of tabular grains having a (100) plane as a main plane is preferable, and such an emulsion is disclosed in US Pat.
264,337, 5,314,798, 5,3
20, 958.
Further, in order to obtain high illuminance characteristics, iridium is doped in a range of 10 ^-9 to 10 ^-3 mol per mol of silver halide, and at least one selected from rhodium, ruthenium, osmium and rhenium to harden the emulsion. 1
It is preferred to dope the seed in the range of 10 ^-9 to 10 ^-3 mole per mole of silver halide.

The silver halide emulsion can be subjected to known chemical sensitization such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization.

The black-and-white silver halide photographic light-sensitive material subjected to the processing of the present invention preferably employs the following techniques.

1) Solid dispersed fine particles of a dye:
No. 5629, page (3), paragraph "0017" to page (16), paragraph "0042" 2) Compound having an acid group: JP-A-62-237445.
No. 292 (8), lower left column, 11th line to 309 (25)
3rd line, lower right column of the page 3) Acidic polymer: JP-A-6-186659, (1)
0) page paragraph “0036” to page (17) page “006”
2) 4) Sensitizing dye Paragraph "0017" on page (3) of JP-A-5-224330
To page (13), paragraph “0040” JP-A-6-194777, page (11), paragraph “004”
2 "to page (22), paragraph" 0094 "JP-A-6-242533, page (2), paragraph" 0015 "
To page (8), paragraph “0034” JP-A-6-337492, page (3), paragraph “0012”
To page (34), paragraph “0056” JP-A-6-337494, page (4), paragraph “0013”
To page (14), paragraph "0039" 5) Supersensitizer JP-A-6-347938, page (3), paragraph "0011"
To page (16), paragraph “0066” 6) Hydrazine derivative JP-A-7-114126, page (23), paragraph “011”
1) to page (32), paragraph “0157” 7) Nucleation accelerator JP-A-7-114126, page (32), paragraph “015”
8 "to page (36), paragraph" 0169 "8) Tetrazolium compound JP-A-6-208188, page (8), paragraph" 0059 "
To page (10), paragraph "0067" 9) Pyridinium compounds JP-A-7-110556, page (5), paragraph "0028"
To page (29), paragraph [0068] 10) Redox compounds JP-A-4-245243, 235 (7) to 250
(22) 11) Syndiotactic polystyrene support JP-A-3-131843, pages 324 (2) to 327
(5) Page About other additives, for example, Research Disclosure No. No. 17643 (December 1978); No. 18716 (November 1979) and the same No. 3
08119 (December, 1989).

[0113]

The present invention will be specifically described below with reference to examples. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example 1 A black-and-white silver halide photographic material was prepared according to the following formulation. The photosensitive material was exposed to a blackening ratio of 50%, and a modified version of an automatic developing machine GR-26SR manufactured by Konica Corporation was used. The replenishment amounts of the developing solution and the fixing solution per 1 m ^{2 of the} silver photographic light-sensitive material were measured under the following processing conditions for 20 days.
200 sheets were processed per day, and the liquid was used as a running liquid.

-Preparation of Eco-Stage Film- (Preparation of Silver Halide Emulsion A) An average thickness of 70 mol% of silver chloride and the balance of silver bromide was 0.05 by a double jet method.
Silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. When mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 per mole of silver.
× 10 ^-8 mol was added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a silver / chloroiodobromide (90 mol% of silver chloride, having a core / shell type monodispersion (coefficient of variation: 10%) having a (100) plane as a main plane having an average thickness of 0.10 μm and an average diameter of 0.25 μm. Silver iodobromide
2 mol%, the balance being silver bromide).

This emulsion was cooled to 40 ° C. and modified with a phenylcarbamoyl group as an aggregating polymer (substitution rate: 90%).
Modified gelatin 13.8% by weight aqueous solution 1800m
was added and stirred for 3 minutes. Thereafter, an aqueous solution of 56% by weight of acetic acid was added to adjust the pH of the emulsion to 4.6, and the mixture was stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.

Thereafter, 9.0 L of distilled water at 40 ° C. was added, and the supernatant was drained after stirring and standing, and 11.25 L of distilled water was further added. After stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% by weight aqueous sodium carbonate solution were added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redispersion, the pH was adjusted to 5.80 pAg at 8.06 at 40 ° C. After desalting, the EAg of this emulsion was 50 ° C.
At 190 mV.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and sodium p-toluenethiosulfonate was adjusted to 1 × 10 ^−3.
After the addition of mol, chloramine T was added at 350 m per mol of silver.
g, 0.6 mg of inorganic sulfur (S8) and 6 mg of trichloroaurate were added, and the mixture was chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained.

After aging, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene per mol of silver was 2 × 10 ⁻³ mol, 1-phenyl-5-mercaptotetrazole was 3 × 10 ⁻⁴ mol, and potassium iodide was 300 mg.
Was added.

(Preparation of Silver Halide Emulsion B) An average thickness of 0.05 μm and an average diameter of 0.1 μm comprising 60 mol% of silver chloride, 2.5 mol% of silver iodide and the remainder of silver bromide were obtained by a double jet method.
5 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added at 2 × 10 4 per mole of silver.
^-8 mol was added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion had an average thickness of 0.
Core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 10 μm average diameter: 0.42 μm,
(I.e., 0.5 mol% of silver iodobromide, the balance being silver bromide). Then, a modified gelatin described in JP-A-2-280139 (in which an amino group in gelatin is substituted with phenylcarbamyl, for example, JP-A-2-28001)
Desalting was performed using Compound No. 39, page 287 (3), exemplified compound G-8). The EAg after desalting was 190 mV at 50 ° C.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ⁻³ mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and 2 × 10 ⁻⁵ mol of chloroauric acid was added.
N'-trimethyl-N'-heptafluoroselenourea was added in an amount of 3 × 10 ^-5 mol and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained. After aging, 4-hydroxy-6-
Methyl-1,3,3a, 7-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.

(Preparation of a silver halide photographic light-sensitive material for a printing plate making scanner for a HeNe laser light source) On one undercoat layer of the above support, a gelatin undercoat layer of the following formula 1 having a gelatin amount of 0.5 g was prepared. / m at ^2, the intermediate protective silver halide emulsion layer 1 formulation 2 thereon silver amount 1.5 g / m ^2, so that the amount of gelatin is 0.5 g / m ^2, further thereon As a layer, the coating solution of the following formula 3 was prepared so that the amount of gelatin was 0.3 g / m ² , and the silver halide emulsion layer 2 of formula 4 was further provided thereon with a silver amount of 1.4 g / m ² and a gelatin amount of 0 g / m ² . so that .4g / m ^2, further amount of gelatin coating solution having the following formulation 5 is simultaneous multilayer coating so as to be 0.6 g / m ^2. On the other side of the undercoat layer, a backing layer having the following formulation 6 was prepared so that the gelatin amount was 0.6 g / m ² .
A hydrophobic polymer layer of the following formula 7 was further formed thereon, and a backing protective layer of the following formula 8 was further formed thereon.
A sample was obtained by simultaneous multi-layer coating with the emulsion layer so as to give g / m ² .

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.5 g / m ² Solid dispersed fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium isoamyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (Silver halide emulsion layer 1 composition) Silver halide emulsion A Solid of dye a so that silver amount becomes 1.5 g / m ² Dispersed fine particles (average particle diameter 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² hydrazine compound ( HA) Amount shown in Table Nucleation promoter: Exemplified compound Na-9 40 mg / m ² Redox compound: RE-1 20 mg / m ² Compound e 100 mg / m ² Latex polymer f 0.5 g / m ² Hardener g 5 mg / m ² S-1 0.7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 30 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² 3 (Intermediate layer composition) Gelatin 0.3 g / m ² S-1 2 mg / m ² Prescription 4 (Silver halide emulsion layer 2 composition) Silver halide emulsion B Sensitized to give a silver amount of 1.4 g / m ² Dye 3 mg / m ² Sensitizing dye d-2 3 mg / m ² Hydrazine compound (HB) Amount shown in Table Nuclear nucleating accelerator Na-9 40 mg / m ² Redox compound: RE-1 20 mg / m ² 2- Mercapto-6-hydroxypurine 5 mg / m ² EDTA 20 mg / m ² Latex polymer f 0.5 g / m ² S-1 1.7 mg / m ² Formulation 5 (emulsion protective layer composition) Gelatin 0.6 g / m ² Dye b Solid dispersion ( 40 mg / m ² S-1 12 mg / m ² Matting agent: monodisperse silica having an average particle size of 3.5 μm 25 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² interface Activator h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener j 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 Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² Formulation 7 (hydrophobic polymer layer composition) Latex (methyl methacrylate) : acrylic acid = 97: 3) 1.0g / m 2 hardener g 6 mg / m ² formulation 8 (backing protective layer) gelatin 0.4 g / m ² mat : Monodispersed polymethylmethacrylate 50 mg / m ² Sodium an average particle diameter of 5 [mu] m - di - (2-ethylhexyl) sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² Dye ^{k 20mg / m 2 H (OCH} 2 CH ₂ ) _68- OH 50 mg / m ² Hardener j 20 mg / m ²

[0124]

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[0125]

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[0126]

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[0127]

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○ Starting developer (HAD-S)
1 L of working solution Pure water 300 ml DTPA / 5Na 1.45 g Sodium sulfite 52 g Potassium carbonate 55 g 8-Mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methylbenzotriazole 0.21 g 1-Phenyl-5-mercaptotetrazole 0.03 g Dimezone S 0 .87g Hydroquinone 20g KOH (55% aqueous solution) and pure water 400mL (p
H). When used, 600 mL of pure water and 400 mL of the above concentrated solution are mixed (pH 10.40).

Preparation of replenishment developer Preparation of development A parts (for 1 L of used solution) 8-mercaptoadenine 0.09 g Dimezone S 1.3 g 5-methylbenzotriazole 0.26 g Sodium sulfite 7.1 g Sodium erythorbate 6 g Hydroquinone 24 g The powder granules in the above ratio were placed in a commercially available agitating granulator and crushed and mixed well for 3 minutes. Then, 5% of water of the total weight was gradually added to perform granulation. The granulated product was transferred to a fluid bed dryer and dried at an air supply temperature of 60 ° C. for about 1 hour.

The obtained granules were placed in a fluid bed granulator GPCG-5 manufactured by Powrex Co., Ltd., and the air supply temperature was 60 ° C. and the air flow was 8 m.
^It was fluidized at ³ / min. The granule surface was coated by spraying 20 g of a 30% aqueous solution of sorbitol per 1 L of the solution with a two-fluid spray.

Preparation of developing B parts (for 1 L of used solution) DTPA · 5Na 4.35 g Sodium carbonate 28.77 g Potassium carbonate 37.5 g Potassium bromide 2.0 g Sodium sulfite 49.5 g LiOH · H ₂ O 9.5 g The powder granules in the above ratio were put into a commercially available stirring granulator and crushed and mixed for 3 minutes. Then, 5% of the total weight of water was gradually added to perform granulation.

The granulated product was transferred to a fluid bed dryer and dried at a supply air temperature of 60 ° C. for about 2 hours.

The obtained granules were placed in a fluid bed granulator GPCG-5 manufactured by Powrex Co., Ltd., and the air intake temperature was 60 ° C. and the air flow was 8 m.
^It was fluidized at ³ / min. The granule surface was coated by spraying a 30% aqueous solution of sorbitol at 60 g per liter using a two-fluid spray.

A. Obtained by the above operation. The two types of granules (b) were prepared in 15 L portions, 2% by weight of the combined weight of sodium 1-octanesulfonate was added, and the mixture was mixed with a cross rotary mixer for 10 minutes. This mixer was tableted with an oil press at a diameter of 30 mm, a filling amount per tablet of 10 g, and a tableting pressure of 1 ton / cm ² .

For comparison, a sample was prepared in which the A and B parts were not sprayed with a two-fluid spray and the granules were similarly tableted without coating.

○ Starting fixer solution 1 L of used solution Pure water 120 ml Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium gluconate 6.5 g Sodium acetate trihydrate 37.8 g Acetic acid (90% aqueous solution) 13.5 g Aluminum sulfate / 18-hydrate 18 g 333 mL using 50% sulfuric acid aqueous solution and pure water (pH 4.0)
81). When used, 667 ml of pure water and 333 ml of the above concentrated solution are mixed and used (pH of the starting solution).
4.85).

Preparation of supplementary fixing tablets Preparation of fixing a parts tablets (1 L of replenisher) Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium bisulfite 14 g Sodium sulfite 1.0 g Sodium acetate 18 g These powders The granules were placed in a commercially available stirring granulator and crushed and mixed well for 3 minutes. Then, 5% of the total weight of water was gradually added to perform granulation.

The obtained granules were transferred to a fluidized bed dryer and dried at a supply air temperature of 60 ° C. for about 2 hours.

The granules were put in a fluid bed granulator GPCG-5 manufactured by Powrex Co., Ltd., and the air supply temperature was 60 ° C. and the air flow was 8 m ³ /
Flowed in min. The granule surface was coated by spraying 40 g of a 30% aqueous solution of sorbitol per 1 L with a two-fluid spray.

Preparation of fixing b parts tablet (for 1 L of replenisher) Boric acid 6 g Tartaric acid 3 g Succinic acid 13.2 g Aluminum sulfate octahydrate 18 g Sodium acetate 10 g Sodium gluconate 10 g D-mannitol 2.5 g D-sorbit 2g Macrogol PEG # 4000 0.75g These granules were placed in a commercially available agitating granulator and mixed for 3 minutes to be crushed well. Then, 5% of the total weight of water was gradually added to perform granulation.

The obtained granules were transferred to a fluid bed dryer and dried at an air supply temperature of 60 ° C. for about 1 hour.

The granules were put into a fluid bed granulator GPCG-5 manufactured by Powrex Co., Ltd., and the air supply temperature was 60 ° C. and the air flow was 8 m ³ /
Flowed in min. The granule surface was coated by spraying 20 g of a 30% aqueous solution of sorbitol per 1 L of the solution with a two-fluid spray.

The two types of granules a and b obtained by the above operation were prepared for each 15 L, and 2% by weight of the combined weight of sodium 1-octanesulfonate was added thereto. Mix on machine for 10 minutes. This mixer was tableted with an oil press at a tableting pressure of 1 ton / cm ² at a filling amount of 10 g per tablet having a diameter of 30 mm.

For comparison, a sample was prepared in which a and b parts were not sprayed with a two-fluid spray, and the granules were similarly tableted without coating.

The pH when the developer was dissolved was 10.
72, when the fixing agent was dissolved, the pH was 4.2.

[0146] ○ Evaluation items and evaluation method (Evaluation of linearity and halftone dot quality) A halftone dot (50% target) exposed by SG-747RU with 8 μm random pattern halftone dots (FM screen) was screened with a 100 × loupe. The point quality (clearness) was evaluated. The highest rank was set to 5, and the rank was lowered and evaluated to 4, 3, 2, 1 according to the dot quality. Ranks 1 and 2 are levels that are not practically desirable. The linearity was obtained by changing the amount of exposure and measuring what percentage of the theoretical amount of exposure should be 2% from what should theoretically be 95% at the amount of exposure that should be 2%. It is desirable that the value be close to 95%. X-Rite361T was used for the measurement.

○ Practical maximum density A 50% original in the above evaluation was placed on a film sample by 5%.
The maximum density at the time of exposure to give an area of 0% was evaluated.

Evaluation of dirt generated in the developing tank.

The degree of dirt generated in the developing tank after running was visually evaluated on a five-point scale as follows.

A: There is no precipitate and the liquid is clear. B: There is no precipitate. C: No precipitate occurs, but there is dirt. P: P is slightly acceptable. E: Precipitate accumulates at the bottom.

保存 Preservation The tablets of 1 L each for the developing and fixing agents were sealed in an aluminum packaging material laminated with a polyethylene film and stored at 50 ° C. for 2 weeks. The state at this time was evaluated as follows.

A: No change from before storage B: No change in shape before storage, but slightly discolored C: Change in shape slightly before storage and slightly discolored D: Shape significantly larger than before storage A and B are judged to be good.

○ Evaluation of black spots The black spots (sand-like failures) in the unexposed portions of the obtained developed samples were visually evaluated using a magnifier of 40 times. Those having no black spots were ranked 5 and evaluated as 4, 3, 2, 1 in order as the number of black spots increased. Ranks 2 and 1 are undesirable levels.

Evaluation of fog The unexposed portion of the obtained developed sample was subjected to X-Rite 361.
The concentration was measured using T. 0.025 or less is a preferable value.

[0155]

[Table 1]

As a result, in the comparative example, the results shown in Table 1 are obtained, which is considered to have an adverse effect on the processed photosensitive material. On the other hand, in the present invention, good results are obtained,
It was practical enough.

Example 2 A black-and-white silver halide photographic material was prepared according to the following formulation, processed and evaluated as described below.

[0158] bright room flashing K ₃ Os (H ₂ O) a Cl ₅ per mol of silver 8 × 10 produced during mixing with (silver Preparation of Halide Emulsion C) simultaneously mixing method of the film
^-5 mol and K ₂ IrCl ₆ were added in an amount of 3 × 10 ⁻⁷ mol per mol of silver, and after desalting by a conventional method, monodispersed (coefficient of variation: 10%) silver chlorobromide having an average particle diameter of 0.10 μm ( An emulsion of cubic grains (consisting of 99 mol% of silver chloride and the remainder being silver bromide) was obtained.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, potassium bromide and citric acid were added to the obtained emulsion to reduce inorganic sulfur to 3 mol / mol of silver.
× 10 ^-6 mol was added and the mixture was chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained. After the ripening, 3-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 3 × 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole and gelatin were added.

(Preparation of a silver halide photographic light-sensitive material for reversing light in a printing plate making method containing a tetrazolium compound) On one undercoat layer of the film of the present invention and a comparative film, the following formulation 1
The gelatin undercoat layer of No. ² was further coated with a silver halide emulsion of Formula 2 so that the amount of gelatin was 0.5 g / m 2.
8 g / m ² and the amount of gelatin is 1.0 g / m ²
Further, as a protective layer, a coating solution of the following formula 3 was simultaneously applied on the upper layer so that the amount of gelatin became 0.5 g / m ² .
Further, after applying the conductive layer of Example 1 described in JP-A-5-188518, pages 360 (14) to 361 (15) on the undercoat layer on the opposite side, the gelatin amount of the backing layer of the following formula 4 was reduced. A polymer layer of the following formula 5 is further coated thereon so as to obtain 0.4 g / m ^2, and a backing protective layer of the following formula 6 is further coated thereon so that the gelatin amount becomes 0.4 g / m ^2. Then, a sample was obtained.

Formulation 1 (Gelatin Undercoat Layer Composition) Gelatin 0.6 g / m ² Dye b (Dispersed into a powder having a particle size of 0.1 μm by ball mill dispersion) 20 mg / m ² Dye k 10 mg / m ² Dye AD -1 80 mg / m ² hydrophilic polymer of styrene-maleic acid copolymer (thickener) 10 mg / m ² S-1 (sodium isoamyl-n-decyl sulfosuccinate) 0.4 mg / m ² Formula 2 tetrazolium compound according to the silver halide emulsion layer composition) present invention (C) table soda amount dodecylbenzenesulfonate shown in 10 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound e 6 mg / m ² latex polymer f 1.0 g / m ² hardener ^{g 40mg / m 2 S-1} 0.7mg / m 2 styrene - hydrophilic polymer maleic acid copolymer (thickener) 20 mg / m ² formulation (Emulsion protective layer composition) Gelatin 0.5 g / m ² Dye ^{k 100mg / m 2 S-1} 12mg / m 2 Matting agent: average particle size 3μm monodisperse silica 15 mg / m ² Matting agent: average particle size 8μm single of Dispersed silica 20 mg / m ² 1,3-vinylsulfonyl-2-propanol 50 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ² Prescription 4 (backing layer composition) Gelatin 0.4 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 hydrophilic polymer of styrene-maleic acid copolymer (thickening 20 mg / m ² Compound i 100 mg / m ² Formulation 5 (polymer layer composition) Latex n (styrene: butadiene: acrylic acid = 30: 65: 5) 1.0 g / m ² Hardener g 10 mg / m ² formulation 6 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: monodispersed polymethylmethacrylate 50 mg / m ² Sodium an average particle diameter of 5 [mu] m - di - (2-ethylhexyl) Sulfosuccinate 10 mg / m ² Surfactant h 1 mg / m ² H (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener j 40 mg / m ² Large total size (508 × 610) of the photosensitive material prepared above
mm) 1 sheet per developer replenisher 130ml / m ^2, 2000 sheets subjected to replenishment of the fixing replenisher 130 ml / m ² (Taizen 1
The exposed portion of the sheet was 20% of the total area).
The automatic processor was modified from GR-26SR (Konica),
It was assumed that tablets could be charged, and evaluation was performed by the following method.

Developing solution formulation Pure water 196 g Potassium carbonate 60 g Hydroquinone 16 g Dimezone S 1.6 g DTPA · 5Na (40 wt%) 3.63 g Potassium bromide 2.5 g 5-Methylbenzotriazole 0.50 g 1-phenyl-5 Mercaptotetrazole 0.02 g 2-mercaptohypoxanthine 0.06 g Sodium sulfite 14.66 g Potassium sulfite 35.15 g Diethylene glycol 50 g Finally, it was finished to 500 ml with pure water. The pH was adjusted to 10.20 with potassium hydroxide. This concentrated liquid was diluted twice with water to obtain a starting liquid (pH: 9.8).

定 着 Formulation of fixing solution The same fixing solution as in Example 1 was used.

Processing Step Development 35 ° C. for 15 seconds Fixing 35 ° C. for 10 seconds Washing at room temperature for 10 seconds Drying at 48 ° C. for 10 seconds Evaluation of gradation reproducibility The above film was exposed using P-627 manufactured by Dainippon Screen Co., Ltd. Processing was performed under the conditions. Gray scale 5 of halftone dots output by the scanner of the exposed photosensitive material
With respect to the exposure amount when the halftone dot returned to 95% on the returning photosensitive material, the halftone dot when 95% halftone dot on the gray scale was returned to the photosensitive material was measured. The numerical value closer to 5.0 indicates that the tone reproducibility is better.

○ Evaluation of a blank character In order to evaluate the quality of a blank character, in the above evaluation, when a proper exposure was performed such that a halftone dot original portion having a halftone dot area ratio of 50% became a halftone dot having a halftone dot area ratio of 50%. The character width to be reproduced is expressed in μm units. Those that can reproduce only characters having a width of 150 μm or more have poor image quality.

What can reproduce 30 μm is a preferable image quality.

The maximum density when the 50% halftone original in the above evaluation was exposed to a 50% halftone dot area on a film sample was evaluated.

Evaluation of dirt generated in the developing tank The degree of dirt generated in the developing tank after running was visually evaluated in five steps as follows.

A: No precipitate at all, and the liquid is clear. B: No precipitate at all. C: No precipitate is generated, but there is dirt. P: P is slightly acceptable. E: Precipitate accumulates at the bottom.

保存 Preservation The tablets of 1 L each for the developing and fixing agents were sealed in an aluminum packaging material laminated with a polyethylene film and stored at 50 ° C. for 2 weeks. The state at this time was evaluated as follows.

A: No change from before storage B: The shape is not changed from before storage, but slightly discolored C: The shape is slightly changed and slightly discolored before storage D: The shape is larger than before storage A and B are judged to be good.

[0172]

[Table 2]

As a result, in the comparative example, the results shown in Table 2 were obtained, which is considered to have an adverse effect on the processed photosensitive material. On the other hand, in the present invention, a good result was obtained, and it was sufficiently practical.

[0174]

The solid developer and solid fixer for black-and-white silver halide photographic light-sensitive materials which do not lower the maximum density, increase the fog and do not degrade the quality of the printed characters even when a single processing agent is used. Could be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view of an example of a fluidized bed granulator.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fluidized bed granulator main body 2 Dust collection filter 3 Sprayer 4 Straightening plate A Exhaust fan B Compressed air C Liquid sending device D Heat exchanger E Air supply filter F Blast fan

Claims (5)

[Claims] 1. A method according to claim 1, wherein at least two part granules include a part granule containing a compound represented by the following general formula (A) and a part granule containing at least one alkaline compound having an acid dissociation constant (pKa) of 9 or more. Wherein the part granules are coated with at least one selected from saccharides or water-soluble polymer compounds, and a solid developer formed as a kind of molded product without localization of the part granules is used. A processing method for black-and-white silver halide photographic materials. Embedded image [In the formula, R ₁₁ and R ₁₂ each represent an alkyl group, an amino group, an alkoxy group, or an alkylthio group, which may have a substituent or may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ] 2. In the above processing method, the molar ratio (HQ / A) of the dihydroxybenzene-based developing agent (HQ mole) to the compound represented by the general formula (A) (A mole) is from 0 to 0.
2. The method for processing a black-and-white silver halide photographic material according to claim 1, wherein the number is 1,000. 3. The method for processing a black-and-white silver halide photographic material according to claim 1, wherein the silver halide photographic material contains a compound represented by the following general formula (H). Embedded image Wherein A represents an aliphatic group, an aromatic group or a heterocyclic group, B represents an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group,
Represents an aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, an oxalyl group, or a heterocyclic group. A ₁ and A _{2 each} represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. ] 4. The method for processing a black-and-white silver halide photographic material according to claim 1, wherein the silver halide photographic material contains a compound represented by the following general formula (C). Embedded image [Wherein, R _c1 , R _c2 and R _c3 represent a hydrogen atom or a substituent, and X ⁻ represents an anion. ] 5. Part granules containing at least one thiosulfate or thiocyanate, and at least two part granules containing at least one water-soluble aluminum salt and gluconic acid, wherein the part granules are A black-and-white silver halide photographic light-sensitive material characterized by using a solid fixing agent coated with at least one selected from saccharides or a water-soluble polymer compound and formed as a type of molded product without localization of the part granules. Material treatment method.