JPH11212221A - Solid processing agent for black-and-white silver halide photographic sensitive material and method for processing this material by using that processing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To restrain the occurrence of powder to the minimum and to prevent the deterioration of hardness after being manufactured in the case of being tabletted, the drop of maximum density even in the case of being low replenished, the rise of fog and the deterioration of linearity. SOLUTION: This solid processing agent for a black-and-white silver halide photographic sensitive material having at least one photosensitive silver halide emulsion layer on a support in which the water content of the base stock of the processing agent is <=2%, is manufactured without using a drying process and it is granulated by using a Henschel mixer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solid processing agent for a black-and-white silver halide photographic light-sensitive material, and a method for processing a black-and-white silver halide photographic light-sensitive material using the solid 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.

[0003] Such a replenisher is usually produced, transported and stored in the form of a concentrate, and is diluted with a certain amount of water before use to be used as a replenisher. However, with regard to plastic bottles used as containers for liquid processing agents, the safety of transporting liquid hazardous materials and regulations on disposal after use have been tightened, and the development of solid processing agents that do not use bottles in the industry has been strong. It has been demanded. In response to such demands, several proposals have been made to make the processing agent into a powder or a tablet.

However, in the case of powder, there is a concern that the powder may fluctuate when preparing the processing liquid, which may adversely affect the human body. Therefore, there is a demand for less dispersible granules and tableted solid processing agents. However, in the case of tableted treatment agents, the hardness changes over time, especially the hardness decreases, the tablet breaks during transportation, powder is generated, etc., and the advantages of conventional tablets are utilized. Serious problems, such as not being done. In addition, when processing is performed in such a state, the maximum density is greatly reduced due to variations in the contents, and when processing is performed using a hydrazine photosensitive material in recent years, fog increases and linearity is significantly deteriorated. Such problems have arisen, and solutions have been strongly desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to minimize the generation of powder, to prevent the hardness from being reduced after production when tableted, and to reduce the maximum concentration even when the amount is reduced. Another object of the present invention is to provide a solid processing agent for a black-and-white silver halide photographic light-sensitive material which does not cause an increase in fog and linearity deterioration, and a method for processing a black-and-white silver halide photographic light-sensitive material using the solid processing agent.

[0006]

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

[0007] 1. A solid processing agent for a black-and-white silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support, wherein the material of the processing agent is 2% or less in water content, and A solid processing agent for a black-and-white silver halide photographic material, wherein the solid processing agent is prepared without using a drying step.

[0008] 2. 2. The solid processing agent for a black-and-white silver halide photographic light-sensitive material as described in 1 above, wherein the solid processing agent is granulated using a Henschel mixer.

3. 2. The solid processing agent for a black-and-white silver halide photographic material according to item 1, wherein the solid processing agent is a developer containing at least one selected from the group of compounds shown below.

Compounds ascorbic acids dihydroxybenzenes 3-pyrazolidones aminophenols 1-aryl-3-aminopyrazolines 4. 2. The solid processing agent for a black-and-white silver halide photographic material as described in 1 above, wherein the solid processing agent is a fixing agent containing at least one selected from the following compound group.

Compound group Thiosulfate Thiocyanate Water-soluble aluminum salt 2. The solid processing agent for a black-and-white silver halide photographic material as described in 1 above, wherein the solid processing agent contains a compound represented by the following general formula (1).

Formula (1) R- (O) _n -SO ₃ M wherein R represents a linear or branched alkyl, alkenyl, or alkynyl group, n represents 0 or 1, and M represents Represents a hydrogen atom, an alkali metal or ammonium] A method for processing a black-and-white silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support, wherein the material of the processing agent is a solid processing agent having a water content of 2% or less; A method for processing a black-and-white silver halide photographic material, wherein the solid processing agent is prepared without using a drying step.

7. 7. The method for processing a black-and-white silver halide photographic material according to the above item 6, wherein the solid processing agent is granulated using a Henschel mixer.

8. 7. The method for processing a black-and-white silver halide photographic material as described in 6 above, wherein the solid processing agent is a developer containing at least one selected from the group of compounds shown below.

Compounds Group Ascorbic acids Dihydroxybenzenes 3-Pyrazolidones Aminophenols 1-Aryl-3-aminopyrazolines 9. 7. The method for processing a black-and-white silver halide photographic material as described in 6 above, wherein the solid processing agent is a fixing agent containing at least one selected from the group of compounds shown below.

Compound group Thiosulfate Thiocyanate Water-soluble aluminum salt 7. The method for processing a black-and-white silver halide photographic material as described in 6 above, wherein the solid processing agent contains a compound represented by the following general formula (1).

Formula (1) R- (O) _n -SO ₃ M wherein R represents a linear or branched alkyl, alkenyl or alkynyl group, n represents 0 or 1, and M represents Represents a hydrogen atom, an alkali metal or ammonium] 7. The method for processing a black-and-white silver halide photographic material as described in 6 above, wherein the black-and-white silver halide photographic material contains a compound represented by the following general formula (2).

[0018]

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[In the formula, A represents an aliphatic group, an aromatic group, or a heterocyclic group, and may have a substituent. B is an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsphinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group , An oxalyl group or a heterocyclic group. B is A
Together with ₂ and the nitrogen atom to which they are attached, they may form a heterocycle. A ₁ and A _{2 each} represent a hydrogen atom or one of them represents a hydrogen atom and the other represents an acyl group or an oxazolyl group.] Hereinafter, the present invention will be described in detail.

As a method for producing the solid processing agent of the present invention, the raw materials to be mixed are mixed and granulated to obtain granules,
Tableting is performed using a tableting machine, but it is preferable to perform mixing and granulation using a Henschel mixer without adjusting the moisture content.

The Henschel mixer is a batch type stirring granulator having a cylindrical container and a shaft seal portion set at a lower portion of the container. Details are shown in FIG.

In FIG. 1, the shape and number of the stirring blades can be selected according to the purpose. Normally, two stages of stirring blades A are mounted and rotated at a high speed. When a liquid binder is used, the outer peripheral speed of the stirring blade A is about 5 to 10 m / s. The peripheral speed for raising the temperature by the frictional heat generated by the rotation of the stirring blade A to form granules is 20 to 30 m.
/ S and 40 m / s. Multiple processes such as reducing the heating time by controlling the temperature of the heating medium and cooling after granulation can be performed by one unit by providing the jacket B on the cylindrical container side wall. is there.

In order to perform granulation without a drying step, it is necessary to reduce the amount of water added during granulation in advance. The amount of water to be added is preferably such that the water content of all the treating agent materials is 2% or less. More preferably, the water content is 0.01
To 1.0%, more preferably 0.05 to
It is between 0.5%.

In the processing of the light-sensitive material, the processing is performed while replenishing a fixed amount of the processing liquid in proportion to the area of the light-sensitive 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.
It is as follows. Preferably 50 to 1 per m ²
90 ml.

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.

Ascorbic acids used in the solid developer of the present invention include ascorbic acid, ersorbic acid and salts thereof, and dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, and 2,3. -Dichlorohydroquinone, 2,
5-dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, and 3-pyrazolidones include 1-phenyl-3
-Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3 -Pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
Examples of pyrazolidone, 1-phenyl-4,4-dihydroxyethyl-3-pyrazolidone, and aminophenols include o-aminophenol, p-aminophenol, and N-aminophenol.
-Methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, N-
(Β-hydroxyethyl) -p-aminophenol, N
-(4-hydroxyphenyl) glycine and 1-aryl-3-aminopyrazolines include 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (N-methyl-p-aminophenyl)- 3-aminopyrazolin and the like.

The thiosulfate used in the solid fixing agent of the present invention includes potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, and the thiocyanate includes potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate. . Examples of the water-soluble aluminum salt used in the solid fixing agent as a hardener include aluminum sulfate, aluminum oxide, potassium alum, and ammonium alum.

The solid processing agent of the present invention preferably contains a compound represented by the general formula (1) as a lubricant from the viewpoint of the effect of the present invention.

Formula (1) 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 Represents a hydrogen atom, an alkali metal or ammonium] Examples of the compound represented by formula (1) preferably used in the present invention are described below.

[0030]

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

The replenishing amount is the total amount of each solid processing agent volume and water volume when the solid processing agent is replenished with a solution in which water is dissolved, 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.

In the case of a solid processing agent, the amount of the processing agent added at one time is preferably 0.1 to 50 g, and the amount of the processing agent is 1 to 2 in a developer.
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 substantially constant, the calculated addition of the solid processing agent and the balance of the components are achieved.

The temperature of the developing, fixing and washing tanks is 10 to 45 ° C.
It is preferable that the respective temperatures be adjusted separately.

Next, the above-mentioned general formula (2) used in the present invention
The hydrazine compound represented by the formula will be described.

In the general formula (2), the aliphatic group represented by A preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
It is preferably a linear, branched or cyclic alkyl group of up to 20. For example, a methyl group, an ethyl group, a t-butyl group, an octyl group, a cyclohexyl group, a benzyl group and the like are mentioned, and these are further suitable substituents (for example, an aryl group, an alkoxy group, an alkylthio group, an arylthio group,
Aryloxy group, sulphite group, sulphonamide group,
Acylamide group, ureido group, etc.).
The aromatic group represented by A is preferably a monocyclic or condensed-ring aryl group, for example, a benzene ring or a naphthalene ring. As the heterocyclic ring represented by A, a heterocyclic ring containing at least one heteroatom selected from at least nitrogen, sulfur, and oxygen of a single ring or a condensed ring is preferable, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring,
Morpholine ring, pyridine ring, pyrimidi ring, quinoline ring,
A thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring and the like.

Particularly preferred as A are 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 an alkyl moiety having 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 having 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) Examples include a hydroxyl group and a phosphoamide group (preferably having 1 to 40 carbon atoms).

A preferably contains at least one of a diffusion-resistant group or a silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group which is relatively inert to photographic performance having 8 or more carbon atoms, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorber described in JP-A-64-90439.

Examples of the substituent represented by B include acyl groups (for example, formyl group, acetyl group, propionyl group, trifluoroacetyl group, methoxyacetyl group, phenoxyacetyl group, methylthioacetyl group, chloroacetyl group). Group, benzoyl group, 2-hydroxymethylbezoyl group, 4-chlorobezoyl group, etc.), alkylsulfonyl group (eg, methanesulfonyl group, 2-chloroethanesulfonyl group, etc.), arylsulfonyl group (eg, benzenesulfonyl group, etc.), Alkylsulfinyl group (eg, methanesulfinyl group, etc.), arylsulfinyl group (eg, benzenesulfinyl group, etc.), carbamoyl group (eg, methylcarbamoyl group, phenylcarbamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl) Group, such as methoxyethoxy group), an aryloxycarbonyl group (e.g., phenoxycarbonyl group), a sulfamoyl group (e.g.,
Dimethylsulfamoyl group), sulfinamoyl group (eg, methylsulfinamoyl group), alkoxysulfonyl group (eg, methoxysulfonyl group), thioacyl group (eg, methylthiocarbonyl group), thiocarbamoyl group (eg, A methylthiocarbamoyl group), an oxalyl group or a heterocyclic ring (for example, a pyridine ring,
Pyridinium ring). B together with A ₂ and the nitrogen atom to which they are attached,

[0041]

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May be formed.

R ₃₃ represents an alkyl group, an aryl group or a heterocyclic group, and R ₃₄ 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 group, trifluoroacetyl group, bezoyl group, etc.), a sulfonyl group (eg, methanesulfonyl group, toluenesulfonyl group, etc.) Or an oxalyl group (eg, an ethoxalyl group).

Of these hydrazine compounds represented by the general formula (2), a compound represented by the general formula (2-a) is particularly preferred.

[0046]

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In the general formula (2-a), R ₃₁ represents an aryl group or a heterocyclic group, and R ₃₂ represents

[0048]

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Represents

The aryl group represented by R ₃₁ 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 ₃₁ includes at least nitrogen, sulfur,
A 5- or 6-membered unsaturated hetero ring containing one hetero atom selected from oxygen is preferable, and examples thereof include a pyridine ring, a quinoline ring, a pyrimidine ring, a thiophene ring, a furan ring, a thiazole ring and a benzothiazole ring.

Preferred as R ₃₁ is a substituted or unsubstituted aryl group. This substituent is represented by the general formula (2)
Having the same meaning as the substituent for A in pH 11.
When the contrast is increased with a developer of 2 or less, it preferably has at least one sulfoamide group.

R ₃₅ and R ₃₆ are each a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, a benzyl group, etc.), an alkenyl group (eg, an allyl group, butenyl group, etc.), an alkynyl group (eg, a propargyl group, a butynyl group) Group), an aryl group (eg, phenyl group, naphthyl group, etc.), a heterocyclic group (eg, 2,2,6,6-tetramethylpiperidinyl group, N-benzylpiperidinyl group, quinolizinyl group, N , N'-diethylpyrazolidinyl group, N-benzylpyrrolidinyl group, pyridyl group, etc.), amino group (eg, amino group, methylamino group, dimethylamino group, dibenzylamino group, etc.), hydroxy group, An alkoxy group (eg, methoxy group, ethoxy group, etc.), an alkenyloxy group (eg, allyloxy group, etc.), an alkynyloxy group (eg, Rugiruokishi group), an aryloxy group (e.g., phenoxy group) or a heterocyclic oxy group (pyridyloxy group, etc.), to form together with the nitrogen atom R ₃₅ and R ₃₆ the ring (pyridine ring, morpholine ring, etc.) Is also good. R ₃₇ represents a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, a methoxyethyl group, a hydroxyethyl group, etc.), an alkenyl group (eg, an allyl group, butenyl group, etc.), an alkynyl group (eg, a propargyl group, a butynyl group) Etc.), an aryl group (phenyl group, naphthyl group, etc.) and a heterocyclic group (eg, 2,2,6,6-tetramethylpiperidinyl group, N-methylpiperidinyl group, pyridyl group, etc.).

[0053] represents the A ₁ and A ₂ group having the same meaning of A ₁ and A ₂ of the general formula (2), and most preferably both hydrogen atoms.

Specific examples of the compound represented by formula (2) are shown below. However, the present invention is not limited to these. In addition, specific examples of the compound represented by the general formula (2) include those described in JP-A-5-241264.

[0055]

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The method for synthesizing the compound represented by formula (2) of the present invention is described in JP-A Nos. 62-180361 and 62-178.
No. 246, No. 63-234245, No. 63-2342
Nos. 46, 64-90439, JP-A-2-37, 2-947, 2-120736, and 2-2302
No. 33, No. 3-125134, U.S. Pat.
167, 4,988,604, 4,994,3
No. 65, EP 253,665, EP 333
435 and the like.

The amount of the compound represented by the general formula (2) is from 5 × 10 ^{-7 to} 5 × 1 per mol of silver halide.
The range of 0 ^-1 mol is preferable, and in particular, 5 × 10 ^{-6 to} 5 × 10
A range of ^-2 mol is preferred.

When the compound represented by the general formula (2) is contained in a light-sensitive material, it is contained in a silver halide emulsion layer or a hydrophilic colloid layer adjacent to the silver halide emulsion.

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.
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 the 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, yttrium oxide, a mixture of 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.

Further, as the automatic developing machine, those employing the following methods or functions 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 paragraph (8), page "0058" Wastewater 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, the particle size distribution is preferably narrow, and a so-called monodispersed emulsion is preferably used. Further, an emulsion composed of tabular grains having a (100) plane as a main plane is preferred. Such emulsions are described in U.S. Pat. Nos. 5,264,337, 5,314,798 and 5,320,958. Can be obtained with reference to the description in Further, in order to obtain high illuminance characteristics, iridium is doped in a range of 10 ^-9 to 10 ^-3 mol per 1 mol of silver halide, and at least one selected from rhodium, ruthenium, osmium and rhenium in order to harden the emulsion. It is preferable to dope one kind in the range of 10 ^-9 to 10 ^-3 mol per mol 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 following techniques are preferably employed for the black-and-white silver halide photographic light-sensitive material to be processed in the present invention.

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 (22)" 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"
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).

[0068]

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 << 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.
μm, silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, 8 × 10 ⁻⁸ mol of K ₃ RuCl ₆ was added per mol of silver. 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. Tabular grain emulsion consisting of 0.2 mol% of silver iodobromide and the remainder being silver bromide).

The emulsion was cooled to 40 ° C. and modified with a phenylcarbamoyl group as an aggregating polymer (substitution rate: 90%).
1800 ml of a 13.8% by weight aqueous solution of modified gelatin
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, 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 the redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C. After desalting, the EAg of this emulsion was 50 ° C.
At 190 mV.

To the obtained 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 completion of 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% comprising silver chloride of 60 mol%, silver iodide of 2.5 mol%, and silver bromide in the remainder 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 obtained 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'-heptafluoropropyl selenourea 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 ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, and 1-phenyl-5-mol.
3 × 10 ^-4 mol of mercaptotetrazole and gelatin were added.

(Preparation of a silver halide photographic light-sensitive material for a printing plate making scanner for a He-Ne laser light source) On one undercoat layer of the above support, a gelatin undercoat layer of the following formula 1 was prepared with a gelatin content of 0. The silver halide emulsion layer 1 of Formulation ² was coated thereon with a silver amount of 1.5 g / m ² ,
A coating solution of the following formula 3 was further applied as an intermediate protective layer on the upper layer so that the amount of gelatin became 0.5 g / m ^2, and a coating solution of formula 4 was further added thereon so that the gelatin amount became 0.3 g / m ² . The silver halide emulsion layer 2 was adjusted so that the silver amount was 1.4 g / m ² and the gelatin amount was 0.4 g / m ^2, and the coating solution of the following formula 5 was adjusted so that the gelatin amount was 0.6 g / m ^2. Coating was applied simultaneously. On the other side of the undercoat layer, a backing layer of the following formulation 6 was further coated with a hydrophobic polymer layer of the following formulation 7 so that the amount of gelatin was 0.6 g / m ² , and further a further formulation of the following A sample was obtained by simultaneously coating the backing protective layer No. 8 with the emulsion layer so that the amount of gelatin became 0.4 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 Prescription 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Solid of dye a so that silver amount becomes 1.5 g / m ² Dispersed fine particles (average particle size: 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 2 -1 20 mg / m ² nucleation accelerator: AM-1 40mg / m ² redox compound: RE-1 20mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener ^{5mg / m 2 S-1 0.7mg} / m 2 2- mercapto-6-hydroxy purine ^{5mg / m 2 EDTA 30mg / m} 2 Colloidal silica (average particle size 0.05μm) 10mg / m ² formulation 3 (the intermediate layer composition ) Gelatin 0.3 g / m ² S-1 2 mg / m ² Prescription 4 (composition of silver halide emulsion layer 2) Silver halide emulsion B Sensitizing dye d-1 3 mg so that the silver amount becomes 1.4 g / m ² / M ² sensitizing dye d-2 3 mg / m ² hydrazine compound 2-2 20 mg / m ² nucleation promoter: AM-1 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 Solid dispersion of dye b (average Diameter ^{0.1μm) 40mg / m 2 S-} 1 12mg / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² 1,3-bis (vinylsulfonyl) -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 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 Ma Preparative 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 Dye k 20mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener j 20 mg / m ²

[0079]

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[0080]

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[0081]

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[0082]

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Starting developer (for 1 L of used 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 0.87 g Hydroquinone 20 g Sodium elsorbate 5 g KOH (55% aqueous solution) and 400 ml using pure water (p
H10.45). When using pure water 60
0 ml and 400 ml of the above concentrated liquid are mixed and used.

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 erysorbate 6 g Hydroquinone 24 g D-sorbitol 5.0 g These granules were put in a commercially available Henschel mixer and mixed for 3 minutes. After adding the amount of water shown in Table 1, the mixture was further mixed for 1 minute to obtain granulated A parts.

As a comparison, the above materials were mixed in a commercially available bantam mill for 30 minutes, further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and then the internal pressure was increased to about 5 mmHg using a batch freeze dryer. After lowering, it was cooled. And -20
The mixture was treated at 12 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated A part.

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 8.8 g D-mannitol (trade name: Kao) 11.7 g D-sorbitol 5 g These granules are put in a commercially available Henschel mixer and mixed for 3 minutes. After adding the amount of water shown in Table 1, the mixture is further mixed for 1 minute, and granulated. Object B parts.

As a comparison, the above materials were mixed in a commercially available bantam mill for 30 minutes, further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and then the internal pressure was increased to about 5 mmHg using a batch freeze dryer. After lowering, it was cooled. And -20
The mixture was treated at 12 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated B part.

A kit for 4 L of each granule of the granules A and B thus produced was prepared.

Starting fixer (for 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 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 Tablet Preparation of Fixing A Parts Tablet (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 Pine flow ( 9 g These granules were placed in a commercially available Henschel mixer, mixed for 3 minutes, added with the amount of water shown in Table 1, and further mixed for 1 minute to obtain granulated A parts.

For comparison, these materials were mixed in a commercially available bantam mill for 30 minutes, further granulated at room temperature for 10 minutes with a commercially available stirring granulator, and then the internal pressure was reduced using a batch freeze dryer. After cooling to 5 mmHg, it was cooled. Then, the mixture was treated at −20 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated A part.

Preparation of fixing B parts tablets (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 D-mannitol 2.5 g D-sorbit 1.2 g Macrogol PEG # 4000 0.75 g These granules were placed in a commercially available Henschel mixer, mixed for 3 minutes, added with the amount of water shown in Table 1, and further mixed for 1 minute to obtain granulated B parts.

As a comparison, the above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator.
After the internal pressure was reduced to about 5 mmHg, cooling was performed. And -2
The mixture was treated at 0 ° C. for 12 hours and dried until the water content became 1% to obtain a granulated B part.

For comparison, granules without a drying step using a commercially available stirring granulator were also prepared.

A kit for 4 L of each granule of the granules A and B thus produced was prepared.

When the above granules were used, they were dissolved in water using a mixer and finished to 4 L.

The pH of the fixing replenisher was 4.2 and the pH of the developing replenisher was 10.72.

The entire size of the photosensitive material prepared above (5
08 × 610 mm) 190 ml /
m ² , replenishment of 190 ml / m ² of fixer replenisher and 2000
(One exposed portion of the total was 20% of the total area). The automatic developing machine was modified from GR-26SR (manufactured by Konica), and the replenishing sections of the developing tank and the fixing tank were modified so that a solid processing agent (granules) could be charged.

◎ Evaluation method ○ Evaluation of linearity and halftone dot quality Exposure with halftone dots (FM screen) of a random pattern of 8 μm by SG-747RU at the middle point (target 5)
0%) was evaluated for halftone dot quality (clearness) using a 100-fold loupe. The highest rank is 5, and depending on the dot quality,
The rank was lowered to 2, 1 and evaluated. 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%. A value close to 95% is desirable. X-Rite361T was used for the measurement.

○ Practical maximum density 5% of the 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.

Amount of Fine Powder Generated Arbitrarily from the obtained treatment agent kit, a given vibration was applied by a vibration tester, and the weight ratio of the fine powder generated immediately after completion was measured. The amount of generated fine powder is 0.
If it exceeds 5%, the powder will dance and adhere to the worker's face and the like.

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.

[0103]

[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, a good result was obtained, and it was sufficiently practical.

Example 2 An experiment and evaluation were conducted in the same manner as in Example 1 except that the developer and the fixing agent were changed from granules to tablets as shown below.

Compound (1) was added to each of parts A and B of the developing granules in an amount of 1.3 g and 0.4 g per 1 L of the treating agent, and the mixture was thoroughly mixed for 10 minutes, and the resulting mixture was mixed with Masina UD. Tablets having a diameter of 30 mm, a thickness of 10 mm, and a weight of 10 g were obtained by compression tableting of 1.5 ton / m ² using a DFE 30/40 tableting machine.

To the A and B parts of the fixing granules, 3 g and 0.5 g of the compound (1) were added, respectively, and the mixture was thoroughly mixed for 10 minutes, and the resulting mixture was mixed with Masina UD.
Tablets having a diameter of 30 mm, a thickness of 10 mm, and a weight of 10 g (for 1 L of replenisher) were prepared by compression tableting of 1.5 ton / m ² using a DFE 30/40 tableting machine.

The developers (A16, B46) prepared above
) And the fixing agent (A76, B20) were each stored in an aluminum bag and stored at 50 ° C. and 70% environment for 2 weeks.

When the above tablets were used, they were dissolved in water using a mixer and finished to 4 liters.

The pH of the fixing replenisher was 4.2.
The pH of the developing replenisher was 10.72.

In addition to the evaluation of Example 1, the following evaluation was performed.

O Hardness: 30 arbitrarily selected tablets were prepared, and their hardness was set to O.
The hardness was measured using TS-50 manufactured by KADA SEIKO, and the average value was calculated, which was defined as the hardness of the tablet.

○ Frittleness Five prepared tablets were arbitrarily selected, and they were operated for 5 minutes using a tablet friability tester manufactured by Medical Science Co., Ltd., and the weight before the experiment and the weight after the experiment were measured. Was measured for the degree of friability. This was repeated five times, and the average value was taken as the friability of the tablet. What does not exceed 3% is a good level without flour.

[0114]

[Table 2]

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

[0116]

According to the present invention, the generation of powder is minimized, and when tableted, there is no deterioration in hardness even after production.
A solid processing agent for black-and-white silver halide photographic light-sensitive materials that does not cause a decrease in fog and linearity deterioration even when the maximum density does not decrease even when the replenishment is reduced, and processing of black-and-white silver halide photographic light-sensitive materials using the solid processing agent A method could be provided.

[Brief description of the drawings]

FIG. 1 is a diagram showing a cross section of a Henschel mixer.

[Explanation of symbols]

 A stirring blade B jacket

Claims (11)

[Claims] In a solid processing agent for a black-and-white silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support, the material of the processing agent has a water content of 2%.
% Of a solid processing agent for a black-and-white silver halide photographic light-sensitive material, wherein the solid processing agent is prepared without using a drying step. 2. The solid processing agent for a black-and-white silver halide photographic material according to claim 1, wherein the solid processing agent is granulated using a Henschel mixer. 3. The black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent is a developer containing at least one selected from the group of compounds shown below. Solid processing agent. Compounds Ascorbic acids Dihydroxybenzenes 3-Pyrazolidones Aminophenols 1-Aryl-3-aminopyrazolines 4. The black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent is a fixing agent containing at least one selected from the group of compounds shown below. Solid processing agent. Compounds Thiosulfate Thiocyanate Water-soluble aluminum salt 5. The solid processing agent for a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent contains a compound represented by the following general formula (1). Formula (1) 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, M represents a hydrogen atom, Represents an alkali metal or ammonium] 6. A method for processing a black-and-white silver halide photographic material having at least one photosensitive silver halide photographic emulsion layer on a support, wherein the material of the processing agent has a water content of 2%.
A method for processing a black-and-white silver halide photographic material, wherein the solid processing agent is as follows, and the solid processing agent is prepared without using a drying step. 7. The method for processing a black-and-white silver halide photographic material according to claim 6, wherein the solid processing agent is granulated using a Henschel mixer. 8. The black-and-white silver halide photographic light-sensitive material according to claim 6, wherein the solid processing agent is a developer containing at least one selected from the group of compounds shown below. Processing method. Compounds Ascorbic acids Dihydroxybenzenes 3-Pyrazolidones Aminophenols 1-Aryl-3-aminopyrazolines 9. The black-and-white silver halide photographic light-sensitive material according to claim 6, wherein the solid processing agent is a fixing agent containing at least one selected from the group of compounds shown below. Processing method. Compounds Thiosulfate Thiocyanate Water-soluble aluminum salt 10. The method for processing a black-and-white silver halide photographic material according to claim 6, wherein the solid processing agent contains a compound represented by the following general formula (1). Formula (1) 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, M represents a hydrogen atom, Represents an alkali metal or ammonium] 11. The method for processing a black-and-white silver halide photographic material according to claim 6, wherein the black-and-white silver halide photographic material contains a compound represented by the following general formula (2). Embedded image [In the formula, A represents an aliphatic group, an aromatic group, a heterocyclic group,
It may have a substituent. B is an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsphinyl group, an arylsulfinyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinamoyl group, an alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group , An oxalyl group or a heterocyclic group. B may form a heterocyclic ring together with A ₂ and the nitrogen atom to which they are bonded. A ₁ and A _{2 each} represent a hydrogen atom or one of them represents a hydrogen atom and the other represents an acyl group or an oxazolyl group.