JP2001242601A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photographic sensitive material which ensures high running stability of a developing solution and a fixing solution, stable sensitivity and γ, gives an image nearly free from residual color and unevenness in development, requires low replenishment and attains high safety. SOLUTION: In the processing method in which a silver halide photographic sensitive material with at least one silver halide emulsion layer on the base is developed, fixed and washed, a developer contains reductones, a developing solution and/or a fixing solution is a solution prepared by dissolving a granular solid development initiator and/or a granular solid fixation initiator and a development replenisher solution and/or a fixation replenisher solution is a solution prepared by dissolving a tablet-shaped solid development replenisher and/or a tablet-shaped solid fixation replenisher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic material (hereinafter simply referred to as a "photosensitive material").

[0002]

2. Description of the Related Art A developing solution containing reductones, for example, a developing solution using ascorbic acid as a developing agent, has a feature that the pH decreases with consumption of the main agent under the influence of air oxidation.

Since a decrease in pH causes a decrease in development activity, the developer in the processing tank and the replenisher in the replenishment tank tend to fatigue due to air oxidation and cause a decrease in activity when running in an automatic developing machine. In particular, since the disposal of effluents into the ocean has been banned by the London Treaty since January 1996, low replenishment of treatment liquids has become the mainstream in line with the reduction of effluents. Had been requested.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an image having a high running stability of a developing solution and a fixing solution, a stable sensitivity and γ, an image having little residual color and development unevenness, and a low replenishment. Another object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having high safety.

[0005]

The above objects of the present invention have been attained by the following constitutions.

(1) In a processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, a developer contains reductones and a developer And / or the fixer
It is a solution in which a granular solid development initiator and / or a granular solid fixing initiator is dissolved, and a developing replenisher and / or a fixing replenisher is a tablet-like solid developing replenisher and / or a tablet-like solid fixing replenisher. A method for processing a silver halide photographic light-sensitive material, which is a dissolved liquid.

(2) In a processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, the developer contains reductones and a developer replenisher. And / or a replenishing rate A and a replenishing solution amount B of the fixing replenisher to the processing tank in a relationship represented by the following formula (1).

Formula (1) 0.001 ≦ A × B ≦ 0.015 In the formula, A represents liter / min, and B represents liter / quarter.

(3) In a processing method for developing, fixing, and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, a developer is supplied by dissolving a solid developer. The developer contains reductones as a developing agent and a sulfite of 0.5 mol / l.
A solid developer consisting of one solid part containing less than and another solid part containing carbonate, wherein each solid part is separately dissolved and mixed just before the timing of replenishment and supplied as a replenisher. A method for processing a silver halide photographic light-sensitive material, characterized in that:

(4) In a processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, a developer and a fixer dissolve a solid developer. The developer is a developer supplied with reductones as a developing agent and a sulfite in 0.1%.
A solid developer comprising one solid part containing less than 5 mol / l and another solid part containing carbonate, wherein the fixing agent contains one solid part containing thiosulfate and aluminum sulfate. It is a solid fixing agent composed of different solid parts, and separately dissolves the solid parts of the developer and the fixing agent, and separately mixes the solution of each part in accordance with the processing timing of the photosensitive material. A method for processing a silver halide photographic material, wherein the material is supplied directly to a developing tank and a fixing tank.

(5) In a processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, a developing solution is prepared by dissolving a tablet-like solid processing agent. The developer is a supplied liquid, the developer contains reductones, and the transport rollers of the transport rack in the developing tank and / or the transport rack in the fixing tank are all immersed in the liquid. A method for processing a silver halide photographic material, wherein all of the outer rollers are out of liquid.

(6) In a processing method for developing, fixing, and washing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the developing solution contains reductones and contains a reductone. When the ratio of the tabular grains having an aspect ratio of 4 or more (expressed as the ratio of the projected area) to the silver halide grains contained in the silver halide emulsion layer is C, and the pH of the developing solution in the developing tank is D, The relationship is expressed by the following equation (2), and the processing time is Dry t
o A method for processing a silver halide photographic material, wherein the processing time is 90 seconds or more.

Formula (2): 50% ≦ C ≦ 100% 9.3 ≦ D ≦ 9.6 20% ≦ C <50% 9.6 <D ≦ 9.80% ≦ C <20% 9.8 <D ≦ 10.0 Hereinafter, the present invention will be described in more detail.

In the present invention, the first aspect of the present invention is such that granules are used as a development initiator and a fixing initiator, and a tablet-like solid processing agent is used as both replenishers. It is possible to stabilize the performance of the development starting solution and the fixing starting solution because the binder and activator (lubricant) can be freed or reduced in amount, so that the subsequent day-to-day running processability can be stabilized. Can greatly contribute.

From the viewpoint of long-term processing stability, the tablet-like treating agent is excellent in storage stability in the form of a kit, and in view of the fact that the replenisher is supplied in a fresher state, the use of the replenishing agent for a longer period of time allows Running stability can be improved.

In addition, compared to tablets, granules have a large surface area and are excellent in solubility, so that they also have the property that the preparation time for starting processing after liquid exchange and after installing a new automatic developing machine is shortened.

The development initiator according to the present invention refers to a developer having a capacity of a developing tank required for starting a developing solution processing in an automatic developing machine. So that you can get closer to
A starter containing an acid (mainly acetic acid) for lowering the pH and KBr as an inhibitor (the starter alone has no developability).

To put it simply, it means the amount required for a given vat when starting the developing solution processing. The development initiator of the present invention is preferably added with a suitable starter (for adjusting the development activity) to start development.

The term "fixing initiator" of the present invention means a fixing agent having a capacity of a fixing processing tank required for starting the processing of a fixing solution in an automatic developing machine. To put it simply, it means the amount required for a given vat when starting the fixer processing.

The granular solid processing agent is prepared by kneading a concentrated solution or a fine powder of the photographic processing agent or a granular photographic processing agent with a water-soluble binder and molding into granules, or forming a water-soluble binder on the surface of the temporarily formed photographic processing agent. Any means such as forming a coating layer by spraying an agent can be adopted (Japanese Patent Laid-Open No. 4-29136).
Nos. 4-85535, 4-85536, 4-
No. 85534, No. 4-172341). The granular solid processing agent is preferably a granule formed by granulating a powdery photographic processing agent.

As the granulation method, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. The obtained granules preferably have an average particle size of 100 to 800 µm, more preferably 200 to 750 µm. Further, the particle size distribution is such that 60% or more of the granular particles are ± 100 to 1%.
Preferably it is within a deviation of 50 μm.

More preferably, at the time of granulation, preservability and solubility are excellent by separately granulating each component such as an alkali agent, a reducing agent, a preservative and the like.

Further, granulating agents are described, for example, in JP-A-2-10.
No. 9042, No. 2-109043, No. 3-39735
And the method described in the specification of JP-A-3-39739.

The granular solid processing agent and tablet solid processing agent of the present invention contain at least one dextrin or sugar alcohol as a water-soluble binder. The content in the solid processing agent is preferably 0.5% or more and less than 30%,
Particularly, the content is preferably 3% or more and less than 20%. The saccharides referred to in the present invention refer to monosaccharides, polysaccharides in which a plurality of these are glycosidically bonded to each other, and degradation products thereof.

The tablet-like solid processing agent of the present invention is obtained by granulating a powdery photographic solid processing agent and then performing a tableting step to solidify the tablet-like solid processing agent. Compared to a solid processing agent formed by simply mixing a photographic processing agent component and forming a tablet, there is an advantage that solubility and storage stability are improved, and as a result, photographic performance is stabilized. Granulation for tablet formation is the same as the method for obtaining a granular solid processing agent. For tablet formation, the average particle size of the obtained granules is the same as the above-mentioned granules in that the granules are mixed and pressed and compressed, and the components become non-uniform, so-called segregation is unlikely to occur. Size is preferred. Next, when the obtained granules are compressed under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a briquetting machine can be used. The tablet processing agent obtained by pressurizing and compression is very advantageous from the viewpoints of productivity and handleability or in that it can solve the problem of dust when used on the user side.

The granular developer and the granular fixing agent can be easily dissolved in advance with a commercially available stirrer or the like, and the dissolved liquid is poured into the processing tank, or the granules corresponding to the processing tank capacity are dissolved in the processing tank. (May be dissolved by circulation stirring of the tank).

The tablet-like developing replenisher and the tablet fixing replenisher consist of one agent or a plurality of agents, but preferably two agents from the viewpoints of storage stability and productivity. In the case of two agents, the developing agent is an alkaline agent (carbonate, etc.), a developing agent (ascorbic acid, dihydroxybenzenes) and an auxiliary agent (phenidone, dimezone S)
) Are preferably separate parts, and the fixing agent is preferably such that the acid agent (aluminum sulfate, chelating acid, etc.) and the fixing agent (thiosulfate) are separate parts.

Reductones contained in the solid processing agent include:
It is represented by the following general formula (A).

[0029]

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Where R₁, R_TwoIs a hydroxy group,
Amino group (as a substituent, an ethyl group, an n-butyl group,
A hydroxyethyl group, an alkyl group having 1 to 10 carbon atoms
Etc.), acylamino group (acetylamino group, benzoyl
Amino group), alkylsulfonylamino group (methane
Sulfonylamino group), arylsulfonylamino
Group (benzenesulfonylamino group, p-toluenesulfo
Nilamino group), alkoxycarbonylamino group
(Methoxycarbonylamino group, etc.), mercapto group
Or an alkylthio group (e.g., methylthio, ethylthio, etc.)
Etc.). R₁, R_TwoPreferred examples of
Xy group, amino group, alkylsulfonylamino group, ant
And a sulphonylamino group. X is 5
Group of atoms necessary to form a 6-membered ring, preferably
A carbon atom, an oxygen atom or a nitrogen atom;
₁, R_TwoIs substituted with two vinyl carbon atoms and carbonyl
And a 5- to 6-membered ring together with the carbon atom. X components
Examples of the body include -O-, -C- (R _Three) (R_Four)-, -C
(R_Five) =, -C (= O)-, -N (R₆)-, -N =
It is configured in combination.

However, R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy, carboxy or sulfo group can be mentioned as a substituent). ), A hydroxy group and a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring.

Examples of the 5- or 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring,
Examples include an azacyclohexenone ring and a uracil ring. Preferred examples of the 5- to 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

The compound represented by formula (A) may form a salt with lithium, sodium, potassium, ammonium and the like.

The specific examples of the compounds of the present invention are shown below.
The present invention is not limited to this.

[0035]

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[0036]

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[0037]

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Preferred among the above specific examples are ascorbic acid or erythorbic acid (stereoisomer) (A-1)
It is. The compound represented by the general formula (A) of the present invention is preferably 30% or more, more preferably 50%, of the total mass of the compound in the solid processing agent.
The above is preferred. The amount added to the processing solution is not particularly limited, but is practically 0.1 to 100 per liter of the processing solution.
g, preferably in the range of 0.5 to 60 g, is desirable for obtaining the effect of suppressing the formation of white precipitate. The treatment liquid of the present invention may contain only one kind of the compound represented by the general formula (A), or may contain two or more kinds thereof.

Next, the developer obtained by dissolving the solid processing agent of the present invention will be described. Specifically, the developer may contain the following developing agents in addition to the reductones.
Examples of black-and-white developing agents include dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5-
Dimethylhydroquinone, potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate) 3-pyrazolidones (for example, 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-
Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2- Benzothiazole)
-3-pyrazolidone, 3-acetoxy-1-phenyl-
3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N
-Methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.),
1-allyl-3-aminopyrazolines (for example, 1-
(P-hydroxyphenyl) -3-aminopyrazoline,
1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-
Aminopyrazoline), pyrazolones (eg, 4-aminopyrazolone), and the like, or a mixture thereof.

These developers can be added to the solid processing agent of the present invention in advance and added to the solution of the solid processing agent of the present invention. In the present invention, it is preferable that dihydroxybenzenes such as hydroquinone are not substantially contained. Substantially free means that the content of the compound is less than 0.001 mol / l.

The solid processing agent of the present invention contains a sulfite. The sulfite and / or metabisulfite in the solid processing agent of the present invention preferably accounts for 1% to 50% of the total mass, and more preferably 3% to 30%. Further, the sulfite is used in a molar ratio of metabisulfite of 85:15 to
0: 100, preferably 60:40 to 0: 1.
00 is more preferable, and 35:65 to 0: 100 is particularly preferable. Furthermore, when the solid processing agent is dissolved to form a processing solution, the amount of sulfite in the processing solution is 0.05 mol / l or more and less than 0.3 mol / l, and further 0.1 mol / l or more and 0.3 mol / l. Less than is preferred.

In addition, buffer agents (eg, carbonates, boric acid, borates, alkanolamines, etc.), alkali agents (eg, carbonates), solubilizers (eg, polyethylene glycols and esters thereof), pH adjusters (Eg, organic acids such as citric acid), sensitizers (eg, quaternary ammonium salts), development accelerators, hardeners (eg, dialdehydes such as glutaraldehyde), surfactants, and antifoggants As an azole organic antifoggant (eg, indazole, imidazole, benzimidazole, triazole, benzotriazole, tetrazole, thiadiazole), for masking calcium ions mixed in tap water used in the treatment liquid Concealing agents sodium hexametaphosphate, calcium hexametaphosphate, There is a re-phosphoric acid salts and the like. Like the above-mentioned developer, it may be contained in the solid processing agent of the present invention in advance, or may be contained in a solution of the solid processing agent of the present invention.

In the present invention, a silver stain inhibitor, for example, a compound described in JP-A-56-24347 can be used.

Further, the amount of carbonate in the developing solution according to the present invention is preferably 0.3 mol / l or more and less than 0.8 mol / l.

Further, the pH of the developer obtained in the present invention is 1
It is preferably in the range of 0.5 or less, more preferably 9
１10.0.

Further, amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer obtained in the present invention.

In addition, the developer obtained in the present invention includes L.
F. A. Messon, "Photographic Processing Chemistry", Focal Press (1966)
Pp. 22-229, U.S. Pat. No. 2,193,015
No. 2,592,364, JP-A-48-64933.
Nos. Or the like may be used.

On the other hand, the solid processing agent of the present invention contains at least one dextrin or sugar alcohol.
The content in the solid processing agent is preferably 0.5% or more and less than 30%, particularly preferably 3% or more and less than 20%.

The saccharides referred to in the present invention refer to monosaccharides, polysaccharides in which a plurality of these are glycosidically bonded to each other, and their decomposed products.

Monosaccharides include single polyhydroxy aldehydes, polyhydroxy ketones and their reduced derivatives,
It is a general term for a wide range of derivatives such as oxidized derivatives, deoxy derivatives, amino derivatives and thio derivatives. Many sugar, is represented by the general formula C _n H _2n O _n, a compound derived from a sugar skeleton represented by the general formula be included, in the present invention is defined as monosaccharides. Preferred among these monosaccharides are
These are sugar alcohols in which the aldehyde group and ketone group of the sugar are reduced to primary and secondary alcohol groups, respectively.

Polysaccharides include celluloses, starches,
Glycogens and the like are included, celluloses include derivatives such as cellulose ethers in which some or all of the hydroxyl groups are etherified, and starches are various degradation products from hydrolysis to maltose. Including certain dextrins. Cellulose may be in the form of an alkali metal salt from the viewpoint of solubility. Those preferably used in these polysaccharides are celluloses and dextrins,
More preferred are dextrins.

Specific examples of monosaccharides that can be preferably used in the present invention are shown below. [Exemplary Compound] B- (1) Glyceraldehyde B- (2) Dihydroxyacetone (including dimer) B- (3) D-erythrose B- (4) L-erythrose B- (5) D-threose B- (6) L-threose B- (7) D-ribose B- (8) L-ribose B- (9) D-arabinose B- (10) L-arabinose B- (11) D-xylose B- (12) L-xylose B- (13) D-lyxose B- (14) L-lyxose B- (15) D-xylulose B- (16) L-xylulose B- (17) D-ribulose B- (18) ) L-Ribulose B- (19) 2-deoxy-D-ribose B- (20) D-allose B- (21) L-allose B- (22) D-altrose B- (23) L-Altro Source B- (24) D-glucose B- (25) L-glucose B- (26) D-mannose B- (27) L-mannose B- (28) D-growth B- (29) L-growth B- (30) D-Idose B- (31) L-Idose B- (32) D-Galactose B- (33) L-Galactose B- (34) D-Talose B- (35) L-Talose B- (36) D-Quinoboth B- (37) Digitarose B- (38) Digitoxose B- (39) Shimarose B- (40) D-Sorbose B- (41) L-Sorbose B- (42) D-Tagatose B- (43) D-fucose B- (44) L-fucose B- (45) 2-deoxy-D-glucose B- (46) D-psicose B- (47) D-fructose B- (4) 8) L-fructose B- (49) L-rhamnose B- (50) D-glucosamine B- (51) D-galactosamine B- (52) D-mannosamine B- (53) D-glycero-D-galactohep Toose B- (54) D-glycero-D-mannoheptose B- (55) D-glycero-L-mannoheptose B- (56) D-glycero-D-gloheptose B- (57) D-glycero-D-idoheptose B -(58) D-Glycero-L-glucoheptose B- (59) D-Glycero-L-taloheptose B- (60) D-Altroheptulose B- (61) D-Mannoheptulose B- (62) D-Altro-3-heptulose B- (63) D-glucuronic acid B- (64) L-glucuronic acid B- (65) N-acetyl D-glucosamine B- (66) Glycerin B- (67) D-trait B- (68) L-trait B- (69) Erythritol (trade name, Mitsubishi Chemical Food Erythritol) B- (70) D-arabit B- (71) L-arabit B- (72) Adonit B- (73) Xylit B- (74) D-Sorbit B- (75) L-Sorbit B- (76) D-Mannit B- (77) L- Mannit B- (78) D-id B- (79) L-id B- (80) D-talit B- (81) L-talit B- (82) Dulcit B- (83) Allozurcit The sugar alcohols preferably used are B- (66) to (83), and more preferably B- (69) and (74) to (83). That.

Specific examples of polysaccharides and saccharide hydrolyzates which can be preferably used in the present invention are shown below.

C- (1) Maltose C- (2) Cellobiose C- (3) Trehalose C- (4) Gentiobiose C- (5) Isomaltose C- (6) Lactose C- (7) Raffinose C- (8) ) Gentianose C- (9) Stachyose C- (10) Xylan C- (11) Araban C- (12) Glycogen C- (13) Dextran C- (14) Inulin C- (15) Levan C- (16) Galactan C- (17) Agarose C- (18) Amylose C- (19) Sucrose C- (20) Agarobiose C- (21) Methylcellulose C- (22) Dimethylcellulose C- (23) Trimethylcellulose C- (24) Ethylcellulose C- (25) Diethylcellulose C- (26) Triethylcellulose C- (2 7) Carboxymethylcellulose C- (28) Carboxyethylcellulose C- (29) Aminoethylcellulose C- (30) Hydroxymethylcellulose C- (31) Hydroxyethylmethylcellulose C- (32) Hydroxypropylcellulose C- (33) Hydroxypropylmethylcellulose C -(34) Hydroxypropylmethylcellulose acetate succinate C- (35) Carboxymethylhydroxyethylcellulose C- (36) α-dextrin C- (37) β-dextrin C- (38) γ-dextrin C- (39) σ- Dextrin C- (40) ε-Dextrin C- (41) α-Limit dextrin C- (42) β-Limit dextrin C- (43) Phosphorylase Limit dextrin C- (44) Soluble starch C- (45) Thin nori starch C- (46) White dextrin C- (47) Yellow dextrin C- (48) British gum C- (49) α-cyclodextrin C- (50) β-cyclodextrin C -(51) γ-cyclodextrin C- (52) hydroxypropyl-α-cyclodextrin C- (53) hydroxypropyl-β-cyclodextrin C- (54) hydroxypropyl-γ-cyclodextrin C- (55) malto Dextrin The dextrins preferably used in these exemplified compounds are C- (36) to (55), and particularly preferably C- (49) to (50), (52) and (5).
3) and (55). The dextrin used in the present invention may have any weight average molecular weight, but is preferably from 10 to 1,000.

Saccharides exist widely and naturally, and commercially available products are easily available. Also, various derivatives can be easily synthesized by performing reduction, oxidation, dehydration, or the like.

As a commercial product, starch decomposed products include Pine Flow, Paindex series, Foodtex, Max100, Glister P, TK-16, MPD, H-PDX, H-PDX, manufactured by Matsutani Chemical Industry Co., Ltd. And Oil Q series manufactured by NOF Corporation.

The solid processing agent of the present invention contains an organic oxide represented by the following general formula (D) in an amount of 0.01% to 3.0% of the total mass.
It contains below. Preferably it is 0.1% or more and 2.5% or less, more preferably 0.5% or more and 2.0% or less.

[0058] In the general formula _{(D) R-S x O} y M formulas, R represents an aliphatic group, an aromatic group or a heterocyclic group, x is 1
Or 2, y represents 2 to 8 and M represents a cation.

In the general formula (D), examples of the aliphatic group represented by R include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include methyl, ethyl, i-propyl, butyl, and t. -Butyl, pentyl,
Each group includes cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl and the like. These alkyl groups further include a halogen atom (for example, chlorine, bromine, fluorine, etc.) and an alkoxy group (for example, methoxy, ethoxy, 1,
1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), an aryloxy group (eg, phenoxy, naphthyloxy), an aryl group (eg, phenyl, naphthyl, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-
Ethylhexylcarbonyl, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl, naphthyloxycarbonyl, etc.), alkenyl group (for example, vinyl, allyl, etc.), heterocyclic group (for example, 2-pyridyl, 3-pyridyl,
4-pyridyl, morpholyl, piperidine, piperazil,
Pyrimidine, pyrazoline, furyl, etc.), alkynyl group (eg, propargyl), amino group (eg, amino, N,
N-dimethylamino, anilino), a cyano group, a sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.).

Examples of the alkenyl group include vinyl and allyl, and examples of the alkynyl group include propargyl.

Examples of the aromatic group represented by R include phenyl and naphthyl. Examples of the heterocyclic group represented by R include a pyridyl group (eg, 2-pyridyl, 3-pyridyl, 4-pyridyl), a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a cyenyl group, a pyrrolyl group, a pyrazinyl group, Examples include a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulfolanyl group, a pipedilinyl group, a pyrazolyl group, and a tetrazolyl group.

The above-mentioned alkenyl group, alkynyl group, aromatic group and heterocyclic group can all be substituted by the same groups as the alkyl group represented by R and the groups shown as the substituent of the alkyl group.

The group represented by M is preferably a metal ion or an organic cation. Examples of the metal ion include a lithium ion, a sodium ion, and a potassium ion. Examples of the organic cation include an ammonium ion (ammonium, tetramethylammonium,
Tetrabutylammonium), phosphonium ion (tetraphenylphosphonium), guanidyl and the like.

Specific examples of the compound represented by formula (D) are shown below, but the present invention is not limited thereto.

D-1 C ₂ H ₅ SO ₃ Na D-2 CH ₃ (CH ₂ ) ₆ SO ₃ Na D-3 CH ₃ (CH ₂ ) ₇ SO ₃ Na D-4 CH ₃ (CH ₂ ) ₅ OSO _{3 Na D-5 CH 3 (} CH 2) 6 OSO 3 Na D-6 CH 3 (CH 2) 7 OSO 3 Na D-7 CH 3 O (CH 2) 2 SO 3 Na

[0066]

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Next, the fixing solution used in the present invention will be described. The fixing solution according to the present invention is preferably prepared by preparing a solid processing agent, dissolving it, and preparing the solution. The fixing agent preferably contains a thiosulfate. The thiosulfate is specifically used as a salt of lithium, potassium, sodium, or ammonium. Preferably, a fixing solution having a high fixing speed can be obtained by using ammonium thiosulfate and sodium thiosulfate.

In addition, iodide salts and thiocyanates can also be used as fixing agents. The fixing solution used in the present invention contains a sulfite. As sulfites,
Lithium, potassium, sodium, ammonium salts and the like are used.

The fixing solution used in the present invention may contain a water-soluble chromium salt or a water-soluble aluminum salt.
Examples of the water-soluble chromium salt include chrome alum and the like.
Examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride, and aluminum chloride.

The fixing solution used in the present invention contains acetate ions. The type of acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates acetate ion in the fixing solution.However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used. Sodium salts and ammonium salts are preferred.

Further, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof may be contained.

Examples of these salts (for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium bitartrate) Potassium, sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate,
Preferred examples include lithium, potassium, sodium, and ammonium salts represented by ammonium succinate and the like.

Among the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof. Examples of other acids include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid and malic acid, but preferably boric acid and aminopolycarboxylic acid. Acids and salts such as acids.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Examples of the fixing accelerator include thiourea derivatives, alcohols having a triple bond in the molecule, thioethers and the like.

The fixing solution has a pH of 3.8 or more, preferably 4.
2 to 5.5. The package of the solid processing agent of the present invention can be implemented using the following materials.

As the synthetic resin material, polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched, unstretched), polychlorinated Vinylidene, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyesters, acrylonitrile-butadiene copolymer, epoxy-phosphate resin (JP-A-63-63037)
Or the polymer described in JP-A-57-32952). Or pulp may be used.

These are preferably made of a single material. When used as a film, the films are laminated and adhered, but may be used as a coating layer or a single layer.

Further, it is more preferable to use various gas barrier films, for example, using an aluminum foil or an aluminum vapor-deposited synthetic resin between the above-mentioned synthetic resin films.

Further, in order to preserve the solid processing agent and prevent the generation of stain, the oxygen permeability of these packaging materials is 50 ml.
/ M ²・ 24hr ・ atm or less (20 ℃ 65% RH
), More preferably 30 ml / m ² · 24 hr · at
m or less.

The total thickness of these laminated films or single layers is from 1 to 3000 μm, more preferably from 10 to 2000 μm.
μm, and more preferably 50 to 1000 μm.

The above synthetic resin film may be a one-layer (polymer) resin film or two or more laminated (polymer) films.
It may be a resin film.

In the present invention, the stability of development processing during running processing (for example, fluctuation due to hunting of temperature is suppressed) by the configuration in which the relation between the replenisher supply speed and the replenishment amount is expressed by the formula (1). Not only increases, but also the fixing property of the fixing process is improved. This is thought to be because the stability of the components was improved because the components of each liquid diffused uniformly into the processing tank at a slower rate.

The effect of the present invention can be exhibited when the relationship between the supply rate A of the replenisher and the amount B of the replenisher is represented by the formula (1), but preferably 0.002 ≦ A × B ≤
It is 0.01. It is preferable that both the developing solution and the fixing solution have the formula (1), but the developing stability and the fixing property can be improved by using only the developing solution or the fixing solution alone.

The supply rate of the replenisher for the developing solution and the fixing solution is 1
It is preferably from 00 ml / min to 600 ml / min, more preferably from 100 ml / min to 400 ml / min.

The replenishing amount of the developing solution is 300 ml / m ² or less, preferably 200 ml / m ² or less, more preferably 150 ml / m ² or less, so that the waste liquid can be reduced more remarkably. The same applies to the replenishing amount of the fixing solution.

In the present invention, the stability of the development processing during long-term running is greatly improved by separately dissolving the main part and the alkali part of the solid processing agent consisting of two parts and mixing them immediately before replenishment. I do. This is because the influence of the oxidative fatigue of the replenisher as well as the developing tank becomes large when the number of processed sheets is small, the replenishment amount is reduced and the residence time is prolonged, etc. Will be. The fact that the kit is a solid processing agent greatly contributes to the improvement of stability.

The above-mentioned solid processing agents can be selected from powders, granules, tablets and the like, but are preferably tablets from the viewpoints of storage stability and behavior.

The amount of sulfurous acid in the part containing the developing agent and the sulfite is less than 0.5 mol / l, preferably 0.1 mol / l.
05 to 0.3 mol / l. At 0.5 mol / l or more, problems such as increased generation of silver sludge tend to occur. The carbonic acid content of the part containing carbonate on the other hand is 0.3 ~
1.0 mol / l is preferred, and more preferably 0.3 to
0.8 mol / l.

The sulfurous acid part and the carbonate part may each be packaged in a moisture-proof packaging material, or the two parts may be packaged in the same manner. In the case of a tablet-like solid processing agent which is a preferred embodiment, the dimensions (diameter and thickness) of the tablet are changed in different parts so that the solid processing agent can be placed at the position where the solid processing agent is charged even if the two-part packaging is the same. By providing a device or a filter for sorting according to the size, it is possible to devise each part so as to fall into a tank for dissolving it.

The dissolution of the solid processing agent was carried out using a TC manufactured by Konica Corporation.
It is preferable to employ any of the dissolution stirring techniques employed in X-201, TCX-701, and TCX-M50. Further, it is preferable to provide a stock tank for storing the prepared part solutions outside the dissolution tank. By dissolving the prepared liquid and supplying it to the stock tank at the same time, for example, when the number of continuously processed photosensitive materials is large, there is a great advantage in that the preparation of the next solid processing agent can be prepared.

The solution of each part prepared by dissolution or the solution sent to the stock tank after that is mixed in a mixing tank provided immediately before replenishment and supplied as a replenisher, or in-line in the middle of a replenisher pipe. It can be in the form of being added and being supplied as a replenisher. When a mixing tank is provided, the opening ratio needs to be 0.03 or less, and more preferably 0.01 or less, in order to suppress oxidative fatigue due to stagnation.

The opening ratio of the stock tank and the dissolving tank of each part should be 0.03 or less, preferably 0.01 or less in order to avoid oxidative fatigue and evaporation and concentration due to liquid retention. This is particularly noticeable in the case of low replenishment.

In the present invention, the stability of the developing process and the fixing property are improved by directly supplying each part solution of the solid processing agent to the processing tank. In this case, since the replenishing component is supplied to the treating agent component without being affected by the oxidation, the effect is particularly remarkable when the replenishing amount is reduced. Further, when the liquid in the developing processing tank and the fixing processing tank is fatigued by long-term running and the performance (sensitometric performance, fixing performance) is deteriorated, it is also possible to supply only the necessary part liquid to adjust the performance. Therefore, it is very useful in that processing performance that is not affected by the usage conditions of the user can be achieved.

The solid processing agent described above can be selected from granules, powders and tablets, but is preferably a tablet. Regarding the replenishment method of directly supplying the solid developer and each part solution in which the solid fixing agent is dissolved to the developing tank and the fixing tank, the supply part of the developer part liquid may be located at any position in the development processing tank. It is preferable that the portions are located at close positions, and the fixing agent part liquid supply portions are each located as far as possible. In the case of the developer, the proximity of the developer increases the uniformity of the developing component, and further enhances the development stability. In the case of the fixing agent, a problem such as precipitation occurs easily when a part mainly composed of the main agent and an acid part mainly composed of aluminum are mixed at similar positions. In the invention of claim 4, the component concentration of the solid developer is preferably within the component concentration range described in the invention of claim 3.

The solid fixing agent contains a thiosulfate in a part containing a sulfite, a chelating agent, and a buffer (acetate, etc.).
May be included, the part containing aluminum includes a chelating agent,
It may contain a buffer agent.

In the present invention, in the roller configuration of the rack, the liquid immersion roller is 100% immersion and the external liquid roller is 100%, without the partial immersion and partial liquid immersion rollers. % Solution. As a result, the stability of development processing and the residual color during long-term running are improved. It is considered that this can suppress the oxidation of the developing solution exposed on the roller that rotates with the conveyance by eliminating the roller partially immersed and partially removed from the liquid, and also suppresses the evaporation and concentration. Further, with this configuration, it is possible to take measures to reduce the opening area of the processing liquid, and it can be said that it is more and more advantageous for improving the oxidation stability.

In the present invention, the roller arrangement in the transport rack constituted by the transport rollers may be a staggered arrangement, a counter arrangement or a combination thereof. The conveying roller preferably has a large contact angle with the treatment liquid, and the contact angle with distilled water is 70 ° or more, more preferably 90 ° or more and 130 ° or less. Thereby, the influence of the contamination of the outlet liquid roller by the processing liquid can be suppressed. Development-fixing and / or
Alternatively, it is preferable to provide a transfer rack for fixing and washing.
Further, it is preferable that a washing tank is provided in the transfer rack.

The solid processing agent used here is preferably a tablet in order to exert the effects of the present invention more.

In the present invention, the ratio of the tabular grains and the pH of the developing solution to be processed are represented by the formula (2) to obtain a developing solution containing reductones, especially ascorbic acid as a developing agent. Improves the stability of long-term running development processing using a liquid. The effect is great in a processing machine having a processing time of 90 seconds or more, and remarkable improvement in development processing stability is recognized.

In the invention according to claim 6, the aspect ratio of the silver halide grains is 4 or more, preferably 5 or more and 20 or less, more preferably 5 or more and 12 or less. The pH of the developing tank is as described in the formula (2), but the pH of the replenisher supplied is 0.1% higher than that of the processing tank.
2 or more high liquid, preferably pH 0.3 or more and 0.7
Or less, more preferably 0.3 or more and 0.5 or less.

The processing time is 90 seconds or more, and the automatic developing machine is larger than a large-sized machine (Konica Corporation SRX-502, Fujifilm Corporation CEPROS-M2, etc.) and a medium-sized machine (Konica Corporation TCX-201, FUJIFILM Corporation CEPRO
S-SV, etc.), and more preferably small machines (Konica Corporation SRX-101, Fujifilm Corporation CEPR)
OS-P, etc.), and the effects of the present invention can be more enhanced.

The photosensitive material used in the present invention is not particularly limited, but preferred examples of elements constituting the photosensitive material will be described below.

The emulsion used in the light-sensitive material of the present invention can be produced by a known method. The silver halide emulsion preferably used includes, for example, monodispersed grains having a high iodine type disclosed in JP-A-2-85846.
The crystal habit of the crystal may be cubic, tetradecahedral, octahedral, and the intervening (111) and (100) planes arbitrarily.

The crystal structure of silver halide may have different silver halide compositions in the inside and the outside. In a preferred embodiment, the emulsion is a core / shell type monodisperse emulsion having a two-layer structure comprising a low iodine shell layer in a high iodine core portion. The silver iodide content of the high iodine part is 20 to
The content is particularly preferably 20 to 30 mol% at 40 mol%.

The silver halide emulsion preferably used in the present invention is tabular grains having an average aspect ratio of more than 4. The advantage of such tabular grains is that they can improve spectral sensitization efficiency, improve graininess and sharpness of an image, and the like. For example, British Patent No. 2,112,157, US Patent No. 4,439,520, 4,433,048, 4,414,310, 4,434,226, JP-A-58-113927, 58-127921, 63-138342, 63-284272 and 63-284272. 6
Emulsions can be prepared by the methods described in these publications. In particular, JP-A-6-138568 (pages 1 to 3),
177535 (pages 2 to 5), JP-A-62-4214
No. 6 (14-15) are preferably used.

A more preferred silver halide emulsion used in the present invention is silver chlorobromide or silver chloride having a silver chloride content of 50% or more. The emulsion described above may be either a surface latent image type for forming a latent image on the grain surface, an internal latent image type for forming a latent image inside the grain, or a type for forming a latent image on the surface and inside. . These emulsions may use cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts. As a preferred water washing method, for example, a method using a sulfo group-containing aromatic hydrocarbon aldehyde resin described in JP-B No. 35-16086, or a coagulated polymer agent exemplified by G3 or G8 described in JP-A-63-158644 may be used. The method used is a particularly preferred desalting method. As the method of chemical ripening of the emulsion used in the light-sensitive material of the present invention, sensitization by a chalcogen compound such as selenium sensitization such as gold sensitization, reduction sensitization and sulfur sensitization, or a combination thereof is preferably used.

The silver halide emulsion of the present invention can be spectrally sensitized. As the spectral sensitizing dye used, cyanine, merocyanine, complex cyanine, complex merocyanine,
Examples include holopolar cyanine, hemicyanine, styryl dyes and hemioxonol dyes.

For example, oxacarbocyanine, benzimidazolocarbocyanine, benzimidazolooxacarbocyanine and the like as described in JP-A-5-113619 are mentioned. Further, dyes having a sensitizing effect in the blue light region described in JP-A-6-332102 are also preferably used. These spectral sensitizing dyes can be used alone or in combination.

The spectral sensitizing dye is preferably added as a solution dissolved in an organic solvent such as methanol. The addition amount of the spectral sensitizing dye is not uniform depending on the type of the dye and the emulsion conditions, but the amount added is 10 mol / mol of silver halide.
It is preferably from 900 to 900 mg, particularly preferably from 60 to 400 mg. The spectral sensitizing dye is preferably added before the completion of the chemical ripening step, and may be added in several portions before the completion of the chemical ripening. More preferably, after the growth step of the silver halide grains and before the completion of the chemical ripening step, particularly preferably before the start of the chemical ripening.

In the present invention, in order to stop the chemical sensitization (chemical ripening), it is preferable to use a chemical ripening terminator in consideration of the stability of the emulsion. Examples of the chemical ripening stopper include halides (eg, potassium bromide, sodium chloride, etc.), and organic compounds (eg, 4-hydroxy-6-methyl-1,3,3) known as antifoggants or stabilizers.
3a, 7-tetrazaindene) and the like. These may be used alone or in combination of a plurality of compounds.

In the emulsion of the light-sensitive material used in the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Examples thereof include a hydrazine compound and a tetrazolium salt.

Examples of the support that can be used in the light-sensitive material of the present invention include those described on page 28 of RD-17643 and page 1009 of RD-308119.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided.

Emulsion layers may be present on both sides of the support.
Only one side may be used. In the case of both sides, both sides may have the same performance or different performances.

[0118]

Example 1 << Preparation of Granular Solid Developer Using Reductones as Developing Agent >> (100 L Amount when Used as Developer) Granular Developer A (part including developing agent) Phenidone 400 g, N -Acetyl-D, L-penicillamine 7 g, glutaraldehyde sodium bisulfite 80
0 g, sodium metabisulfite 1050 g, sodium erythorbate (monohydrate) (monosodium salt of compound A-1) 7000 g, and D-sorbitol 400 g were put into a Henschel mixer FM10C / I (manufactured by Mitsui Mining Co., Ltd.). The mixture was mixed at 300 rpm for 30 seconds. Next, rotation speed 6
While stirring and mixing at 00 rpm, 80 ml of water was spray-added in a mist and mixed for 5 minutes to granulate. After that, the rotation speed 3
It dried under reduced pressure for 45 minutes, rotating at 00 rpm. Further, 13 g of sodium octanesulfonate was added and the number of rotations was 30.
The mixture was stirred and mixed at 0 rpm for 30 seconds to obtain a granular developer A.

Granule developer B (part containing alkaline agent (carbonate)) 9500 g of potassium carbonate, 400 g of sodium sulfite, 5-
Mercapto (1H) -sodium tetrazolyl acetate 8
g, 40 g of 1- (3-sulfophenyl) -5-mercaptotetrazole sodium, 600 g of potassium iodide, D
160 g of TPA5Na, 750 g of mannitol, and 300 g of D-sorbit were mixed with a Henschel mixer FM10C / I.
(Mitsui Mining Co., Ltd.) and mixed at 300 rpm for 1 minute. Next, 180 ml of water was spray-added while stirring and mixing at a rotation speed of 600 rpm, and mixed for 7 minutes to granulate. Thereafter, the substrate was dried under reduced pressure for 45 minutes while rotating at a rotation speed of 300 rpm. Further, 14 g of sodium octanesulfonate was added, and the mixture was stirred and mixed at a rotation speed of 600 rpm for 30 seconds to obtain a granular developer B.

The stirring blades attached to the Henschel mixer are of the So type for the lower blade and of the Y1 type for the upper blade (all manufactured by Mitsui Mining Co., Ltd.).

The obtained granule developer A and granule developer B were mixed with O
NY (15 μm) / SiOxPET (12 μm) / OP
P (25 μm) / LLDP (40 μm) pillow wrapping material 4 L as a developer under 25 ° C. 40% or less humidity control condition
Was filled and sealed. Note that the granular developers A and B are mixed in the same packaging material, but they were filled in the order of B → A without mixing in advance. The package of the encapsulated and packed granular developer was designated as α. Also, granule developer A
In addition, a packed body β of the granular developer was prepared by separately packaging the granular developer B in an amount of 4 L in the packaging material of the same material.

<< Preparation of tablet-like solid processing agent containing reductone as a main agent >> (100 L amount when used as a developer) Granule developer C (part including developing agent) In the preparation of the above-mentioned granule developer A 80 D-sorbitol
The same procedure was followed except that the amount of sodium octanesulfonate was 0 g and the amount of sodium octanesulfonate was 130 g to obtain a granular developer C.

Granule Developer D (Part Containing Alkaline Agent (Carbonate)) In the preparation of the above granule developer B, mannitol 1500 was used.
g, D-Sorbit 600 g, and the amount of sodium octanesulfonate were changed to 140 g to obtain a granule developer D.

The granule developer C and the granule developer D thus obtained were compressed and compressed at 25 ° C. and a humidity of 40% RH or less using a rotary tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. Perform each developing tablet (C),
(D) was produced.

The filling amount per tablet was (C) 10 g,
(D) The weight was 12.4 g. (C) 88 pieces, (D) 8
Four pieces (an amount that gives a volume of 8.4 L after dissolution) were sealed and packaged in a pillow bag of the same packaging material as the granular developer.

<< Preparation of Granular Solid Developer Containing Requine-Free Hydroquinone as Main Agent >> Comparison (100 L amount when used as developer) Granular developer a (part containing hydroquinone) 3000 g of hydroquinone, 200 g of phenidone, Dimezone S 400 g, N-acetyl-D, L-penicillamine 10 g, glutaraldehyde sodium bisulfite 800
g, sodium sulfite 600 g, D-sorbitol 50
0 g was placed in a Henschel mixer FM10C / I (manufactured by Mitsui Mining Co., Ltd.) and mixed at a rotation speed of 300 rpm for 30 seconds. Next, while stirring and mixing at 600 rpm, water 75
ml was spray-added in a mist and mixed for 5 minutes to granulate.
Thereafter, the substrate was dried under reduced pressure for 45 minutes while rotating at a rotation speed of 300 rpm. Add one more sodium octanesulfonate
0 g was added, and the mixture was stirred and mixed at a rotational speed of 300 rpm for 30 seconds to obtain a granular developer a.

Granule developer b (part including an alkaline agent) 5200 g of potassium carbonate, 50 g of potassium bicarbonate, 200 g of potassium bromide, 160 g of DTPA5Na, 200 g of lithium hydroxide monohydrate, 1-phenyl-5-mercaptotetrazole 5 g, 10 g of 5-methylbenzotriazole, 6000 g of potassium sulfite, 750 g of mannitol, and 300 g of D-sorbitol were put into a Henschel mixer FM10C / I (manufactured by Mitsui Mining Co., Ltd.) and the rotation speed was 3
Mix for 1 minute at 00 rpm. Next, at 600 rpm
While stirring and mixing with water, 180 ml of water was spray-added and mixed for 7 minutes to granulate. After that, the rotation speed 300rpm
and dried under reduced pressure for 45 minutes while rotating at m. Further, 10 g of sodium octanesulfonate was added, and the rotation speed was 300 rpm.
For 30 seconds to obtain a granular developer b.

The stirring blades attached to the Henschel mixer are a So type lower blade and a Y1 upper blade (both manufactured by Mitsui Mining Co., Ltd.).

The obtained granule developer a and granule developer b were mixed with O
NY (15 μm) / SiOxPET (12 μm) / OP
P (25 μm) / LLDP (40 μm) pillow wrapping material 4 L as a developer under 25 ° C. 40% or less humidity control condition
Was filled and sealed. Incidentally, the granule developers a and b are to be mixed in the same packaging material, but they were charged in the order of b → a without mixing in advance. The package of the encapsulated and packaged granular developer was designated as α-2. In addition, a granular developer package β-2 in which 4 L of the granular developer a and the granular developer b were separately packaged in the same packaging material was also prepared.

<< Preparation of tablet-like solid processing agent mainly containing hysoloquinone not containing reductone >> Comparison (100 L amount when used as a developer) Granular developer c (part including developing agent) The above-mentioned granular developer In the preparation of a.
A granule developer c was prepared in the same manner except that the amount of sodium octanesulfonate was 0 g and the amount of sodium octanesulfonate was 200 g.

Granule developer d (part including alkali agent) In the preparation of the above-mentioned granule developer b, mannitol 1500 was used.
g, D-Sorbit 650 g, and the amount of sodium octanesulfonate were changed to 200 g to prepare a granular developer d.

The granule developer c and the granule developer d thus obtained were compressed and compressed at 25 ° C. and a humidity of 40% RH or less by a rotary tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. Perform each developing tablet (c),
(D) was produced.

The filling amount per tablet is (c) 10 g,
(D) The weight was 12.4 g. (C) 49 pieces, (d) 9
Four pieces (an amount that would give a volume of 8.4 L after dissolution) were packaged together in a pillow bag of the same packaging material as the granular developer.

<< Preparation of Granular Solid Fixing Agent >> (100 L amount when used as fixing solution) Granular fixing agent (E) (part including aluminum) <First mixture> Sodium gluconate 250 g Succinic acid 1100 g Tartaric acid 150 g D-mannitol 100 g D-sorbitol 10 g The above compound was placed in a Henschel mixer FM10C / I (manufactured by Mitsui Mining Co., Ltd.) and stirred and mixed at a rotation speed of 1100 rpm for 30 seconds. The mixture was stirred and mixed at a rotation speed of 1500 rpm for 1 minute and 30 seconds.

In the same manner as the stirring and mixing, Blue No. 1
g of granulated combined water containing 14 g of mist was sprayed and granulated. The granulated water was pressurized with compressed air from a spray nozzle attached to the lid of a Henschel mixer and added to the mixer as a mist.

<Second Mixing> Subsequently, 1500 g of aluminum sulfate octahydrate and 1400 g of sodium acetate were added to the granules in the mixer, and the mixture was stirred and mixed at a rotation speed of 1100 rpm for 30 seconds.

<Third Mixing> Next, 14 g of sodium 1-hexanesulfonate was added, and the mixture was stirred and mixed at 1,100 rpm for 30 seconds to obtain a granule fixing agent (E).

The stirring blades attached to the Henschel mixer are a So type lower blade and a Y1 upper blade (both manufactured by Mitsui Mining Co., Ltd.).

Granule Fixing Agent (F) (Part Containing Thiosulfate) <First Mixing> Ammonium Thiosulfate / Sodium Thiosulfate (9/1) 14,600 g Sodium Metabisulfite 900 g Mercaptothiazole 50 g Pine Flow 400 g The mixture was placed in a mixer FM10C / I (manufactured by Mitsui Mining Co., Ltd.) and mixed with stirring at a rotation speed of 2200 rpm for 1 minute. Subsequently, the mixture was stirred and mixed at a rotation speed of 2200 rpm for 1 minute. Simultaneously, 70 ml of granulated combined water containing 0.05 g of Blue No. 1 was spray-added and granulated at the same time as mixing. This combined water was added to the mixer in the form of a mist by pressurizing with compressed air from a spray nozzle attached to the lid of the Henschel mixer.

<Second Mixing> 1000 g of thioether compound OH (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH and 40 g of sodium 1-hexanesulfonate were added to the granules in the mixer at a rotation speed of 1100 rpm. Stir and mix for 30 seconds.

<Third Mixing> 1400 g of sodium acetate was added and mixed at a rotation speed of 1100 rpm for 30 seconds to obtain a granule fixing agent (F).

The obtained granule fixing agent (E) and granule fixing agent (F) were mixed with ONY (15 μm) / SiOxPET (12 μm).
m) A pillow packaging material of / OPP (25 μm) / LLDP (40 μm) was filled / enclosed and packaged in an amount of 4 L as a fixing solution at 25 ° C. and a humidity control condition of 40% or less. Note that the granule fixing agents E and F are mixed in the same packaging material, but they were filled in the order of E → F without mixing in advance. The package of the encapsulated and packed granular developer was designated as γ. In addition, a granule fixing agent package Ω in which 4 L of the granule fixing agent E and the granule fixing agent F were separately packaged in the packaging material of the same material was also prepared.

<< Preparation of Tablet Fixing Agent >> (100 L Amount when Used as Fixing Solution) Granule Fixing Agent G (Part Containing Aluminum) In the preparation of the granule fixing agent E, 200 g of mannitol was added.
A granule fixing agent G was obtained in the same manner except that the amount of sodium 1-hexanesulfonate was changed to 140 g.

Granule Fixing Agent H (Part Containing Alkaline Agent (Carbonate)) In the preparation of the granule fixing agent F, 900 g of pine flow,
A granule fixing agent H was obtained in the same manner except that the amount of sodium 1-hexanesulfonate was changed to 150 g.

The granule developer G and the granule developer H thus obtained were compressed and compressed at 25 ° C. and a humidity of 40% RH or less using a rotary tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. Perform each developing tablet (G),
(H) was produced.

The filling amount per tablet was (G) 10.5 g,
(H) The weight was 8.9 g. (G) 155 pieces, H) 47
Each of the pieces (an amount that gives a volume of 8.4 L after dissolution) was sealed and packaged in a pillow bag of the same packaging material as the granular developer.

Development Starter Formulation (Amount Added to 1 L of Developer) 90% acetic acid 15 g N-acetyl D, L-penicillamine 0.1 g KBr 8.0 g Thioether compound OH (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH) ₂ ) 0.06 g of ₂ OH Finished with pure water 35 ml A tablet dissolving chemical mixer TCX-M50 (manufactured by Konica Corporation) was used as a device for dissolving tablets and supplying a replenisher. For both development and fixing, set each packaging bag (8.4L amount) that was opened by hand at the inlet of each solid processing agent, drop it into the chemical mixer, and at the same time drop hot water (tap water temperature) according to the temperature of the environment. (If the temperature is low, warm water of 25 ° C. or higher is used. If the temperature of the tap water is high, the temperature is not adjusted.). After the preparation, the solution is supplied to a spare tank tank provided in the TCX-M50, and is used as a replenisher for replenishment from the spare tank tank. The capacity of the spare tank was 24.4 L, and the sensor was controlled so that 17 L remained before the next tablet preparation. The opening ratio of the preliminary tank was adjusted to be 0.01 when the liquid was FULL.

Each of the granule developer and the granule fixing agent is put in a chemical tank containing 8 L (2 packs of 4 L) for 10 L, filled with predetermined water, and agitated with a three-one motor. Stir to dissolve and finish to 8L volume. The dissolution time was about 12 minutes for the developer and 8 minutes for the fixing agent at a water temperature of 15 ° C.

When the same volume of the tablet developer and the tablet fixing agent were dissolved, it took about 40 minutes for the developer and 30 minutes for the fixing agent.

The automatic developing machine used was TCX-201.
In order to supply replenishment from TCX-M50, it was used after changing to an external chemical mixer connection specification.

At the start, a 7.8 L amount of the solution of the granular developer prepared above was filled in the developing tank, and a 5.6 L amount of the solution of the granule fixing agent similarly prepared was filled in the fixing tank. The above starter was added to the developing tank at a rate of 35 ml / developing 1 L, and the developing treatment was started.

As shown in Tables 1 and 2, a method of dissolving a tablet-like solid processing agent, filling each processing tank as a starting solution, and starting development processing was also carried out as a comparative processing. In addition, comparative processing using a solid developer mainly containing hydroquinone not containing reductone (granular solid processing agent, tablet solid processing agent) was also performed in the same manner.

<Preparation of photosensitive material> (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 Ossein gelatin 24.2 g Water 9657 ml Compound (SU-4 below) (10% ethanol aqueous solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g With water 2825 ml D1 1.75 N aqueous solution of potassium bromide Silver potential control amount below Compound SU-4: HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (N + m = 5-7) JP-B-58-58288 and 58-5828 at 42 ° C
The solution B was added to the solution A1 using the mixing stirrer shown in No. 9.
1 and solution C1 were each added in an amount of 464.3 ml by a double jet method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again heated. B1 and the solution C1 were added at a flow rate of 55.4 ml / min for 42 minutes by the simultaneous mixing method. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was +8 mV using the solution D1. And +16 mV.

After the addition was completed, the pH was adjusted to 6 with a 3% aqueous potassium hydroxide solution, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm, and the average diameter ( It was confirmed by an electron microscope that the (diameter in circle) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Emulsion Em-1) The above seed emulsion-1
And four kinds of solutions shown below were used to prepare a tabular silver halide emulsion Em-1.

A2 Ossein gelatin 34.03 g Compound (SU-3) (10% aqueous solution of ethanol) 2.25 ml Seed emulsion-1 1.18 mol equivalent Equivalent to 3150 ml with water B2 1734 g potassium bromide Equivalent to 3644 ml with water C2 Silver nitrate 2478 g Finished to 4165 ml with water D2 Equivalent to 0.080 mol of fine grain emulsion composed of 3% by mass of gelatin and silver iodide grains (average particle size 0.05 μm) Here, the fine grain emulsion is 0.06 mol of potassium iodide To 6.64 liters of a 5.0% by mass aqueous gelatin solution containing
Two liters each of an aqueous solution containing 06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 60 ° C., and a part of the solution B2, a part of the solution C2, and half of the solution D2 were added thereto by a double jet method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. The total amount of the remaining solution B2 and solution C2 to 33
Added over minutes. During this time, the pH was adjusted to 5.8 and pAg
Kept 8.8 at all times. Here, the solution B2 and the solution C2
The addition rate was varied as a function of time to match the critical growth rate. Further, the above solution D2 was added in an amount corresponding to 0.15 mol% with respect to the total silver amount to perform halogen substitution.

After the addition was completed, the emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% (by mass) of modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added as an aggregating polymer agent, and added for 3 minutes. Stirred. Thereafter, a 56% (mass) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.
After stirring for 3 minutes, the mixture was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then 4
9.0 liters of distilled water at 0 ° C. was added, the supernatant was drained after stirring and standing, and 11.25 liters of distilled water was further added. After stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% (by mass) aqueous sodium carbonate solution were added, and p
H was adjusted to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was adjusted to 5.8 at 40 ° C.
0 and pAg were adjusted to 8.06.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.11 μm and the average thickness was 0.2.
5 μm, average aspect ratio about 4.5, width of particle size distribution 1
It was 8.1% tabular silver halide grains. The average twin plane distance was 0.020 μm, and grains having a twin plane distance to thickness ratio of 5 or more accounted for 97% (number) of all tabular silver halide grains.

Next, after the above emulsion (Em-1) was heated to 60 ° C., a predetermined amount of the following spectral sensitizing dyes (SD-1 and SD-2) was added thereto, and the following (a) was added as a solid fine particle dispersion. 10 minutes after the addition, the following (b) was added as a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and a dispersion of selenium sensitizer (Se-1),
After a further 30 minutes, a silver iodide fine grain emulsion was added and ripening was performed for a total of 2 hours. After aging, a predetermined amount of the stabilizer (ST-1) was added.

The above additives and their amounts (AgX1
(Per mole) is shown below. Spectral sensitizing dye (SD-1): 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydrous 400 mg Spectral sensitizing dye (SD- 2): 5,5'-di- (butoxycarbonyl) -3,3'-di (4-sulfobutyl) -benzimidazolocarbocyanine sodium salt anhydride 4.0 mg selenium sensitizer (Se-1) triphenyl Phosphine selenide 0.2 mg ST-1: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 500 mg adenine 15 mg potassium thiocyanate 95 mg chloroauric acid 2.5 mg sodium thiosulfate 2.0 mg iodide 280 mg of silver fine particles (a) A solid fine particle dispersion of a spectral sensitizing dye is prepared by adding a predetermined amount of a spectral sensitizing dye to water previously adjusted to 27 ° C. At a speed stirrer (dissolver) at 3,500rpm 30~12
Obtained by stirring for 0 minutes.

(B) The dispersion of the selenium sensitizer was prepared as follows. Se-1: triphenylphosphine selenide 120
g was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in pure water, and 93 g of a 25% by mass aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Then this 2
The liquid was mixed and dispersed at 50 ° C. by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm.
Per second for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% by mass or less. afterwards,
The dispersion was diluted with pure water to make up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation of Emulsion Coating Solution) The following various additives were added to each of the emulsions obtained above.

1,1-Dimethylol-1-bromo-1-nitromethane 0.1 mg / m ² t-butyl-catechol 1.75 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 13.5 mg / m ² polystyrene sulfonic acid Sodium 40 mg / m ² Trimethylolpropane 110 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 28 mg / m ² Latex (L) 1.27 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 260 mg / m ² Colloidal silica (Ludox AM: manufactured by DuPont, particle size 0.013 μm) 2.55 g / m ² Dextran (average molecular weight 40,000) 320 mg / m ² Thallium nitrate 0 0.5 mg / m ² However, the amount of gelatin applied was adjusted to 1.5 g / m ² did.

(Preparation of Coating Solution for Protective Layer) Matting agent comprising gelatin 0.8 g / m ² polymethyl methacrylate (area average particle size 6.0 μm) 27 mg / m ² Compound P 50 mg / m ² compound (SU-1) 4.4 mg / m ² compound (SU-2) 185 mg / m ² compound (SU-3) 48 mg / m ² Topside 300 (manufactured by Perchem Asia Co., Ltd.) 0.6 mg / m ^{2 The} amount of silver applied is one side. Was adjusted to 1.6 g / m ² .

(Preparation of Coating Solution for Crossover Cut Layer)
Glycidyl methacrylate / methyl acrylate / butyl methacrylate copolymer (50: 10: 40% by mass)
On both sides of the dispersion (concentration 10 mass% so as dilution) coated thickness 175μm blue-colored polyethylene terephthalate as a lower引液(PET) support, as the coating amount per surface 1 m ² is the following composition A support coated with a crossover cut layer was prepared.

Solid fine particle dispersion dye (SF) 12.8 mg Gelatin 0.2 g Latex (L) 312 mg Sodium polystyrene sulfonate 44 mg Topside 300 (manufactured by Perchem Asia) 0.4 mg

[0170]

Embedded image

Compound (SU-1): dihexyl sodium sulfosuccinate Compound (SU-2): C ₇ F ₁₅ CH ₂ (CH ₂ CH ₂ O) ₁₃
OH compound (SU-3): C ₁₁ H ₂₃ CON ((CH ₂ CH
₂ O) _m H) (CH ₂ CH ₂ O) _n H, Mw (mass average molecular weight) = 640 (Preparation of photosensitive material No. 1) Using these coating solutions,
Using two slide hopper type coaters at a speed of 120 m / min on the above support so that the coating amount is 1.6 g / m ² per one side and the amount of gelatin is 2.5 g / m ^2. Then, both sides were simultaneously coated with the following layer constitution, dried for 2 minutes and 20 seconds, and dried. 1 was produced.

<< Layer Composition >> Layer Position Layer Type Layer Amount of gelatin per side (g / m ² ) Upper protective layer 0.8 Intermediate layer Emulsion layer 1.5 Lower layer Crossover cut layer 0.2.

<Photosensitive material No. Preparation of 2> (Preparation of seed emulsion-2 [monodisperse cubic system]) Seed emulsion-2 was prepared as follows.

Solution A3 Ossein gelatin 30 g Potassium bromide 1.25 g 0.1 mol / L nitric acid 150 ml Distilled water 7700 ml Solution B3 Potassium bromide 6 g Potassium iodide 0.16 g Distilled water 740 ml Solution C3 Potassium bromide 680 g Iodide Potassium 20 g 2480 ml with distilled water Solution D3 8.4 g of silver nitrate 32 ml of 0.1 mol / L nitric acid 32 ml 740 ml with distilled water Solution E3 991.6 g of silver nitrate 80 ml of 0.1 mol / L nitric acid 2480 ml with distilled water Solution B3 and Solution D
3 was added over 10 minutes by the double jet method.
Then, the solution C3 and the solution E3 were added by a double jet method over 140 minutes. At this time, the initial addition flow rate was ８ of the final addition flow rate, and the sensitization was linearly sensitized with time. During the addition of these solutions, pH = 2, pA
g was constantly adjusted to 8. After completion of the addition, the pH was raised to 6 with sodium carbonate, 150 g of potassium bromide was added, and immediately after that, desalting and washing were carried out to obtain a single particle of silver iodobromide having an average grain size of 0.3 μm and containing 2 mol% of silver iodide. Dispersed cubic seed emulsion-2
I got According to the electron microscope, the twin generation rate is 1
% Or less.

(Preparation of Normal Crystal Core / Shell Emulsion Em-2) Normal crystal silver iodobromide containing 2.0 mol% of silver iodide was prepared using the above seed emulsion-2 and the following five kinds of solutions. Emulsion E
m-2 was prepared.

Solution A4 Ossein gelatin 75.5 g Compound (SU-4) 10% methanol aqueous solution 15 ml Seed emulsion-2 equivalent to 0.40 mol 4000 ml with distilled water Solution B4 Silver nitrate 46.2 g Equimolar amount of ammonia solution and distilled water And 259 ml of solution C4 647.6 g of silver nitrate An equimolar amount of an ammonia solution and distilled water were added to 1088 ml of solution D4 22.6 g of potassium bromide 13.5 g of potassium iodide 259 ml of distilled water 453.3 g of solution of potassium bromide 453.3 g of distillation The solution A4 was kept at 40 ° C. in a 1088 ml reactor with water, and the pH was adjusted to 9.5 by adding aqueous ammonia and acetic acid. After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, the solution B4 and the solution D4 were added by a double jet method while keeping the pH and the pAg constant, and a silver iodobromide layer containing 30 mol% of silver iodide was added. Was formed. PH 9.0 using acetic acid and potassium bromide, pAg
Was adjusted to 9.0, solution C4 and solution E4 were simultaneously added, and the mixture was grown until it reached 90% of the particle size.
At this time, the pH was gradually lowered from 9.0 to 8.2.
A potassium bromide solution was added to adjust the pAg to 11, and a solution C4 and a solution E4 were further added to grow the solution while gradually lowering the pH to 8, to obtain a silver iodobromide emulsion containing 2 mol% of silver iodide. After completion of the addition, precipitation and desalting were performed by the following method to remove excess salts.

(1) The mixed solution was heated to 40 ° C.
20 g / AgX of 1 mol of the aggregating gelatin agent is added, the pH is lowered by adding 56% by mass of acetic acid, and the mixture is allowed to stand and decanted.

(2) 1.8 liters / Ag of pure water at 40 ° C.
X1 mol is added, and after stirring for 10 minutes, it is left still and decanted.

(3) The above step (2) is repeated once. (4) An aqueous gelatin solution containing 92.2 g of ossein gelatin was added to 2500 ml, followed by stirring and redispersion to obtain Em-2.

About 1,000 Em-2 particles were observed and measured by an electron microscope, and the shape was analyzed. As a result, monodispersed spherical particles having an average particle diameter of 0.51 μm and a distribution width of 12% were obtained.

Next, the emulsion Em-2 was subjected to spectral sensitization and chemical sensitization in the following manner. After the emulsion was brought to 50 ° C., the spectral sensitizing dye (SD-1) was added as a solid fine particle dispersion in the same manner as in the above Em-1 so as to be 40 mg per mol of silver, and then the following selenium sensitizer (Se) was added. -2) is 7.0 × 10
^-6 mol, and ammonium thiocyanate was added in an amount of 4.0 × 10 ^-4 mol per mol of silver and 3.2 × 10 ^-6 mol of chloroauric acid.
And 3.4 × 10 ⁻⁵ mol of sodium thiosulfate, and after 40 minutes, the silver iodobromide fine grain emulsion was added to 1.7 × 10 ⁻⁵ mol.
After adding 10 ^-3 mol / Agmol, 1.2 × 1 of ST-1 was added.
Stabilized at 0 ^-2 mol.

Selenium sensitizer (Se-2): diphenyl
Pentafluorophosphine selenide (Preparation of photosensitive material No. 2) The following various additives were added to the obtained emulsion to prepare an emulsion coating solution. The amount of addition is shown in an amount per mole of silver halide.

T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl-triphenyl-phosphonium chloride 50 mg resorcin-4- Ammonium sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g Compound (G) 150 mg Compound (H) 70 mg The additives used for the protective layer are as follows. The amount of addition is shown in an amount per 1 g of gelatin.

Matting agent (polymethyl methacrylate having an area average particle diameter of 7 μm) 7 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 mg Compound (I) 12 mg 2,4-dinonylphenol / ethylene oxide 12 mol adduct 15 mg C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₀ CH ₂ CH ₂ OH 3 mg Compound (SU-2) 5 mg (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ O 36 mg

[0185]

Embedded image

The above coating solution was uniformly coated on both surfaces of an emulsion layer and a protective layer on a 175 μm thick undercoated blue-colored polyethylene terephthalate film base and dried. 2 was produced. The silver coverage of the silver halide emulsion layer was 2.20 g / m ² per side.
And

The photosensitive material Nos. 1 and N
o. 2 was subjected to uniform exposure so as to have a density of 1.0, and the processing was continued for 3 months in a processing mode of 60 sheets, each having a size of 40 pieces per day. The daily operating time of TCX-201 was 8 hours. The processing conditions are as follows.

Developing temperature 36 ° C. Fixing temperature 35 ° C. Rinse tap water temperature Drying temperature 55 ° C. Replenishment amount Replenishment amount for development and fixing is as described in Tables 1 and 2 (ml / m ² ). When 8.4 L is supplied for both development and fixing, TCX-M50 (manufactured by Konica Corporation) notifies the next tablet dissolution preparation with a buzzer, puts in the next tablet, dissolves it, and supplies it to the spare tank side. . The tablets prepared as described above were forcibly raised in storage conditions, and after storage at a temperature of 40 ° C., were prepared at 20 ° C. after preparation. Tablets stored at the start of the development processing were stored under the forced conditions, and the tablets stored at 40 ° C. for 2 weeks were used. After 3 months of running, the tablets stored for 3 months + 2 weeks were used.

<Evaluation of Processing Stability> The following photosensitive material sample was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corporation) and irradiated with X-rays under the conditions of a tube voltage of 90 KVP, a current of 20 mA and a time of 0.05 second. The sensitometry curve was prepared by the distance method, and the sensitivity was determined. The sensitivity value in Table 2 is fog +1.0
Is determined as the reciprocal of the X-ray dose required to obtain the concentration of the evaluation NO. It was expressed as a relative value when 1 was taken as 100.

Running was started from the starting solution, and several days from the first day, one month, and three months later, sensitometric evaluation was performed.

<Evaluation of unevenness in development> The photosensitive material obtained below was cut into large-sized pieces, subjected to uniform exposure so as to have a processed density of 1.0 and processed, and the image quality of the processed film was evaluated according to the following criteria. Was visually evaluated according to the following.

4: No density unevenness is observed. 3: Slightly streak-like unevenness is observed. Practical marginal level 2: There is some dark unevenness. Unsuitable for practical use 1: Intense unevenness is observed throughout. <Evaluation of residual color> A photosensitive material sample was developed without exposure and used as a sample for evaluation of residual color. This was visually evaluated.

4: There is no residual color at all. 3: Partial light color residual is observed. 2: Color residual is observed in a range of less than 1/2 of the photosensitive material. 1: Reddish color residual is observed in the entire photosensitive material. Be

[0194]

[Table 1]

[0195]

[Table 2]

As can be seen from the results shown in Tables 1 and 2, it is understood that the solid processing agent treatment using the granular solid processing agent as the initiator according to the present invention is excellent in running stability, density unevenness and residual color. It can also be seen that the effects of the present invention (particularly running stability) are excellent even when a tablet-like solid processing agent is used under forced storage conditions of 40 ° C.

Example 2 A tablet dissolving chemical mixer TCX was used, using the developed tablet containing reductone as a main ingredient, the developing tablet containing hydroquinone not containing reductone as a main ingredient, and a fixing tablet described in Example 1.
-The tablet was dissolved with M50 (manufactured by Konica Corporation). This was connected to the following automatic developing machine so that a replenisher could be supplied. The automatic processor is TCX-201 (Konica Corporation)
And SRX-101 (manufactured by Konica Corporation) were modified and used so that the replenishment supply rate and replenisher volume could be controlled.

As a development starting solution, a solution prepared by dissolving a tablet with TCX-M50 (manufactured by Konica Corporation) was supplied to fill the processing tank, and the starter described in Example 1 was added in an amount of 35 ml / development 1 L. . Fixing start solution is TCX-M
In step 50, a solution in which a fixing tablet was dissolved was supplied.

The TCX-201 was processed under the same processing conditions as in Example 1 (processing time, temperature, and replenishment amount are described in Table 3), and the photosensitive material prepared in Example 1 was processed into quarter-size sheets of 40 pieces each day. Then, 2400 sheets were treated for 60 days to prepare a running equilibrium solution accompanied by oxidative fatigue. 8 working hours per day
Time.

The SRX-101 was processed under the following processing conditions, and the photosensitive material prepared in Example 1 was cut into four pieces a day, and each piece was processed into 10 pieces. Prepared. The daily operating time was 8 hours.

[0201] <Evaluation of development stability> As shown in Table 3, the replenishment supply speed × the replenisher amount was adjusted, and the running process was performed in accordance with the above. Was evaluated.

The sensitivity was evaluated in the same manner as in Example 1. The difference between the minimum value and the maximum value of the sensitivities of the first to tenth sheets was expressed as a fluctuation width. The average value is also shown in Table 3.

<Evaluation of Fixing Property> The photosensitive material No. 1 prepared in Example 1 was used. Sample No. 1 was subjected to development processing without exposure to obtain a sample for evaluation of residual silver. One drop of an aqueous solution of 2.6 × 10 ⁻³ mol / l sodium sulfide was dropped as a residual silver evaluation solution, and after leaving for 3 minutes, the solution was wiped off and allowed to stand at room temperature and normal humidity for 15 hours.

Thereafter, using a PDA-65 densitometer (manufactured by Konica Corporation), the transmission density of blue light was measured between the portion where the residual silver evaluation liquid was dropped and the portion where the residual silver evaluation solution was not added. As a guide. If the value is 0.03 or less, there is no problem if the value is more than 0.03, the silver image will be discolored with time and the density will be reduced. Table 3 shows the results 60 days after the running.

[0205]

[Table 3]

As shown in Table 3, it can be seen that the sensitivity is high and stable and the development stability (variation width) and fixing property are excellent by adopting the constitution of the present invention.

Example 3 A developing tablet containing reductone as a main ingredient as described in Example 1 and a developing tablet containing hydroquinone containing no reductone as a main ingredient and a fixing tablet described in Example 1 were prepared in which the amount of sulfite was changed to Table 4. did. Tablet dissolution chemical mixer TCX-M5
0 (manufactured by Konica Corporation), a tank for dissolving the developing agent part (including the stirring and dissolving means), a spare tank for storing the dissolving solution, and a tank for dissolving the part containing carbonate (including the stirring and dissolving means) And a spare tank for storing the solution. Each of the above tablet parts was dissolved in the present apparatus. This modified TCX-M50 is an automatic processor (SRX-M50).
101 (manufactured by Konica Corporation)) so that the liquid for each part of the development could be supplied.

The dissolution finishing amount of the main part of the development was 5 L, and the dissolution finishing amount of the alkali part was 3.4 L. SRX-101 has been modified so that two kinds of tablet part liquids supplied with the processing are mixed in a single hose in-line immediately before entering the processing tank, and the mixed liquid is contained in the processing tank. Is injected as a replenisher.

As a comparison, TCX-M50 (Konica Corporation)
2 parts are melted in the same tank, without remodeling, stored in a spare tank and supplied with replenisher.
The process of connecting to RX-101 was also performed.

<Evaluation of long-term running stability> SRX-
Sample No. 101 was prepared under the following processing conditions, and the photosensitive material prepared in Example 1 was cut into four pieces a day, each having a size of 10 sheets, and then processed for 600 sheets over 60 days to prepare a running equilibrium solution accompanied by oxidative fatigue. The daily operating time was 8 hours.

[0211] The sensitometric performance (sensitivity) after 30 days and 60 days was evaluated in the same manner as in Example 1 and is shown in Table 4. The average gradation (Δdensity difference / Δexposure amount (LogE)) of fog + 0.25−fog + 2.0 of the obtained characteristic curve was expressed as a γ value.

[0212]

[Table 4]

[0213] As shown in Table 4, it can be seen that the constitution of the present invention is greatly excellent in long-term running stability.

Example 4 A developing tablet containing reductone as a main ingredient described in Example 1 and a developing tablet containing hydroquinone containing no reductone as a main ingredient and a fixing tablet described in Example 1 were prepared by changing the amount of sulfite to Table 5. did. Tablet dissolution chemical mixer TCX-M5
0 (manufactured by Konica Corporation), a tank for dissolving the developing agent part (including the stirring and dissolving means), a spare tank for storing the dissolving solution, and a tank for dissolving the part containing carbonate (including the stirring and dissolving means) And a spare tank for storing the solution. Also on the fixing side, a tank for dissolving the part containing thiosulfate (including the stirring and dissolving means), a spare tank for storing the dissolving solution, and a tank for dissolving the part containing the aluminum sulfate (including the stirring and dissolving means) And a spare tank for storing the solution. Each of the above tablet parts was dissolved in the present apparatus. The dissolution finishing amount of the main part of the development was 5 L, and the dissolution finishing amount of the alkali part was 3.4 L. The dissolution finishing amount of the thiosulfate part for fixing was 4 L, and the dissolution finishing amount of the aluminum sulfate part was 4.4 L. This modified TCX-M50 is connected to an automatic processor (SRX-101 (manufactured by Konica Corporation)),
The liquid for each part of the development was supplied.

The SRX-101 has been modified so that two types of tablet part liquid, each of the developer and the fixing agent supplied with the processing, enter directly into the processing tank. On the protruding side of the processing tank circulation agitation) and on the fixing side, the two types of injection are placed in different positions (one is the protruding side of the circulation agitation and the other is the suction side)
And The replenishment supply amount was as shown in Table 5, and the supply amount of each part could be controlled separately.

For comparison, TCX-M50 (Konica Corporation)
2 parts are melted in the same tank, without remodeling, stored in a spare tank and supplied with replenisher.
The process of connecting to RX-101 was also performed.

The long-term running stability was evaluated in the same manner as in Example 3. Further, in the same manner as in Example 1, evaluation of development unevenness during long-term running processing was performed.

[0218]

[Table 5]

As shown in Table 5, it can be seen that the constitution of the present invention is excellent in development stability and development unevenness.

Example 5 A tablet dissolving chemical mixer TCX was used, using the developed tablet containing reductone as a main ingredient, the developing tablet containing hydroquinone not containing reductone as a main ingredient, and a fixing tablet described in Example 1.
-The tablet was dissolved with M50 (manufactured by Konica Corporation). This was connected to the following automatic developing machine so that a replenisher could be supplied. The automatic processor is TCX-201 (Konica Corporation)
) And SRX-101 (manufactured by Konica Corporation) were modified and used as described below.

The transport rollers of the developing and fixing transport racks are immersed in 100% liquid. In TCX-201, the photosensitive material transported from the immersion roller at the developing tank outlet is transported directly to the developing-fixing transfer rack. A device has been devised in the transport direction. Further, the photosensitive material was modified so that the surface of the developing solution and the surface of the fixing solution were covered with an oxidation / evaporation preventing plate while leaving an area necessary for transportation. With this modification, the opening ratio of the developing tank of TCX-201 was 0.038 → 0.01, and the opening ratio of the fixing tank was 0.038.
4 → 0.01, the opening ratio of the developing tank of SRX-101 is 0.11 → 0.012, and the opening ratio of the fixing tank is 0.08 →
It becomes 0.015.

As a development starting solution, a solution prepared by dissolving a tablet with TCX-M50 (manufactured by Konica Corporation) was supplied to fill the processing tank, and the starter described in Example 1 was added in an amount of 35 ml / development 1 L. . Fixing start solution is TCX-M
In step 50, a solution in which a fixing tablet was dissolved was supplied.

The TCX-201 was processed under the same processing conditions as in Example 1 (processing time, temperature, and replenishment amount are described in Table 6), and the photosensitive material prepared in Example 1 was processed into quarters of 40 pieces each day. Then, 2400 sheets were treated for 60 days to prepare a running equilibrium solution accompanied by oxidative fatigue. 8 working hours per day
Time.

The SRX-101 was processed under the following processing conditions, and the light-sensitive material prepared in Example 1 was cut into four pieces a day and processed into 10 pieces each, and 600 sheets were processed over 60 days to prepare a running equilibrium solution accompanied by oxidative fatigue. Prepared. The daily operating time was 8 hours.

[0225] After 30 days for both TCX-201 and SRX-101, 60
The sensitivity after days was evaluated.

The evaluation of residual color was performed in the same manner as in Example 1. After 60 days, the specific gravity of the processing solution in the developing tank and the fixing tank was measured, and the concentration was calculated.

[0227]

[Table 6]

As shown in Table 6, it is understood that the constitution of the present invention is excellent in long-term running stability and residual color.

Example 6 A tablet dissolving chemical mixer TCX was used, using the developed tablet containing reductone as the main ingredient, the developing tablet containing hydroquinone not containing reductone as the main ingredient, and the fixing tablet described in Example 1.
-The tablet was dissolved with M50 (manufactured by Konica Corporation). This was connected to the following automatic developing machine so that a replenisher could be supplied. Automatic developing machine is SRX-101 (Konica Corporation)
Was used.

The developer containing reductone as the principal agent has a dissolution pH
Was 10.14, and the pH of the developing tank at the start of the developing process was 9.8 by adding the starter of Example 1.
It becomes 0. The dissolution pH of the fixing agent is 4.34, and this solution is used as a starting solution. The developer replenishment amount and the fixing replenishment amount are each 180.
When the light-sensitive material described in Example 1 was processed at a rate of 10 ml / m ^{2 at a} rate of 10 ml / m ² and processed for 100 days (to be a running equilibrium solution), the pH of the developing tank was 9.70, and the fixing was performed. The pH of the treatment tank was 4.65.

As shown in Table 7, the pH of the developer solution (used as a replenisher) was changed (acetic acid was added to lower the pH, and KOH was added to raise the pH) to reduce the pH of the running equilibrium solution. The pH was adjusted.

The light-sensitive material used in each running with the pH changed was a silver halide emulsion (described below) in which the proportion (C) of tabular grains having an aspect ratio of 4 or more as shown in Table 7 was prepared.

In the case of the photosensitive material No. described in Example 1, 50% ≦ C ≦ 100%. 1 was used. 0% ≦ C <20% is the value of photosensitive material No. 2 was used. No. The silver halide grains of No. 2 have almost 0% tabular grains.

<Photosensitive material No. 3 (20% ≦ C <50
%) The tabular grains having an aspect ratio of 2.5 to 3.7 can be obtained by changing the silver potential, pH, flow rate, and gelatin concentration when preparing the silver halide grains of the light-sensitive material described in Example 1. A silver halide emulsion occupying 97% of the total silver halide grains was prepared. This silver halide emulsion and the photosensitive material amount No. The silver halide emulsion prepared in Example 1 (aspect ratio 5 or more, 97%) was mixed at a ratio of 7: 3, and the ratio of tabular grains having an aspect ratio of 4 or more was about 30%. 3 was produced. Preparation of the light-sensitive material after the emulsion MIX is described in the light-sensitive material no. Performed in the same manner as 1.

In the same manner as in Example 1, the sensitivity was evaluated, and in the same manner as in Example 3, the γ evaluation was made 50 days and 100 days after the date. The pH of the developing tank at that time is also shown in Table 7.

Similarly, TCX-201 (60-second processing, 90-second processing) was subjected to long-term running with a processing of 40 sheets per day / quarter size to evaluate sensitivity and gamma.

[0237]

[Table 7]

As shown in Table 7, it can be understood that the constitution of the present invention is excellent in long-term running stability.

[0239]

According to the present invention, a silver halide photographic light-sensitive material having a high running stability of a developing solution and a fixing solution, giving an image with less sensitivity, residual color, and less development unevenness, and having low replenishment and high safety. Was obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) G03C 5/395 G03C 5/395 G03D 3/06 G03D 3/06 A

Claims (6)

[Claims] 1. A processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the developer contains reductones, and The fixing solution is a solution in which a granular solid development initiator and / or a granular solid fixing initiator is dissolved, and the developing replenisher and / or the fixing replenisher is a tablet-like solid developing replenisher and / or a tablet. A method for processing a silver halide photographic light-sensitive material, wherein the liquid is a solution in which a solid fixing replenisher is dissolved. 2. A processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the developer contains reductones, And / or a replenishing rate A and a replenishing solution amount B of a fixing replenisher to a processing tank in a relationship represented by the following formula (1). Formula (1) 0.001 ≦ A × B ≦ 0.015 (In the formula, A represents liter / min, and B represents liter / quarter unit.) 3. In a processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, the developing solution is supplied by dissolving a solid developer. A liquid developer, wherein the developer is a solid developer comprising a reductone as a developing agent, one solid part containing less than 0.5 mol / l of sulfite and another solid part containing carbonate, and A method for processing a silver halide photographic light-sensitive material, wherein each solid part is separately dissolved, mixed immediately before replenishment timing and supplied as a replenisher. 4. A processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the developing solution and the fixing solution are obtained by dissolving a solid developer. The developer is a solid developer comprising a reductone as a developing agent, one solid part containing less than 0.5 mol / l of sulfite and another solid part containing carbonate. The fixing agent is a solid fixing agent consisting of one solid part containing thiosulfate and another solid part containing aluminum sulfate,
And the developer, the solid part of each fixing agent is dissolved separately,
And a method of processing the silver halide photographic light-sensitive material, wherein the solution of each part is separately supplied directly to the developing tank and the fixing tank without mixing the solution in accordance with the processing timing of the light-sensitive material. 5. A processing method for developing, fixing and washing a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein a developing solution is supplied by dissolving a tablet-like solid processing agent. The developing solution contains reductones, and the conveying rollers of the conveying rack in the developing tank and / or the conveying rack in the fixing tank are all immersed in the liquid, All the rollers are out of liquid. 6. A processing method for developing, fixing and washing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the developer contains reductones and the halogen of the light-sensitive material is reduced. When the ratio of the tabular grains having an aspect ratio of 4 or more to the silver halide grains contained in the silver halide emulsion layer (expressed as the ratio of the projected area) is C, and the pH of the developer in the developing tank is D, Equation (2)
And the processing time is Dry to Dr
A method for processing a silver halide photographic light-sensitive material, wherein the processing time is 90 seconds or longer. Formula (2) When 50% ≦ C ≦ 100% 9.3 ≦ D ≦ 9.6 20% ≦ C <50% 9.6 <D ≦ 9.80% ≦ C <20% 9 .8 <D ≦ 10.0