JPH06236001A - Solid fixing agent for processing black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a fixing-hardening agent excellent in solubility in water, to improve working efficiency and further to suppress the production of water dross by incorporating at least one kind of aluminum chlorate and/or aluminum nutrate into a fixing agent and constituting the agent as a solid processing kit. CONSTITUTION:The aluminum chlorate and/or aluminum nitrate for the hardening agent of the fixing liquid are such compds. having water of crystallization and generally expressed as Al(ClO3)3.9H2O and Al(NO3)3.9H2O, respectively. The adding quantity is 0.05-1.00mol, and preferably 0.05-1.00mol per one liter of the solid fixing agent prepared as liquid. The aluminum chlorate and aluminum nitrate are used in a single or a combined form. These compd. have an effect for preventing the production of water dross in a washing tank. Thereby. it is preferable to determine the quantity of these compds. considering the quantity necessary to prevent the production of water dross in the washing tank and to obtain the effect to harden films.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing agent for a silver halide photographic light-sensitive material, and more particularly to a black-and-white silver halide photographic light-sensitive material processing material which has excellent solubility and has an action of preventing water stains in a washing tank. It relates to a solid fixing agent for use.

[0002]

2. Description of the Related Art Generally, a processing solution for silver halide photographic light-sensitive materials can be prepared by separating the components of the processing solution to prevent the reaction, and handing it to the user as a concentrated solution and simply diluting it. .

For example, a black-and-white fixing solution for X-rays is constituted and distributed as a concentrated solution of a kit containing a hardening agent and a kit containing a preservative. However, due to the formation of a precipitate of the concentrate during transportation and the packaging form. There are major problems such as soaring costs.

Therefore, in the case of a so-called powder treatment agent in which the constituent components of the treatment agent are solidified, the size and weight of the treatment agent can be greatly reduced as compared with the conventional liquid type agent, which is very advantageous in terms of transportation and storage. Therefore, various improvements such as lightening the load of liquid preparation work have been added, and it is still used.

A photographic fixing agent is a hard film for suppressing softening and swelling of a gelatin film during the processing of a light-sensitive material to improve the drying property or to reduce the occurrence of reticulation and scratches during the processing. As the agent, an aluminum compound such as potassium alum, chrome alum or aluminum sulfate is used. In particular, the fixing hardener is an indispensable material because the fixing process time is shortened at the time of rapid processing, the drying load is increased, and failures such as scratches at the time of conveyance are likely to occur.

The present inventor, while proceeding with the study of solidification of the above-mentioned aluminum sulfate compounds as a fixing agent, it takes a long time to prepare the liquid because the compound has poor water solubility, and as a result, the working efficiency is remarkably increased. The problem of decrease was found and new measures were needed.

Further, if the processing by the automatic processor is continuously performed, there is a problem that water stains are generated in the washing tank after the fixing of the automatic processor, which causes a trouble such as adhesion to the film, and therefore this improvement is also desired. It was rare.

[0008]

Therefore, a first object of the present invention is to provide a solid processing agent kit containing a hardening agent having properties as a hardening agent for a fixing agent and having good water solubility. Another object of the present invention is to provide a solid fixing agent having rapid processing suitability.

A second object of the present invention is to provide a solid fixing agent having an effect of suppressing scales generated in a washing tank of an automatic developing machine.

[0010]

The above problems have been solved by the present invention described below. That is, in the processing agent used for the automatic processor processing of the exposed black and white silver halide photographic light-sensitive material, the fixing processing agent contains at least one kind of aluminum chlorate and / or aluminum nitrate, and is used as a solid processing agent kit. And a solid fixing agent for processing a black-and-white silver halide photographic light-sensitive material. Hereinafter, the present invention will be described in detail.

The hardeners for fixers used in the present invention, aluminum chlorate and aluminum nitrate, are those obtained with water of crystallization and generally have the formulas Al (ClO ₃ ) ₃ .9H ₂ O and A.
l (NO ₃₎ represented by ₃ · 9H ₂ O. The addition amount may be 0.05 mol to 1.00 mol, and preferably 0.10 mol to 0.50 mol, relative to 1 liter when the solid fixing agent is prepared. The above aluminum chlorate and aluminum nitrate may be used alone or in combination.

If the amount added is too large, the film hardens too much, resulting in residual color contamination or residual silver on the film. Conversely, if the amount added is too small, rapid hardening results in poor film hardening, causing reticulation and scratches. Or, it may cause poor drying, which is not preferable.

It was unexpected that the above-mentioned aluminum chlorate and aluminum nitrate according to the present invention had the effect of preventing scales generated in the washing tank, and therefore the scales in the washing tank were It is preferable to determine the optimum amount from both aspects of the amount required to prevent the occurrence and the above hardening effect.

The fixing hardener of the present invention may be supplied after being coated and protected with an inert substance when granulating the solid fixing agent.
There is no deterioration of water solubility by coating. As a coating protection method, a solid polymer, a natural polymer, a water-soluble or acid-soluble polymer is dipped in an inert solvent for the constituents to form a film, or a coating solution is applied to the particle surface by a pan coating method. Examples include a method of forming a coating by spraying.

Regarding the packaging of the obtained solid processing agent, it is preferable that the packaging is obtained by sealing under a reduced pressure so that the pressure inside the packaging becomes lower than atmospheric pressure. The packaging material in this case is not particularly limited as long as it can withstand vacuum packaging, that is, a material having gas impermeability and does not react with the treating agent. Specifically, a metal foil such as aluminum whose surface is coated with a resin such as polyethylene, polypropylene, nylon, or vinylidene chloride and a thick resin material having pressure resistance are preferably used.

By making such a vacuum state, it is possible to eliminate the influence of oxygen and moisture on the photographic processing agent. In order to form a package, a solid processing agent obtained by granulating each component is supplied into the package, and then vacuum packaged according to a known method.

The solid of the solid processing agent according to the present invention means a solid in a general sense, and includes powder, granule tablet, sheet-like laminate, paste and the like, and may be a mixture thereof. In addition, two or more kinds may be encapsulated in the kit in a separate form in order to increase the preservability of the treating agent.

As a method for forming the solid processing agent used in the present invention, it is obtained by mixing existing processing agents for silver halide photographic light-sensitive materials and granulating.

In order to form a granulated product, it is preferable to use a commonly used granulating aid, and an additive such as crystallization water, a small amount of water, water-soluble or alkali- or acid-soluble polymer is used. For example, gelatin, pectin, polyacrylic acid, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, alginic acid, xanthate gum, gum arabic, tragacanth gum, karaya gum, carrageenan. , Methyl vinyl ether, maleic anhydride copolymer, polyoxyethylene ethyl ether, polyoxyethylene stearyl ether, and other polyoxyethylene alkyl ethers, polyoxyethylene noctylphenol ether, polyoxyethylene nonylphenol ether, and other polyoxyethylene alkylphenol ethers Or, as described in Japanese Patent Application No. 2-203165 by the same applicant as the present invention It can be used in combination with at least one binder selected from among soluble binder.

The stabilizer for the granulated solid fixing agent satisfies the following conditions.

1) It does not function as a photographic processing agent 2) It is not a constituent of the photographic processing agent 3) It does not affect the photographic performance when it is mixed in the processing solution as a soluble or insoluble substance. .

As a stabilizing method, a film may be formed by the same method as the above-mentioned coating protective layer. Examples of such an inert film-forming substance include gelatin, pectin, polyacrylic acid and salts thereof, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, Examples thereof include alginic acid, xanthate gum, gum arabic, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, glucose and sugars typified by glucose.

The granulation method applied to the solid fixing agent of the present invention includes rolling granulation method, extrusion granulation method, compression granulation method,
A crushing granulation method, a stirring granulation method, a spray dry method, a dissolution solidification method, etc. can be used, and an extrusion granulation method and a compression granulation method are particularly preferable.

The particle size and shape of the granulated product suitable for the present invention vary depending on the desired properties, but generally, the solubility desired for the photographic processing agent and the amount of residual powder in the waste packaging material after preparation or transportation are required. Considering the durability against breakage of the granulated product due to vibration at the time, in the case of granules, the spherical equivalent particle size may be about 0.5 mm to 50 mm, preferably about 1 mm to 15 mm, and the shape may be cylindrical, spherical or cubic. , Rectangular parallelepiped, and more preferably spherical or cylindrical.

Also in the case of tablets, a diameter of about 2 mm to 5 cm is preferable although it depends on the desired characteristics. Further, when it is desired to improve the solubility, a flat tablet having a reduced tablet thickness, a flat tablet having a further reduced central portion thickness, a hollow donut tablet and the like are also useful. On the contrary, the diameter may be further increased for the purpose of slow dissolution.

The surface condition (smoothness, porosity, etc.) may be changed to control the solubility.

Giving different solubilities to a plurality of granules,
It is also possible to take multiple shapes in order to match the solubilities of materials with different solubilities.

The photographic processing agent used in the present invention is not particularly limited, and any known photographic processing agent can be applied.

The fixing agent in the solid fixing agent of the present invention preferably contains thiosulfate. The thiosulfate is supplied as a solid, specifically as a salt of lithium, potassium, sodium or ammonium, but preferably supplied as sodium thiosulfate or ammonium thiosulfate and used by dissolving. More preferably, a fixing solution having a high fixing rate can be obtained by supplying it as an ammonium salt and dissolving it, but a sodium salt is preferable from the viewpoint of retention.

The concentration of thiosulfate as the fixing solution is preferably 0.1 to 5 mol / liter, more preferably 0.1.
5 to 2 mol / liter, more preferably 0.7 to 1.
It is 8 mol / liter. As other fixing agents, iodide salts and thiocyanates can also be used.

The fixing agent contains sulfite as a preservative,
The concentration of the sulfite is 0.2 mol / liter or less, preferably 0.1 mol / liter or less when the thiosulfate and the sulfite are dissolved and mixed in water. As sulfite, solid lithium, potassium, sodium,
An ammonium salt or the like is used, and it is used by dissolving it together with the solid thiosulfate salt. Further, the fixer preferably contains citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof, and examples of these salts include 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 potassium tartrate, 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.
One kind or a combination of two or more kinds can be used.

Of the above compounds, more preferred are citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof.

The above-mentioned citric acid, tartaric acid, malic acid, succinic acid, etc. are supplied as a solid and used by dissolving in an aqueous solvent. The preferred content in the fixing solution after dissolution is 0.05 mol / liter or more, and the most preferred content is 0.2-
It is 0.6 mol / liter. In addition to the above compounds, various acids, salts, chelating agents, surfactants, wetting agents,
Also, the above-mentioned fixing accelerator and the like can be contained.

Examples of the above-mentioned acid include salts of inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and boric acid, formic acid, propionic acid,
Examples thereof include organic acids such as oxalic acid and malic acid, and preferred are acids and salts such as boric acid and aminopolycarboxylic acid. The preferable addition amount is 0.5 to 20 g / liter.

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 sulfuric acid esterified products and sulfonated products, nonionic surfactants such as polyethylene glycol-based and ester-based surfactants, and amphoteric surfactants described in JP-A-57-6840. And so on.

Examples of the wetting agent include alkanolamine and alkylene glycol.

Examples of fixing accelerators include JP-A-45-35754
Nos. 58-122535 and 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, US Patents
Examples thereof include thioethers described in 4,126,459. As the developer used in the present invention, dihydroxybenzenes, 3-pyrazolidones, aminophenols, 1-allyl-3-aminopyrazolines, ascorbic acid, pyrazolones and the like as a developing agent, or a mixture thereof is used. To be

[0039] In addition, LFA Mason Photographic Proce
ssing Chemistry (Focal Press, 1966), 226-229
Pages, those described in JP-A-48-64933 and the like may be used. Preservatives (eg sulfite, bisulfite, etc.), buffers (eg carbonate, boric acid, alkanolamine, etc.), alkaline agents (eg carbonate, etc.), solubilizers ( Such as polyethylene glycols and their esters), pH adjusters (eg organic acids such as citric acid), sensitizers (eg quaternary ammonium salts), development accelerators, hardeners (eg glutaraldehyde etc.) Dialdehydes), a surfactant and the like can be contained.

The developer further contains an azole organic antifoggant (eg, indazole type, imidazole type, benzimidazole type, triazole type,
Benztriazo type, tetrazole type, thiadiazole type) may be used. Furthermore, sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate or the like may be used as a concealing agent for hiding calcium ions mixed in tap water used in the treatment liquid.

The solid body fixing agent according to the present invention is for X ray,
It can be applied to various black-and-white silver halide photographic light-sensitive materials such as printing plate-making, general black-and-white, laser light source, CRT photographing, duplication, and II indirect light-sensitive materials.

Next, a method of dissolving the solid fixing agent according to the present invention will be described. Dissolution may be done manually or mechanically as in the usual liquid preparation method, and the dissolution tank may be inside or outside the automatic processor, or directly in the processing tank without using the dissolution tank. You may. The treatment agent may be supplied manually or automatically by using a control means. There is no particular limitation as long as each component of the treatment agent does not scatter, for example, a method of wrapping a solid treatment agent with a water-soluble polymer film and directly feeding it, wrapping with a surface-treated paper such as polyethylene, There is a method to prevent the splattering and residue from being added to the tank.

Granules or tablets are preferable as the solid form in view of the solubility of the processing agent in water, but some photographic processing agents are poorly soluble in water, and these substances precipitate in the processing solution. In order to avoid this, potassium metabisulfite, for example, as described in US Pat.
A method of stably dissolving the treatment agent component using phthalic anhydride, maleic anhydride, benzoic acid, salicylic acid, phthalimide or the like may be used.

Further, a method of using boric anhydride described in US Pat. No. 2,606,118, a method of using boric anhydride and phthalic anhydride described in 2,666,702, a method of using metaboric acid described in 2,666,703, and a delta described in 2,666,716. A method using glucolactone, a method using phthalic anhydride, boric acid anhydride, metaboric acid hydrate stabilized with metaboric acid, etc. described in No. 2,685,513 are known, but these methods may be used. .

Next, a black-and-white silver halide photographic light-sensitive material in which the solid fixing agent of the present invention can be used will be described. As for the black and white silver halide photographic light-sensitive material, the silver halide emulsion may be any silver halide such as silver iodobromide, silver iodochloride, silver iodochlorobromide, etc. From the viewpoint, silver iodobromide is preferable.

These emulsions may be prepared by using a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof in the stage of physical ripening or grain preparation. Good.

The size of silver halide grains used in the emulsion is not limited, but those having a size of 0.05 to 2 μm are preferable.
It is preferable that at least 40% of the silver halide grains are substantially cubic or dodecahedral grains by weight or the number of grains, and the apex of the crystal surface is rounded.

The size distribution of silver halide grains may be monodisperse or polydisperse, but monodispersion is preferred. Here, the monodisperse is a dispersion system in which 95% of particles fall within a size of ± 40% of the number average particle diameter. The internal structure of the silver halide grains is arbitrary, but core / shell structures having different silver halide compositions are preferred.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method to remove soluble salts. For example, an aromatic hydrocarbon aldehyde containing a sulfo group described in JP-B-35-16086. Method using resin, or aggregating polymer agent described in JP-A-2-7037, Ex. G
A particularly preferable desalting method is a method using 3, G8 or the like.

The silver halide emulsion can use various photographic additives in the steps before and after physical ripening or chemical ripening, for example, Research Disclosure (RD) N.
o.17643 (December 1978), No. 18716 (November 1979) and No. 308119 (December 1989). The types of compounds shown in these three RDs and their locations are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 III Desensitizing dye 23 IV 998 B Dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 ~ 7 VI Whitening agent 24 V 998 V Surfactant 26 ~ 7 XI 650 Right 1005 ~ 6 XI Charge Inhibitor 27 XII 650 Right 1006 to 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008 to 9 XVI Binder 26 XXII 1009 to 4 XXII Support 28 XVII 1009 XVII Use for photosensitive materials Examples of the support that can be used include those described in RD-17643, page 28 and RD-308119, page 1009.

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

[0053]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Example 1 (Preparation of Film Sample) Preparation of Seed Emulsion 1 2 mol% of silver iodide having an average grain size of 0.3 μm was contained by a double jet method while controlling at 60 ° C., pH = 8 and pH = 2.0. Silver iodobromide monodisperse cubic grains were prepared. The obtained reaction solution was stored at 40 ° C in Kao Atlas Demol N.
After desalting with an aqueous solution and an aqueous solution of magnesium sulfate, a gelatin aqueous solution was added and redispersed to obtain a seed emulsion. Growth from Seed Emulsion 1 Grains were grown as follows using the above seed emulsion. First
The seed emulsion was dispersed in a gelatin aqueous solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. To this solution, an aqueous solution of ammoniacal silver nitrate ion and an aqueous solution of potassium bromide and potassium iodide were added by the double jet method. During the addition, pAg = 7.3 and pH were controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method. The pAg is kept at 9.0 and the pH is 9. up to 95% of the target particle size.
It was continuously changed from 0 to 8.0. After that, pAg is set to 11.0
Was adjusted to pH 8.0 and grown to a target particle size while maintaining pH at 8.0. Then, it was lowered to pH = 6.0 with acetic acid, and 5,5'-dichloro-9-
400 mg of ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride (sensitizing dye GD-1)
/ Mol AgX was added, desalting was performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then a gelatin solution was added and redispersed.

By this method, the average grain size is 0.40 μm and 0.65 in a tetrahedron with rounded vertices having an average silver iodide content of 2.0 mol.
μm, 1.00 μm, coefficient of variation (δ / r) 0.17, 0.1
Monodisperse silver iodobromide emulsions of 6 and 0.16 were prepared as (A), (B) and (C).

Seed Emulsion Preparation 0.2 with hydrogen peroxide treated gelatin at 40 ° C. with vigorous stirring.
A double jet method was used to add an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin to a 05N potassium bromide aqueous solution.
After the liquid temperature was lowered to ℃, 80 ml of ammonia water (28%) was added per mol of silver nitrate, and stirring was continued for 5 minutes.

After that, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous solution of Demol N manufactured by Kao Atlas and an aqueous solution of magnesium sulfate, and then an aqueous gelatin solution was added and redispersed. The resulting seed emulsion was spherical grains having an average grain size of 0.23 μm and a coefficient of variation of 0.28.

Growth from Seed Emulsion 2 Grains were grown as follows using the above seed emulsion. 75 ° C
Vigorously stirred with ossein gelatin and propyloxy-
An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added to the aqueous solution containing polyethyleneoxy-disuccinate-disodium salt by the double jet method. During this time
The pH was kept at 5.8 and the pH was kept at 9.0. After the addition was completed, the pH was adjusted to 6.0 and the sensitizing dye GD-1 was added at 400 mg / mol AgX. Further, the mixture was desalted at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas, and then an aqueous gelatin solution was added and redispersed.

By this method, a tabular silver iodobromide emulsion (D having a projected area diameter of 0.96 μm, a coefficient of variation of 0.25 and an aspect ratio (projected area diameter / grain thickness) of 4.0 with an average silver iodide content of 1.5 mol% (D ) Was prepared.

Preparation of Samples Each of the obtained emulsions (A), (B), (C) and (D) was at 55 ° C.
With the above-mentioned sensitizing dye GD-1, 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl)
Anhydrous of benzimidazolocarbocyanine sodium salt (sensitizing dye GD-2) (weight ratio of 200: 1) (A) 975 mg, (B) 600 mg, (C) per mol of silver halide Is 390 m
500 mg of g and (D) was added.

After 10 minutes, chloroauric acid, sodium thiosulfate,
Ammonium thiocyanate was added for chemical ripening.
15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3
3x a, 7-tetrazaindene per mol of silver halide
10 ^-2 mol was added and dispersed in an aqueous solution containing 70 g of gelatin.
Of the four ripened emulsions, (A), (B), and (C) were mixed at a weight ratio of 15:65:20 to form Emulsion-I, and (D) remained as an emulsion- II.

Additives as shown in JP-A-2-301744, page 95, line 16 to page 96, line 20 were added to each of Emulsion-I and Emulsion-II.

Further, 1.2 g of the dye emulsion dispersion shown below was added to prepare an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresylphosphate and 85 liters of ethyl acetate.
This is called an oil-based solvent.

On the other hand, 1.35 kg of anionic surfactant (AS)
A 9.3% gelatin aqueous solution containing is called an aqueous solvent. Next, put the oil-based solvent and the water-based solvent in the dispersion kettle and set the liquid temperature to 40
Dispersion was performed while maintaining the temperature at ℃.

[0066]

[Chemical 1]

The additives used in the protective layer are as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Coating liquid for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle diameter of 5.0 μm) 1.1 g Silicon dioxide particles (Matting agent having an area average particle size of 3.0 μm) 0.5 g Ludox AM (DuPont colloidal silica) 30 g Glyoxal 40% aqueous solution (hardener) 1.5 ml CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg

[0069]

[Chemical 2]

The emulsion layer is 2.0 g in terms of silver per side.
/ M ^2, the amount with gelatin 2.1 g / m ^2, the protective layer at a speed per minute 90m by two slide hopper type coater so that the 0.99 g / m ² as a weight with gelatin, glycidyl methacrylate and methyl acrylate A 175 μm polyethylene terephthalate base coated with an aqueous dispersion of a copolymer obtained by diluting a copolymer of butyl methacrylate and butyl methacrylate (50:10:40 wt%) to a concentration of 10 wt%. An emulsion layer and a protective layer were simultaneously coated on both sides and dried for 2 minutes and 15 seconds to obtain a film sample.

Preparation of Solid Processing Agent (Preparation of Solid Developer) From the developer formulations shown below, sodium carbonate as an alkali agent, potassium sulfite as a preservative,
Gelatin corresponding to 5% of the weight ratio was added to the constituent components excluding potassium metabisulfite, and the mixture was extruded to a particle size of 2.5 mm and granulated by a granulation method.

The obtained granules were placed in a rotary drum (pan) of a vacuum drying type pan coating apparatus VG (manufactured by Kikusui Seisakusho Co., Ltd.), and 10% polyvinyl alcohol solution was sprayed on the granules moving in the pan.

Similarly, 5% by weight of gelatin was added to a mixture of sodium carbonate, potassium sulfite and potassium metabisulfite, and the mixture was extruded to a particle size of 2.5 mm and then similarly sprayed with a 10% polyvinyl alcohol solution.

The obtained two kinds of granules were combined and vacuum packed by a conventional method to obtain a solid developer.

Developer formulation (1 liter of working solution) 1,4-dihydroxybenzene 15.0 g 1-phenyl-3-pyrazolidone 0.5 g potassium bromide 9.0 g hydroxyethylethylenediamine triacetate trisodium 1.0 g 5-methylbenzotriazole 0.160 g 4-methyl-1-phenyl 5-mercaptotetrazole 0.020g 5-nitroindazole 0.150g cyclodextrin 5.0g sodium carbonate 66g potassium sulfite 49.5g potassium metabisulfite 3.0g (preparation of solid fixing agent) Of these, 5% by weight of gelatin was added to the constituents other than tartaric acid and the fixing hardener of the present invention, and then granulated by the extrusion granulation method with a particle size of 2.5 mm. V
It was placed in a rotating drum (bread) of G (manufactured by Kikusui Seisakusho Co., Ltd.), and 10% polyvinyl alcohol solution was sprayed to coat the granules moving in the pan.

Next, 5% by weight of gelatin was added to the mixture of tartaric acid and the fixing hardener of the present invention, and the granules granulated by the extrusion granulation method having a particle size of 1.5 mm were processed into the above-mentioned vacuum drying type pan coating apparatus. The granules were placed in a rotating drum and tumbled in a pan and spray coated with 10% polyvinyl alcohol solution. These two types of granules were vacuum-packed by a conventional method to obtain a solid fixing agent. Fixing agent formulation (use liquid 1 liter formulation) AB Ammonium thiosulfate 170g-Sodium thiosulfate-180g Compound (A) -35g Anhydrous sodium sulfite 8g 8g Sodium citrate 2g 2g Sodium oxalate 2g 2g Boric acid 5g 5g Ethylenediaminetetraacetic acid disodium 0.5g 0.5g Tartaric acid 5g 5g Hardener for fixer Shown in Table 1

[0077]

[Chemical 3]

<Evaluation of Solubility> The evaluation of solubility in water is as follows.
The obtained granular sample was dissolved in 19 liters of a required amount of water with a finished formulation of 19 liters under stirring at room temperature, and the time until complete dissolution was measured to determine the solubility. If it takes more than 5 minutes to dissolve, manual dissolution and workability with an automatic liquid preparation machine (chemical mixer) will be poor and not practical, and the commercial value as a rapid processing agent will be impaired. .

The results obtained are shown in the table.

<Evaluation of Dryability> 100 sheets of sample films (quarter size) prepared in the above examples were exposed so that the transmission density after development was about 1.0, and the above solid developer and solid fixing were carried out. Roller type automatic processor SRX-502 (Konica Corporation) by the following processing steps using the processing solution prepared by dissolving the agent
100 sheets were continuously processed.

The developing solution was prepared by dissolving the solid developer in 16.5 liters of water and the fixing solution in 10 liters of water using a chemical mixer to prepare a processing solution, which was supplied to the developing tank and the fixing tank. The developing temperature is 35 ° C, the fixing temperature is 33 ° C, the washing water is 18 ° C, and 3.5 l / min is supplied.
At 0 ° C., the entire process step was processed in 45 second mode. The processing steps are shown below.

Processing step Processing temperature (° C) Processing time (sec) Replenishment amount Insertion-1.2 Development + crossover 35 14.6 33 ml / quarter fixing / crossover 33 8.2 63 ml / quarter washing + crossover 18 7.2 Squeeze 40 5.7 Dry 50 8.1 Total-45.0 320 ml of XD-SR-S (manufactured by Konica Corporation) was added as a starter to the initial supply of the developing treatment liquid. Last 10
Immediately after coming out of the drying rack for each of the samples, the dryness was evaluated by the feel of the bare hands according to the following evaluation criteria.

A: The texture is dry (sufficient dryness) B: It shines by reflection as if it was partially wet with water (insufficient dryness (lower limit of dryness)) C: Feels slightly wet Yes (insufficient dryness) D: Wet (insufficient dryness) <Evaluation of scale in the washing tank> SR of medical X-ray photosensitive material
G, SRH, SRL, SR-IC, SRD, LP633 (all manufactured by Konica Corporation) are treated in the order of 60%, 10%, 5%, 5%
% And 10% were used for running experiments. The average amount of processed light-sensitive material per day was about 200 sheets in quarter cut size conversion. The automatic processor and processing conditions used in this experiment are the same as above. After the treatment for one day was completed, all the washing water in the washing tank was drained, and this was repeated every day. The generation status of the obtained scale was visually evaluated and shown in the table.

<Evaluation of Residual Silver> The sample film prepared in the above example was left unexposed to 45 by using the above automatic developing machine.
Second processing was performed to obtain a sample for evaluating residual silver. The residual silver evaluation method is as follows: drop 2.6 drops 10 ^-3 mol / l aqueous solution of sodium sulfide as a residual silver evaluation liquid on the above evaluation film, leave it for 3 minutes, wipe the liquid well and keep it at room temperature. 15 under moist
Left for hours.

Then, a photo densitometer PDA-65 (Konica Corporation)
Manufactured) was used to measure the blue light transmission densities of the portion where the residual silver evaluation liquid was dropped and the portion where the residual silver evaluation liquid was not dropped, and the difference was used as a measure of the residual silver. The larger the value (difference) in the table, the higher the residual silver concentration in the processed film.

The results obtained above are shown in Tables 1 and 2.

[0087]

[Table 1]

[0088]

[Table 2]

As is clear from the table, the solid fixing agent using the fixing hardener of the present invention is excellent in solubility in water, and therefore the working efficiency is remarkably improved. Further, the drying property was not deteriorated even by rapid processing, and the film after processing had a small amount of residual silver and had sufficient fixing performance. Further, according to the present invention, it can be seen that the generation of scale is remarkably suppressed. As can be seen from the table, the use amount of the fixing hardener according to the present invention is largely related to the generation of scale and residual silver, and shows that the addition amount range of the present invention is excellent.

[0090]

The solid fixing agent according to the present invention can significantly improve the working efficiency because the fixing hardener has excellent water solubility, and the deterioration of the drying property even after the rapid processing and the residual silver in the film after the processing. A fixing agent having a small and sufficient fixing performance was obtained. Furthermore, according to the present invention, the generation of scale can be significantly suppressed.

Claims (1)

[Claims] 1. A processing agent used for automatic processor processing of exposed black-and-white silver halide photographic light-sensitive material, wherein the fixing processing agent contains at least one kind of aluminum chlorate and / or aluminum nitrate, and solid processing A solid fixing agent for processing a black-and-white silver halide photographic light-sensitive material, which is configured as an agent kit.