JPH02197836A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the deposition of white powder on the transfer rock between fixing and washing in the method for processing a silver halide photographic sensitive material to be processed in order of developing, fixing, washing and drying by executing the above-mentioned fixing processing by a fixer contg. polyhydric alcohol having at least >=2 hydroxyl groups. CONSTITUTION:The polyhydric alcohol to be used the fixer for a fixing tank 2 is preferably the alcohol which has 2 to 12 hydroxyl groups and 2 to 20C and in which the hydroxyl group and the hydroxyl group are not conjugated with a conjugation chain, i.e. which cannot write the oxidized type. The more specific examples of the above-mentioned polyhydric alcohol include 2, 3, 3, 4-tetramethyl-2, 4-pentamediol, 1, 3-propanediol, cis-1, 2-cyclopentanediol, etc. The above-mentioned polyhydric alcohol is added in the fixer at a ratio of preferably 0.05 to 100g/l, more preferably 0.5 to 80g/l.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide photographic materials.

[Background of the invention]

In order to shorten processing time and handle large quantities of exposed photographic material, automatic processors are used to develop, fix, wash, and dry exposed photographic materials. In an automatic processing machine, photographic materials are guided from one processing station to another, and contamination due to the diffusion of various components from the photographic materials and loss of developer activity are prevented by continuous liquid replenishment and periodic replenishment. The problem was solved by introducing a new processing solution.

However, it has been found that when the process is repeated, white powder adheres to the transfer roll between the fixing stationary unit and the washing stationary unit, making it difficult to convey the photographic material smoothly.

This is thought to be due to the fact that during film processing, the fixing treatment liquid that has soaked into the film adheres to the transfer roll when the film passes through the transfer roll, and components in the liquid decompose or precipitate on the transfer roll.

Furthermore, since white powder deposited on the transfer roll is difficult to wash off, maintenance of the automatic developing machine becomes difficult. Furthermore, white powder is transferred to the photographic material, lowering 111F,
When the photographic material is medical X-ray film, there are also drawbacks such as the risk of misdiagnosis.

This problem is especially serious when rapid processing is performed in an automatic processing machine where the amount of water for washing is limited.

(Disclosure of the Invention) An object of the present invention is to prevent white powder from being deposited on the fixing-washing rack during the processing of silver halide photographic materials in which processing is performed in the order of development, fixation, water washing, and drying. It is.

The object of the present invention is to provide a method for processing a silver halide photographic material in which development, fixing, washing, and drying are performed in the order, in which the fixing process uses a fixing solution containing a polyhydric alcohol having at least two or more hydroxyl groups. This is achieved by a method for processing a silver halide photographic material, which is characterized in that it is carried out.

In addition, as the above-mentioned polyhydric alcohol, for example, 2 hydroxyl groups are used.
~! An alcohol having 2 to 20 carbon atoms, and in which the hydroxyl groups are not conjugated with each other through a conjugated chain, that is, an oxidized form cannot be formed, is preferable.

Hereinafter, one example of a preferred specific example of the polyhydric alcohol will be given, but the compound is not limited to the following examples.

2.3.3.4-tetramethyl-2,4-bentanediol, 2.2-dimethyl-1,3-propanediol,
2,2-dimethyl-1,3-bentanediol, 2,2
．． 4-trimethyl-1,3-bentanediol, 2.5
-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,6-hexanediol, l, 8
-octanediol, 1.9-nonanediol, 1.
10-decanediol, 1.11-undecanediol, 1゜12-dodecanediol, 1.13-)lysocanediol, 1.14-tetradecanediol, i, t2
-Octadecanediol! , 18-octadecanediol, cis-2,5-dimethyl-hexene-2°5-diol, trans-2,5-dimethyl-3-hexene-
2,5-diol, 2-butyne-1゜4-diol, 2
．． 5-dimethyl-3-hexyne-2,5-diol, 2
．． 4-hexadiyne-1゜6-diol, 26-octadiyne-1,8-diol, 2-methyl-2,3,4-
butanetriol, 2,3.4-hexanetriol,
2゜4-dimethyl-23,4-pentanetriol, 2
．． 4-dimethyl-2,3,4-hexanetriol, pentamethylglycerin, 2-methyl-2-oxymethyl-1,3-propanediol, 2-isopropyl-2-
Oxymethyl-1,3-propanediol, 2,2-dihydroxymethyl-1-butanol, erythritol,
D-triit, L-traint, rac-)reit, pentaerythritol, 1.2,3.4-pentanetetrol, 2.3,4.5-hexanetetrol, 2
．． 5-dimethyl-2,3,4,5-hexanetetrol, 1,2.5.6-hexanetetrol, 1.3,4.
5-hexanetetrol, 1,6-(erythro-3,4
)-hexanetetrol, 3-hexene-1,2,5,
6-tetrol, 3-hexyne-1,2,5,6-tetrol, adonitol, D-arabitol, L-arabitol, rac-arabitol, xylitol, L-mannitol, dulcitol, diethylene glycol, 1
．． 4-butanediol, 2.2-dimethyl-13-propanediol, 1,2.6-hexanetriol, glycerin, 2.4-dimethyl-2°4-bentanediol, ethylene glycol, 1°2-propanediol, 1
．． Examples include 3-propanediol, cls-1+ 2-cyclobentanediol, and the like.

The polyhydric alcohol as mentioned above is 0% in the fixing solution.
．． 05~100g/'J! , more preferably 0.5-8
It is desirable that it is added at a rate of 0 g/Il.

The silver halide emulsion of the light-sensitive material used in the present invention includes silver bromide, silver iodobromide, silver chloride, silver chlorobromide,
Any grains commonly used in silver halide emulsions, such as silver chloroiodobromide, can be used, and the silver halide grains may be those obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform halide mu composition distribution within the grain, or may be core/shell grains in which the halide sI composition differs between the grain interior and the surface layer, with the latent image mainly on the surface layer. It may be a particle that is formed inside the particle, or it may be a particle that is formed mainly inside the particle.

Any shape of the halogenated root particles used in the present invention can be used. One preferred example is (10
0) plane as a crystal surface. Also, U.S. Patent No. 4,183,756, JP-A-55-26589
Specification of issue, etc., The Journal of Photographic Science (J, Photogr, 5cO41,
8 by the method described in the literature such as 39 (1973).
Particles having shapes such as a face, tetradecahedron, and dodecahedron can also be prepared and used. Furthermore, particles having twin planes may be used.

The silver halide grains used in the present invention may be of a single shape or may be a mixture of grains of various shapes.

Further, although grains having any grain size distribution may be used, monodisperse emulsions are preferred in the present invention.As monodisperse silver halide grains in monodisperse emulsions, the average grain size r
It is preferable that the silver halide superposition contained within a grain size range of ±20% around , is 60% or more of the total silver halide grain weight, particularly preferably 70% or more, and still more preferably 80% or more. It is.

Photosensitive silver halide emulsions are made without chemical sensitization.
Although the so-called Prlmitlve emulsion can be used as is, it is usually chemically sensitized.

For chemical sensitization, Glafkldes or Zel i
Kw + an et al.'s book, or H. Fr1eser Akebono D.
ie Gruntllagender Photog
raphlschen Prozesse wit
Silberhalogenlden, Ak
ademlsche V@rlagsgesellsc
Haft, 1968 can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidisulfinic acid, silane compounds, etc. can be used. For noble metal sensitization, in addition to total complex salts, the periodic table of platinum, iridium, palladium, etc.
After the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,3
+3a-7-chitrazaindene, 5-mercapto-1-
Various stabilizers can also be used, including phenyltetrazole, -mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as dioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The halogenated root particles used in the present invention are cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts, in the process of particle formation and/or growth. Metal ions can be added and contained inside the particles and/or on the surface of the particles.

In the silver halide photographic light-sensitive material used in the present invention, the photographic emulsion has a sensitizing dye that emits relatively long-wavelength blue light.
Dyes used that may be spectrally sensitized to green or infrared light include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemin cyanine dyes, styryl dyes and hemioxonol dyes. etc.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. especially,
It is advantageous to use dye concentrations that do not substantially reduce the inherent sensitivity of the silver halide emulsion. from about 1.0X10-" to about 3X10-" of sensitizing dye per mole of silver halide.
The sensitizing dyes advantageously used in the present invention are preferably used in concentrations of about 5X10-' to 1.5 Specifically, the following can be mentioned, for example. As a sensitizing dye used for blue-sensitive silver halide milk scraps, for example, West German Patent No. 92
No. 9080, U.S. Patent No. 3,672.897,
No. 694,217, No. 4,025.349, No. 4,0
46,572, British Patent No. 1.242.588, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 52-24844, Japanese Patent Publication No. 48-73137, Japanese Patent Publication No. 61-172140, etc. Examples of sensitizing dyes used in green-sensitive silver halide emulsions include U.S. Patent No. 2,945,763, British Patent No. 505,979,
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent Publication No. 48-42172, which are further used in red-sensitive and infrared-sensitive silver halide emulsions. As the sensitizing dye, for example, U.S. Pat. No. 2.454.629,
Typical examples include cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in Japanese Patent Publication No. 2,776.280, Japanese Patent Publication No. 49-17725, Japanese Patent Application Publication No. 61-29836, Japanese Patent Application Publication No. 60-80841, etc. It can be mentioned as follows.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is U.S. Patent No. 2.
No. 688.545, Special Publication No. 43-4936, No. 53-
No. 12375, JP-A-52-110618, JP-A No. 52-
109925 etc.

Further, in the silver halide photographic emulsion used in the present invention, at least 50% or more of the amino groups of the gelatin molecules are acyl,
Desalting may be carried out using modified gelatin substituted with carbamoyl, sulfonyl, thiocarbamoyl, alkyl and/or aryl groups in an amount of 5 to 70%, preferably 10 to 50% of the total amount of gelatin in the emulsion layer.

Further, in the silver halide photographic material used in the present invention, a hydrazine compound or a tetrazolium compound may be added in order to obtain a high-contrast image.

Specific examples of hydrazine compounds are described in U.S. Patent No. 4.272.
No. 606, No. 4,311,781, No. 4.478.9
No. 28 and Japanese Unexamined Patent Publication No. 62-210458, these can be used.

The amount of the hydrazine compound added is preferably 104 to 5 x 10-'' mol/1 mol, more preferably to-' to 2
xlO-'' mole/IPj1 mole.

Specific examples of tetrazolium compounds are disclosed in JP-A-62-112
No. 53, these compounds can be used.

The tetrazolium compound is 1X10-' mol to 10 mol per mol of silver halide contained in the light-sensitive material of the present invention,
In particular, it is preferable to use the amount in the range of 2×10 −′ mol to 2×10 −′ mol.

The hydrazine compound and the tetrazolium compound are added to the silver halide emulsion layer and/or the non-photosensitive fl (II aqueous colloid layer) on the side of the silver halide emulsion layer on the support.
However, it is preferably the silver halide emulsion layer and/or its lower layer.

Gelatin is usually used as a binding or protective colloid for the silver halide emulsion used in the present invention, but in addition to gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, Single or copolymerized cellulose derivatives such as hydroxyethyl cellulose and carboxymethyl cellulose, agar, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyN vinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. In the silver halide photographic light-sensitive material used in the present invention, a variety of synthetic hydrophilic polymeric substances can be used, such as filter dyes in the hydrophilic colloid layer, irradiation prevention,
Harareshiran prevention and other i! A water-soluble dye may be included for l'- purposes.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.

In the silver halide photographic light-sensitive material used in the present invention, when the hydrophilic colloid layer contains a dye, a cotton absorbent material, etc., they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. That is, many compounds known as stabilizers can be added, such as azoles, heterocyclic mercapto compounds, thioketo compounds, azaindenes, benzenethiosulfonic acids, benzenesulfinic acids, and the like.

An example of a compound that can be used is by Mees, The
Theory of Photographic P
rocess, 3rd edition, 1 bss, citing the original literature.

For more detailed examples of these and how to use them, see, for example, U.S. Pat.
The descriptions in the specifications of No. 2.947 and No. 4,021,248 or Japanese Patent Publication No. 52-28660 are referred to.

In addition, silver halide photographic light-sensitive materials contain U.S. Pat. No. 3,411,911 and U.S. Pat.
and Japanese Patent Publication No. 45-5331.

In addition, the silver halide photographic material may contain the following various additives, such as thickeners or plasticizers, such as those described in U.S. Pat.
．． Specification No. 960.404, Japanese Patent Publication No. 43-4939, West German Application Publication No. 1, 904, Specification 604, Japanese Patent Application Publication No. 63715-1982, Japanese Patent Publication No. 15462-1983
Belgian Patent No. 762,833, U.S. Patent No. 3.767.410, Belgian Patent No. 558.1
Substances described in each specification of No. 43, such as styrene-sodium maleate copolymer, dextran sulfate, etc., various hardening agents such as aldehyde type, and ultraviolet absorbers, such as U.S. Pat. No. 3,253.921 , and the compounds described in the specifications of British Patent No. 1.309, 349.

Furthermore, as coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials, British Patent No. 548.532, Special Anionic, cationic, nonionic or amphoteric compounds described in JP-A-48-101118 etc. can be used, and among these, anionic surfactants having a sulfonic group, such as succinic acid Preferred are ester sulfonates, alkylnaphthalene sulfonates, alkylbenzenesulfonates, and the like.

In addition, as an antistatic agent, Japanese Patent Publication No. 46-24159, Japanese Patent Application Laid-Open No. 48-89979, and U.S. Patent No. 2.88
There are compounds described in the specification of No. 2,157 and JP-A-47-33627.

In the light-sensitive material used in the present invention, the constituent layers include matting agents, such as inorganic particles such as silica described in Swiss Patent No. 330.158, and U.S. Pat. No. 2.322.0.
Organic particles such as starch described in Japanese Patent Publication No. 44-3643 and polyvinyl alcohol described in Japanese Patent Publication No. 44-3643 can be included.

The photosensitive material used in the present invention includes a higher aliphatic alcohol ester, casein, and U.S. Patent No. 3.042.5.
Dispersions of liquid paraffin, which may contain slipping agents such as silicon compounds, as described in No. 22, 3.489.567, can also be used for this purpose.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure No. 176@Ite*
17643 (December 1975) and 187@It
ea 18716 (November 1979).

In a silver halide photographic light-sensitive material, for example, an emulsion layer and other layers can be constructed by coating one or both sides of a flexible support commonly used in photographic light-sensitive materials.

Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.
Baryta layer or α-olefin polymer (e.g. polyethylene, polypropylene, ethylene/butene copolymer)
paper coated or laminated with etc. The support is
The surface of these supports, which may be colored with dyes or pigments or may be made black for the purpose of blocking light, is immediately subjected to an undercoating treatment to improve adhesion with the emulsion layer and the like. The undercoating treatment is as per JP-A-52-104913 and JP-A-59-189.
Publication No. 49, Publication No. 59-19940, Publication No. 59-19
The treatment described in Japanese Patent No. 941 is preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In silver halide photographic materials, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For application, dip application method,
A roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

Next, the development, fixing, washing, and drying steps in the present invention will be described.

The developing agents used in the black and white developer used in the present invention include the following.

IO-(CR-CI) Representative examples of n-OH type developing agents include hydroquinone, as well as catechol, hyrocarol and its derivatives, ascorbic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, ．．
3-dichlorohydroquinone, 2.5-dichlorohydroquinone, 2.3-dibromohydroquinone, 2.5-
Examples include dimethylhydroquinone.

Also, as )IQ-(CO-C1l)n-N1m type developing agents, ortho and rose aminophenols are representative, N-methyl-ρ-aminophenol, and 4 others.
-There are also aminophenols, etc.

Examples of HxN-(C)l-cH) n-N11t type developing agents include 4-amino-2-methyl-N, N-diethylaniline, and p-phenylenediamine.

Examples of the heterocyclic type developer include l-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone,! -phenyl-4,4-dihydroxymethyl-3-pyrazolidone and the like.

The above developing agents may be used alone or in combination of two or more.

The developing agent is preferably used in an amount of usually 0.01 mol/i to 1.2 mol/l.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfite is 0.1 mol/72 or more, especially 0.3 mol/! The above is preferable, and the upper limit is preferably up to 2.5 mol/l.

The pH of the developer used in the present invention is preferably in the range of 9 to 13, more preferably in the range of 9.5 to 12.

Alkaline agents used for setting pn include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and p-potassium phosphate.
Contains njIII agents.

JP-A-61-28708 (borates), JP-A-60-
No. 93439 (e.g. sucrose, acetoxime,
5-sulfosalcylic acid), phosphates, carbonates, and the like may also be used.

In addition to the above components, additives include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol = 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulunic acid sodium salt, etc. It may contain antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, benztriazole compounds such as 5-methylbenztriazole, and if necessary, hardeners such as formaldehyde and glutaraldehyde. , color improver, surfactant, antifoaming agent, water softener, JP-A-56-1
It may also contain the amino compounds described in No. 06244.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

In the developer of the present invention, amine compounds such as alkanolamines described in JP-A-56-106244 can be used.

This 4hL, p, a, written by Meson [Photographic
``Brosecin Chemistry'', published by Focal Press (
1966), pp. 226-229, U.S. Patent No. 2,19
No. 3.015, No. 2,592.364, Japanese Unexamined Patent Publication No. 1973-
64933 and the like may be used.

Development processing temperature and time are approximately 25°C to approximately 50°C and 5 to 50°C.
It can be carried out for 90 seconds, preferably 8 seconds to 1 minute at 30°C to 40°C.

In the present invention, the development processing time refers to the time from when the photosensitive material to be processed is immersed in the developing tank solution of an automatic processing machine until it is immersed in the next fixing solution.

The constant @ solution is an aqueous solution containing thiosulfate, preferably p
H3.8 or more, more preferably 4.0 to 5.5.

Examples of fixing agents include sodium thiosulfate and ammonium thiosulfate, but those containing periosulfate ions and ammonium ions as essential components are preferred, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed.

The amount of fixing agent used can be changed as appropriate, and is generally about 0.
．． 1 to about 6 mol/l.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride,
Examples include ammonium sulfate and potassium alum.

In the fixing solution used in the present invention, it is preferable to use tartaric acid, citric acid, malic acid, succinic acid or a derivative thereof, and aminopolycarboxylic acid, aminopolyphosphonic acid or a salt thereof alone or in combination. The effect of the present invention can be further enhanced by adding 0.004 mol or more of the compound per 1ffi of the fixer.

Specifically, citric acid, isocitric acid, malic acid, acetic acid and their photoisomers, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, lithium tartrate, potassium tartrate, sodium tartrate. , potassium sodium tartrate, lithium hydrogen tartrate, lithium potassium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, ammonium hydrogen tartrate, magnesium hydrogen tartrate, potassium boron tartrate, ammonium tartrate, ammonium ion tartrate, aluminum potassium tartrate, antimonyl potassium tartrate, Lithium, potassium, sodium, represented by antimonyl sodium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc.
Ammonium salts, etc., and specific examples of aminopolycarboxylic acids and aminopolyphosphonic acids include JP-A No. 63-182
A-1 to A-12 in the 1st O page of Publication No. 650
There are compounds such as.

Preservatives (sulfite, bisulfite) may be added to the fixer if desired.
, pH buffer (acetic acid, nitric acid), pH! Ml conditioner (e.g. sulfuric acid), chelating agent capable of hard water softening, and patent application 1980-
213562 may be included. The amount of preservative used can be changed as appropriate, and is preferably about 0.
05~I mol/l.

Fixing temperature and time are approximately 20°C to approximately 50°C, 6 seconds to 90°C.
It can be carried out in seconds, and more preferably at 30° C. to 40° C. for 6 seconds to 60 seconds. The fixing processing time is defined as the time from when the photosensitive material to be processed is immersed in the fixing tank solution to the next washing tank solution (
This refers to the time it takes to reach a stable temperature.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

Any method known in the art can be applied to the water washing or stabilization treatment, and water containing lll1h additives known in the art can also be used as the washing water or stabilizing liquid. Photosensitive materials can be washed with anti-mold water or used as a stabilizing solution! Not only is it possible to save water by reducing the replenishment amount to less than 31 per -8, but it also eliminates the need for piping for installing an automatic processor, making it possible to further reduce the number of stock tanks.

When washing with a small amount of water, a patent application from 1983 to 1729
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water depending on the treatment, is disclosed in Japanese Patent Application Laid-Open No. 60-23
As described in Japanese Patent No. 5113, it can also be used in a processing liquid having a fixing ability, which is a pre-processing step.

Furthermore, antibacterial agents, anti-inflammatory agents, surfactants, etc. described in JP-A No. 57-8542 and the like can also be used in combination.

Furthermore, in the washing bath, R, T, Kreia+an @J,
Iaage+Tech 10. (6) 242 (1984
), etc., patent application No. 1983
-51396, etc. are used as antibacterial agents (Mi
It can also be used in combination as crobiocide.

It is preferable that the water treated with anti-mildew measures and stored in a water stock tank be used both as dilution water for the undiluted solution of processing solutions such as the developer and fixer, and also as washing water, since it takes up less space. The dilution water treated with anti-mold and the washing water (or stabilizing liquid) can be stored separately in separate tanks, or only one of them can be taken directly from the tap.

When stored separately in separate tanks, the washing water (or stabilizing bath) can contain various additives in addition to applying anti-mildew measures as in the present invention.

For example, a chelate compound having a log K value of chelate stability with aluminum of 10 or more may be included. If the fixer contains an aluminum compound as a hardening agent, these compounds may be used to prevent scuttling in washing water. It is valid.

Specific examples of chelating agents include ethylenediaminetetraacetic acid (IogK 16.1. The same applies hereinafter), cyclohexanediaminetetraacetic acid (17,6), diaminopropanoltetraacetic acid (13,8), diethylenetriaminepentaacetic acid (18
,4) ,)lyethylenetetraminehexaacetic acid (19,7)
etc., and their sodium salts, potassium salts, and ammonium salts, and the amount added is preferably 0.01 to 10 g.
/J! , more preferably 0.1 to 5 g/l.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing water droplet unevenness. As the surfactant, any of the cationic type, negative ionic type, nonionic type, and amphoteric type may be used. Specific examples of surfactants include "Surfactant Handbook" published by Kogaku Tosho Co., Ltd. There are compounds listed in ``.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image.For example, to adjust the membrane pH (for example, pl(
3-8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples are aldehydes such as formalin, etc.] and aldehydes such as formalin.Other examples include chelating agents, bactericidal agents (thiazole-based, isothiazole-based, halogenated phenols, sulfanilamide, benzotriazole, etc.), and surfactants. , optical brighteners, hardeners, and the like may be used, and two or more compounds for the same or different purposes may be used in combination.

Also, depH the processing solution! ! ! It is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a stabilizer in order to improve image storage stability.

The water washing or stabilization bath temperature and time by the above method are 0°C ~
The washing time is preferably from 6 seconds to 90 seconds at 50 DEG C. The washing time is the time during which the photosensitive material to be processed is immersed in the water washing tank liquid. In addition, the drying time in the present invention refers to the drying time
The automatic processing machine is equipped with a drying zone where hot air of 5° C. to 100° C., preferably 40° C. to 80° C., is blown.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, that is, by using a squeeze roller method. Drying is carried out at a temperature of about 40°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but it is usually about 5 seconds to 90 seconds, more preferably at 40°C.
~80°C for about 5 seconds to 60 seconds.

Incidentally, the total processing time of so-called dry to dry processing from development, fixing, washing and drying is within 55 minutes, preferably within 4 minutes, and more preferably within 100 seconds.

(Examples) Examples of the present invention will be described in detail below.It goes without saying that the present invention is not limited to the examples described below.

Example 1 [Preparation of film] An iodine film containing 2.0 mol% of silver iodide with an average grain size of 0.28 # A silver bromide monodisperse cubic emulsion was obtained.

Then, a part of this emulsion was cored and used for growth as follows. That is, an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added to the solution containing the core particles and gelatin at 40°C, 24 g 9.0, and ρ 119.0 using a double jet method, and 30 mol of silver iodide was added. 1st cover including %! ! ! formed a layer. And further pAg・9.
0, pH 9.0, ammoniacal silver nitrate solution and potassium bromide solution were added by double jet method to form a second coating layer of pure silver bromide, and a cubic monolayer with an average particle size of 0°63 μm was formed. A dispersed silver iodobromide emulsion was prepared.

After removing excess salt by coagulation-precipitation method, 8 x 10-' mol of chlorauric acid, 7 x 10-' mol of sodium thiosulfate, and 7 x 10-' mol of ammonium thiocyanate were added per 111 mol of halide to optimally dissolve gold and sulfur. Sensitization was carried out, and the following sensitizing dyes (A) and (B) and 1 x to' mol of potassium iodide (1 mol^gX) were added to optimally spectral sensitize.

Sensitizing dye (A) After spectral sensitization, 90 g of lime-treated ossein gelatin per mole of silver halide as an emulsion layer additive, [-butyl-catechol 40 (lag, 4-hydroxy6methyl-L3.3a, ?-) Tetrazaindene 3g 1 polyvinylpyrrolidone (molecular weight 10,000) 1.Ou, styrene-maleic anhydride copolymer 2.5g, )limethylolpropane 10g, diethylene glycol 5g, nitrophenyl-triphenylphosphonium chloride 59mg, t, 4 g of ammonium 3-dihydroxybenzene-4-sulfonate 15 mg of sodium 2-mercaptobenzimidazole-5-sulfonate, sensitizing dye
(B) υ■ 1.1-dimethylol-1-brome-! -10-g of ditromethane and the like were added to prepare an emulsion layer coating solution.

In addition, the following compounds can be added as protective layer additives to protect! I
! A membrane layer coating solution was prepared. That is, per gram of gelatin, CaF*SOs plus CqF+, 0(CIIxCIItO)+. Cl1IC
I+! 51F on 3 wheels of 118 sodium chloride! 3mg (n is a mixture of 2 to 5) Formalin 201g, Glyoxal 30ml 1゜ Matting agent 7+wg consisting of polymethyl methacrylate with an average particle size of 5μm, 70mg of colloidal silica from the city of 0.013μm in average particle size
etc. were added.

The above-mentioned emulsion 115 coating solution was coated with this protective film J? ! 5 Coating solution and a 180 μ thick undercoat treatment agent were coated on both sides of a blue-colored polyethylene terephthalate support with a slide hopper coating machine, with an amount of silver of 2.4 g/m'' on one side and gelatin of 3.8 g on one side. /1%t to obtain Film 1.

Next, in lt of water, 30 g of gelatin, 10 g of potassium bromide
．． 5g, thioether (IO(CHt)zs(C1lt)zs(Cllt)t
s(CHzhOI() 0.5 wt% aqueous solution (10-l) was added and dissolved in a solution kept at 65°C (pAg=9.
1. A mixed solution of 0.88 mol of nitric acid 11 solution 30@2 and 0.88 mol of potassium iodide and potassium bromide (molar ratio 96.5:3.5>30) was brought to pH=6.5) with stirring.
After simultaneous addition of vI11 for 15 seconds, a 1 molar mixed solution 6 consisting of 600 ml of 1 molar nitric acid II solution and potassium bromide and potassium iodide in a molar ratio of 96.5:3.5 was added.
00+w l over 70 minutes to prepare a tabular silver iodobromide emulsion with an average grain size of 1.18 μ-, a thickness of 0.15 #si, and a silver iodide content of 3.5%. did.

Then, after removing the excess salt by a coagulation-sedimentation method, these emulsions were treated in the same manner as the above film 1 to obtain film 2.

[Preparation of fixer]

Next, a fixer solution having the following composition was prepared.

[Fixer A]

Ammonium thiosulfate 150g Sodium sulfite 15g EDTA 0.1g Citric acid 2g Boric acid
7g sodium acetate
15g glacial acetic acid
68 aluminum sulfate 10
g sulfuric acid 12 with 5 g water
shall be. However, use acetic acid to adjust pn to 4.20.

Fixers B-H were also prepared with the same formulation as this fixer A and the following polyhydric alcohols or additives added.

Fixer B CHs (C1 mountain→ko> (0(JlsC
IIg) +5-OH2gs Cn-butyl alcohol 2g〃 D Diethylene glycol
3.58 E Glycerin 8.2
8-F2,5-hexanediol 17.2g〃G2
-Methyl-2.3.4-butanetriol 23.5g-Hl, 2.6
-Hexandriol 35.7g (white powder stain test) X-ray film automatic processor KX-50 manufactured by Konica Corporation
0 was used, and Konica Corporation's χTo90 was used as the developer.
Using the above film 1 and film 2 and fixer A
A running treatment was performed using a combination of -H, and the state of white powder stains on the wading rack after fixing and washing with water was evaluated.

In the running process, Film 1 and Film 2 were each exposed to a density of 1.1, and 100 quarter-sized sheets were cut each day for one week. continued.

Further, processing conditions using an automatic developing machine were set as follows.

Temperature Replenishment amount Development 35℃ 33cc/4-cut 1 sheet fixing
33℃ 63cc/P! 1 cut, washed with water
Dry at 20°C, set to 1.51/++in.
The state of white powder stains treated at 45° C. for 90 seconds was evaluated in terms of the following three items.

■ Precipitation condition of white powder One week after starting running, fixation in the mouth - Check the condition of the wading rack after washing with water? It was worth 52 if.

Evaluation, A: There is almost no precipitation of white powder on the Watari rack.

C: White powder was precipitated on a part of the Watarirak.

E: White powder was precipitated all over the Watari rack.

and B and D were each in an intermediate state.

■ Transferability of white powder to film 1 after starting running! ! After one hour had elapsed, the transfer of white powder stains to the running film was visually evaluated.

Evaluation, A: There is almost no transfer to the film.

C: There is some transfer to the film, but it is not noticeable.

E: Transfer to the film is clearly visible.

and B and D were each in an intermediate state.

(2) Cleanability of White Powder One week after the start of running, the ease with which white powder stains were washed off from the fixing-washing Watarirak was evaluated.

Evaluation, A: Just sprinkle water on it and it will come off right away. C: It will come off if you pour water on it and rub it with a sponge.

E: It almost never falls.

and B and D were each in an intermediate state.

The results are shown in Table-1.

(Margin below) table (Margin below) The effects of the present invention are clear from the results shown in Table 1.

[Example-2] Running film was manufactured by Konica Corporation IJ! Mc-3R
Evaluations were conducted in the same manner as in Example 1, using the automatic processor 5RX-501 manufactured by Konica Corporation and the developer XII-3R manufactured by Konica Corporation. However, the running treatment conditions were as follows.

Temperature Replenishment amount Development 35℃ 33cc/4-cut 1 sheet fixing
33℃ 63cc/1 piece cut into 4 pieces washed with water 20
℃ 1.57! /Ill set to dry 45
The results of processing for 4S seconds at °C were the same as in Example-1, and the fixers D to H of the present invention were
It has been found that this method has a remarkable effect on white powder stains and stains on Watari rack during fixing and washing with water.

[Example-3] Example-II! - Film-3 and film-4 were produced in the same manner. However, the amount of hardener added was determined so that the swelling percentage of the coating film defined below would be 110%.

Method for measuring swelling ratio a) Incubate the coated sample at 38°C and 50% relative humidity, b) Measure the layer thickness, c) Immerse in distilled water at 21°C for 3 minutes, and d ) Determine the percentage change in the layer thickness compared to the layer thickness measured in step b).

Next, concentrated solutions of developer and fixer having the following compositions were prepared.

(Developer concentrate) Potassium hydroxide 60g Sodium sulfite 100g Potassium sulfite 12.5g Diethylenetriaminepentaacetic acid 68 ml
257! hydroquinone
87.5g diethylene glycol
28g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 4.2g 5-methylbenzotriazole 0. Replenisher kit size: Make up to 1 liter with 5 g water (adjust to pH 11,00) Replenisher kit size
51 (Fixer n condensate) I Ammonium thiosulfate 560g Sodium sulfite 608 Ethylenediaminetetraacetic acid disodium dihydrate 6g Tartaric acid
3g sodium hydroxide 24g Make up to 11 with water (adjust pH to 5.1O with acetic acid).

Replenisher kit size 51 Also, fixer concentrate II with the same formulation as fixer concentrate mat but with the following polyhydric alcohol or additives added? Solution I JP was prepared.

Additive #Kl-hydroxyethylidene diphosphonic acid' L tert-butyl alcohol M Ethylene glycol addition amount g 0g 40-kun IN 2.4-dimethyl-2,4-bentanediol 52g0 2.3.4-hexanetriol 20g #P 1.6-hexanediol 60s Also, the following solution was prepared as a water stock tank solution.

(Water stock tank liquid) Ethylenediaminetetraacetic acid di 560g Sodium salt, trihydrate salt, trihydrate salt (anti-spiking agent) O, 5g/
12 The automatic developing machine shown in Fig. 1 is used.
o Dry was processed for 60 seconds.

The temperature of the developing tank 1 was 7.51, and the developing process was carried out at 35°C x 11.5°C.
The temperature of the 5-second fixing tank 2 was 7.51, and the fixing process was performed at 35°C x 12.
5 seconds water washing tank 3 is 61, water washing process is 20℃ x 7 degrees, 5 seconds squeeze roller washing tank 7 is 200ml, water stock tank liquid is 251, drying is 50℃ However, in order to maintain the temperature of both the developing and fixing tanks I used a heater, but did not use cooling water.

When starting the development process, each tank was filled with the following processing solution.

Developing tank 1: 400 ml of the above developer wIiI solution, 600 m of water A! Then, 10-l of an aqueous solution containing 28 g of potassium bromide and 1.8 g of acetic acid was added to adjust the pH to 10.50.

Fixing tank 2: 250ml of the above fixer concentrate! and 150 ml of water Washing tank 3 and washing tank 7: Same composition as the above water stock tank solution.As shown in the schematic diagram of the automatic developing machine in Fig. 1, the above photosensitive material B4 size (25.7 cm x 36.4 cm) 1
Each time a sheet is processed, 20ml of developer concentrate is added to developer tank 1.
A total of 30 ml of stock tank water and 10 mj of fixer concentrate in fixing tank 2! Add 30ml of the overflow liquid from the water washing tank 3 to the water washing tank 3 from the squeeze roller washing tank 7 (in the opposite direction to the film direction) and replenish 60ml of stock tank water, and cut into quarters on -day. Running processing of 100 sheets (film density: 1.1) was continued for one week. During this time, whenever the developer, fixer, and water ran out, new replenishers were added in the same way.

After one week of running, white powder stains on the Watarirak after fixing and washing were evaluated in the same manner as in Example-1. The results are shown in Table-2.

(Margin below) As shown in Table 2, the effects of the present invention are clear.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an automatic processor that can be used to implement the present invention. 1...Developer tank, 2...Fixer tank, 3...Water wash tank, 4...Water stock tank, 5...Developer concentrate stock tank, 6...Fixer concentrate stock tank , 7... squeeze roller cleaning tank. Procedural amendment (voluntary) June 8, 1999

Claims (1)

[Claims] A method for processing a silver halide photographic light-sensitive material, which is processed in the order of development, fixing, washing, and drying, characterized in that the fixing process is performed with a fixing solution containing a polyhydric alcohol having at least two or more hydroxyl groups. A method for processing silver halide photographic materials.