JPH03228049A - Processing method for silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To prevent the corrosion of the constituent members of a processing tank made of stainless steel by using Mo added stainless steel as the material of the members brought into contact with a processing soln. in the tank and placing a member made of stainless steel not contg. Mo in the tank so that the member is brought into contact with the processing soln. CONSTITUTION:When an exposed photosensitive material is color-developed and processed with a processing soln. having bleaching ability filled into a processing tank, the constituent members of this tank are made of stainless steel contg. <=0.1% C, >=10% Cr, >=2% Ni and >= 0.08% Mo and a member made of stainless steel obtd. by thermally degenerating part of the surface of the above-mentioned stainless steel by heat melting or stainless steel not practically contg. Mo is placed in the processing tank. Since the placed member is liable to corrode away as compared with the constituent members, it undergoes corrosion first and the corrosion of the constituent members is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for processing silver halide color light-sensitive materials.

<Conventional technology> Silver halide color photosensitive material (hereinafter referred to as photosensitive material).

) is processed through steps such as color development, desilvering, water washing, and stabilization after exposure. A color developing solution is used for color development, a bleach solution, a bleach-fix solution, and a fixing solution are used for desilvering treatment, tap water or ion exchange water is used for washing, and a stabilizing solution is used for stabilization treatment. The temperature of each processing solution is usually adjusted to 30 to 40°C, and the photosensitive material is immersed in these processing solutions to be processed.

A processing device such as an automatic processor is usually used for such processing, and the photosensitive material is processed by being sequentially transported between processing tanks filled with the above-mentioned processing solution.

In the desilvering treatment of color photosensitive materials, treatment using a processing solution having bleaching ability is essential, and a reaction occurs in which the silver produced by the color development treatment is oxidized.

Processing solutions that have this bleaching ability include bleaching solutions and bleach-fixing solutions, and these processing solutions contain various chemicals such as bleaching agents that are oxidizing agents, bleaching accelerators, and rehalogenating agents. There is.

For this reason, corrosion resistance is required for the metal materials applied to the constituent members of the processing tank filled with a processing solution having bleaching ability.

Specific examples of structural members to which the metal material is applied include members, rollers, roller bearings, springs, shafts, side plates, partition plates, mounting plates, gears, screws, and the like.

In this case, from the viewpoint of corrosion resistance, it is advantageous to use Ti, Ni, etc., but these metals are expensive.

disadvantageous in terms of Furthermore, Ti and the like also have the disadvantage of poor workability.

For this reason, stainless steel, especially Mo-added stainless steel, is advantageous in terms of corrosion resistance, etc., and specifically, 5US
316 etc. are commonly used.

<Problems to be Solved by the Invention> However, even members made of Mo-added stainless steel such as 5US316 do not have sufficient corrosion resistance, and cannot be kept in contact with bleaching liquids for long periods of time due to continuous processing. If there is, corrosion such as pitting corrosion will occur.

The object of the present invention is to provide Mo-added 5O among the members constituting a processing tank used by filling a processing solution with bleaching ability.
A method for processing a photosensitive material that provides a method for processing a silver halide color photosensitive material that can prevent corrosion of members made of stainless steel such as 3316 and increase the service life of a processing tank.

〈Means for solving problems〉 The above object is achieved by the present invention (1) below.

(1) A method for processing a silver halide color light-sensitive material in which the exposed silver halide color light-sensitive material is subjected to color development processing and then processed with a processing solution having bleaching ability filled in a processing tank, wherein the processing in the processing tank is performed. The components that come into contact with the liquid include C≦0.1%, Cr210%, Ni22%, Mo≧0.
In addition to the member made of stainless steel, the treatment tank includes a member made of stainless steel containing 0.8%, and in addition to the member made of stainless steel, stainless steel or MO that has been thermally altered by thermally melting at least a part of its surface is placed in the treatment tank. A silver halide color photosensitive material (for use) characterized in that a member made of stainless steel that does not substantially contain . After color development processing, the film is processed with a processing solution having bleaching ability.

At this time, a Mo-added stainless steel such as 5US31'6 or a non-Mo-added stainless steel whose surface has been thermally altered by melting at least a part of the surface is placed in the processing tank filled with a processing solution having bleaching ability. Since the members made of stainless steel such as 5U8304 are installed separately from the members that make up the processing tank, this separately installed member will be subject to corrosion. Corrosion of members made of stainless steel such as 5US316 that come into contact with the processing liquid is prevented.

Specific composition> Hereinafter, a specific configuration of the present invention will be explained in detail.

The method for processing the silver halide color photosensitive material (hereinafter sometimes abbreviated as photosensitive material) of the present invention is to subject the exposed photosensitive material to color development treatment, and then to process it with a processing solution having bleaching ability. .

This processing solution having bleaching ability is used by filling a processing tank, and the constituent members of this processing tank include C≦0.1%, especially C≦0.08%, Cr210%, especially Cr216%, N
1≧2%, particularly those made of stainless steel containing 24% Ni and Mo≧0.08%.

In addition, in this specification, % of alloy composition is weight %.

The above-mentioned constituent members are members used in contact with the above-mentioned processing liquid, and specifically include a seed material, a member for transporting a photosensitive material, or an auxiliary member thereof.

Particularly, items to which resin materials cannot be applied due to strength, workability, etc. include roller shafts and bearings, springs for pressing rollers, screws, bolts, nuts, etc.

Among the stainless steels constituting the above structural members, among those having the above contents, C: 0.01 to 0.08%, Cr: 16 to 30%, Ni 4 to 20%, Mo: 0 A content of .08 to 7% is preferred.

Specifically, as such stainless steel, 5US3
16.5US317. Examples include 5US317J and 5US329J.

In the present invention, in the treatment tank, apart from its constituent members, there is also a material made of stainless steel that has been thermally altered by thermally melting at least a part of the surface of the stainless steel, or a stainless steel that does not substantially contain Mo. The constituent members are installed.

This member, when the processing tank is filled with the processing liquid,
It is installed in such a way that it comes into contact with the above treatment liquid, and specifically,
The photosensitive material may be suspended by appropriate means at a location that does not interfere with the transportation of the photosensitive material and immersed in the processing solution.

Furthermore, it is sufficient to install this member in a small proportion of the constituent members of the processing tank made of stainless steel of the above composition, for example, the contact area of this member to the above processing liquid is 115 or less, preferably 1/10 or less, particularly preferably 1/100 to 1/1 of the contact area of the constituent members
It should be set so that it becomes 0000.

Among the above, thermal alteration of Mo-containing stainless steel such as 5O3316 may be carried out by metal melting technology applied during electric welding.

Among these, it is possible to melt at least a part of the surface of the stainless steel using metal melting technology in arc welding, especially inert gas arc welding using argon gas. You can easily get what you get.

For details on this technique, refer to pages 66 to 118 of "Mechanical Engineering Handbook (Revised 6th Edition)," edited by the Japan Society of Mechanical Engineers, Volume 17, "Machine Work," edited by the Japan Society of Mechanical Engineers. Just use it.

This thermal melting causes scratches on the stainless steel surface due to thermal alteration, leaving the grain boundaries of the metal structure exposed, and these areas are susceptible to corrosion such as rusting.

Therefore, members made of such stainless steel are more likely to corrode than the above-mentioned constituent members of the processing tank, and this member will be the first to suffer corrosion, preventing corrosion of the constituent members of the processing tank. Ru. In this case, the constituent members of the processing tank and this member may be connected by conductive wires or semiconducting wires.

On the other hand, stainless steel that does not substantially contain Mo includes 5US201.5US301.5US304.5US3
05.5US303.5US321.5US347.5
Examples include US309.5US310.5US302, and it is preferable to use 5US304 from the viewpoint of cost and availability.

Stainless steel that does not substantially contain Mo has a passive film that is not sufficiently strengthened against pitting corrosion (corrosion occurs easily) compared to stainless steel that contains Mo. For the same reason as in the case of stainless steel, which has become easier to corrode, corrosion of the constituent members of the treatment tank is prevented.

The processing solution having bleaching ability in the present invention includes a bleaching solution and a bleach-fixing solution, and the composition of the processing solution preferably used is as follows.

The concentration of Br is the total amount of Br derived from bromide originally added to the processing solution as a rehalogenating agent and Br eluted from the photosensitive material during processing and functioning as a rehalogenating agent. Yes, 10g/j in terms of NH4Br
Above all, those having an amount of 20 to 140 g/j are particularly preferable.

A complex salt of a ferric ion and a chelating agent, which will be described later, is preferably used as the bleaching agent, and contains 755.10 to 200 g/l of this iron (Ill) chelate.

If necessary, a bleach accelerator is added, especially to the bleach solution, but the bleach accelerator is not more than 3 g72, especially 0.2 to 2 g/
Those containing j are preferred.

Further, the pH is 4 to 8.

Furthermore, when it is a bleach-fix solution, it contains a fixing agent, and 50 to 200 me/R of ammonium thiosulfate (70%), which is preferably used as a fixing agent, is contained.

In a processing tank filled with a processing solution having bleaching ability of the above composition, corrosion such as pitting corrosion is likely to occur depending on the concentration conditions of the Br-bleach agent, bleaching accelerator, fixing agent, and pH conditions. The invention effectively prevents this.

In addition, in processing tanks filled with a processing solution that has bleaching ability, a method is adopted in which air is introduced into the processing solution in order to restore the oxidizing power of the bleaching agent during processing. It is preferable to apply the present invention to a processing tank.

This is because a treatment liquid with increased oxidizing power is more likely to cause corrosion.

Methods for introducing air in this way include a method of air aeration, a method of introducing pressurized air through a porous material disclosed in JP-A No. 62-251747, and an oxygen-permeable plastic material. Examples include methods using , and an appropriate selection can be made from these methods.

In addition, the replenisher for the processing solution with bleaching ability, which is normally used in continuous processing, is installed in the processing tank. It is preferable to add more chelating agent than the mother liquor.

As mentioned above, the amount of the chelating agent added in the replenisher can be adjusted to, for example, 7 mol % or more, further 10 mol % or more, especially 10 to 10 mol %.
The amount of replenishment can be reduced by increasing the amount in excess by 30 mol%. Furthermore, aeration, which introduces air into the processing liquid, can be omitted.

Next, a bleach solution and a bleach-fix solution, which are processing solutions having bleaching ability in the present invention, will be described.

Bleaching agents used in bleach or bleach-fix solutions include:
It is a ferric ion complex or a complex of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof (iron (m) chelate).
Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Examples of alkali metals include sodium, potassium, and lithium, and examples of water-soluble amines include alkyl amines such as methylamine, diethylamine, triethylamine, and butylamine, ring amines such as cyclohexylamine, and aryls such as aniline and m-toluidine. amines, and polyamines such as pyridine, morpholine, and piperazine.

Typical examples of chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, or their salts include ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylendiaminetetraacetic acid diammonium salt, and ethylenediaminetetraacetic acid. Tetra(trimethylammonium) acetate salt, ethylenediaminetetraacetic acid tetrapotassium salt, ethylenediaminetetraacetic acid tetrasodium salt, ethylenediaminetetraacetic acid trisodium salt, diethylenetriaminepentaacetic acid, diethylenetriamyrepentaacetic acid pentanatomonium salt, ethylenediamine-N-(β-oxyethyl )-N.

N'N'-triacetic acid, ethylenediamine-N-(
β-oxyethyl)-N,N,N triacetic acid trisodium salt, ethylenediamine-N-(β-oxyethyl)-
N, N'N'-triammonium triacetate, 1.2
-Diaminopropanetetraacetic acid, 1,2-diaminopropanetetraacetic acid disodium salt, 1゜3-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid diammonium salt, nitrilotriacetic acid, nitrilotriacetic acid trisodium salt, cyclohexanediamine Tetraacetic acid, cyclol-bexanediaminetetraacetic acid disodium salt, iminodiacetic acid, dihydroxyethylglycine, ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropano -Rue N, N, N", ゛N゛Nthiramethylenephosphonic acid, ethylenediamine-N, NN'N'
-tetramethylenephosphonic acid, 1°3-propylenediamine-N,N,N'N°-tetramethylenephosphonic acid, but are not limited to these exemplified compounds.

Iron ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid or phosphonocarboxylic acid.

When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used. In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron coco is preferred, and the amount added is preferably as described above.

Examples of useful bleach accelerators optionally used in bleach or bleach-fix solutions include U.S. Pat.
, No. 812, West German Patent No. 1.29,812, No. 2,
No. 059,988, Japanese Unexamined Patent Publication No. 53-32736, No. 53
-57831, 53-37418, 53-65
No. 732, No. 53-72623, No. 53-95630
No. 53-95631, No. 53-104232,
No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure 1
Compounds having a mercapto group or a disulfide group described in No. 7129 (July 1978), etc.;
Thiazolidine derivatives as described in No. 140129;
No. 2, No. 53-32735, U.S. Patent No. 3,706,
Thiourea derivatives described in No. 561; West German Patent No. 1.
127.715, iodide described in JP-A-58-16235; West German Patent No. 966.410, JP-A No. 2,748;
Polyethylene oxides described in No. 430;
Polyamine compounds described in JP-A-49-42434, JP-A-49-59644, and JP-A-53
-94927, 54-35727, 55-26
Examples thereof include the compounds described in No. 506 and No. 58-163940, as well as iodine and bromide ions. Among these, compounds having a mercapto group or a disulfide group are preferred because they have a large promoting effect, and are particularly preferred as disclosed in US Pat.
, No. 893.858, West German Patent No. 1,290,812, and JP-A-53-95630 are preferred. The amount added is preferably as described above.

In addition to the above, the bleach or bleach-fix solution may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. iodide). ammonium) rehalogenating agent.

Among these, bromide, particularly ammonium bromide, is preferably used, and the amount added is preferably as described above.

Furthermore, if necessary, one type with pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. The above inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

Addition of this corrosion inhibitor is also effective in the present invention.

Fixing agents used in the case of bleach-fixing solutions include known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; ethylene bisthioglycolic acid, 3,6-cythia-1,8-octanediol, etc. These are water-soluble silver halide solvents such as thioether compounds and thioureas, and these can be used alone or in combination of two or more. Also, JP-A-51-1
A special bleach-fixing solution made of a combination of constant W all and a large amount of a halide such as potassium iodide as described in No. 55354 can also be used. Among them, it is preferable to use thiosulfate, especially ammonium thiosulfate. The amount added is preferably as described above.

Bleach-fix solutions also contain sulfites as preservatives (e.g.
sodium sulfite, potassium sulfite, ammonium sulfite, etc.) Bisulfites (e.g., sodium bisulfite,
(e.g., potassium bisulfite, ammonium bisulfite, etc.) and metabisulfites (e.g., sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, etc.). These compounds are preferably contained in an amount of 0.02 to 0.50 mol/liter in terms of sulfite ions.

As a preservative, sulfite is generally added, but other substances such as ascorbic acid, carbonyl bisulfite adducts, or carbonyl compounds may also be added.

In addition, various other optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, buffering agents, chelating agents, antifungal agents, etc. may be added to the bleach-fixing solution as necessary. Good too.

The pn of the processing solution having bleaching ability is within the above range,
Especially in the case of bleach solution 4-6, in the case of bleach-fix solution 4.5
It is preferable to set it to 8 to 8, so that the effects of the present invention can be exhibited.

To adjust the pH, add hydrochloric acid, sulfuric acid, nitric acid,
Acetic acid, bicarbonate, ammonia, caustic potash, caustic soda,
Sodium carbonate, potassium carbonate, etc. may be added.

The processing temperature with a processing liquid having bleaching ability is 15 to 40°C, and the processing time is about 5 seconds to 6 minutes, and can be appropriately selected depending on the type of color photosensitive material to be processed.

Note that the bleach-fix solution may be a solution prepared by mixing a bleach solution and a fix solution.

In the present invention, in the desilvering process, a fixing liquid is used along with the above-mentioned processing liquid, if necessary.

Examples of the constant @ solution include those having a composition obtained by removing the bleaching component from the bleach-fixing solution described above.

In the present invention, the color developing solution used prior to the desilvering treatment is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidine diamine compounds are preferably used, and a representative example thereof is 3-methyl-4-amino-N,N-diethylaniline. , 3-methyl-4-amino-
N-ethyl-N-β-hydroxylethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates and hydrochlorides , phosphate or p-toluenesulfonate, tetraphenylborate, p-(t
-octyl)benzyl sulfonate and the like.

These diamines are generally more stable in their salt form than in their free form, and are therefore preferably used.

Examples of aminophenol derivatives include 0-aminophenol, p-aminophenol, 4-amino-2
-methylphenol, 2-amino-3-methylphenol, 3-oxy-3-amino-14-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F. A. Mason, Focal Press (1966) (L. F. A. Mason.

”Photographic Processing
Chemistry”, FocalPress) 2
Those described in pages 26 to 229, U.S. Pat. No. 2,193.015, U.S. Pat. If necessary, two or more color developing agents may be used in combination.

Color developers may contain pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. ;
Preservatives such as hydroxylamine, triethanolamine, the compounds described in OLS No. 2,622,950, sulfites or bisulfites; Alcohol, polyethylene glycol, quaternary ammonium salt,
Amines, thiocyanate, 3,6-thiaoctane-1
, 8-diol; dye-forming couplers: competitive couplers; nucleating agents such as sodium boron hydrate; auxiliary developers such as 1-phenyl-3-pyrazolidone; tackifying agents; .4°-diamino-2,2
Optical brighteners such as °-disulfostilbenes:
Ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and JP-A-1988
-195845 Aminopolycarboxylic acid, 1-hydroxyethylidene-1,1, represented by compounds listed in Tsukasa 2
゛Diphosphonic acid, Research Disclosure 181
70 (May 1979), aminophosphonic acids such as Amino, Nodris (methylene phosphonic acid), ethylenediamine-N,N,N No-tetramethylene sulfonic acid, JP-A-52-102726, 53-4273
No. 0, No. 54-121127, No. 55-4024,
No. 55-4025, No. 55-126241, No. 55
65955, No. 55-65956, and Search Disclosure No. 18170 (May 1979).

The color developing agent is generally used at a concentration of from about 0.1 g to about 20 g per liter of color developer, more preferably from about 0.5 g to about 10 g per liter of color developer.

The pH of the color developer in the present invention is usually 7 or more, and for boat fishing, it is used at a pH of about 9 to about 13, more preferably from 9 to II.

Further, the developability of the color developer can be improved by replenishing the color developer using a replenisher in which the concentration of halides, color developing agents, etc. is adjusted.

In the present invention, the processing temperature of the color developer for color photosensitive materials for photography such as color negative film is 20 to 50°C.
is preferable, and more preferably 30 to 40''C. The processing time is 20 seconds to 10 minutes, more preferably 30 seconds to 4 minutes. The processing temperature for the photosensitive material for color paper is 30 to 48°C. C, preferably 35 to 42° C. The processing temperature may be the same as that for color photosensitive materials for photography. The processing time is 20 seconds to 10 minutes, more preferably 30 seconds to 4 minutes.

In addition, the processing temperature for color reversal photosensitive materials is 33
-50°C, preferably 38-45°C. The treatment time is 30 seconds to 10 minutes, more preferably 90 seconds to 8 minutes.

The processing temperature for autopositive (direct positive type) color paper is 33 to 50°C, preferably 38 to 45°C.

- Processing time is 30 seconds to 10 minutes, more preferably 90 seconds to 8 minutes.

The first black-and-white developer used for reversal processing in the present invention can contain various additives that are used in black-and-white developers for processing black-and-white silver halide photosensitive materials.

Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as kanium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. can be mentioned.

In addition, the reversal process in the invention refers to a processing method in which black and white development (first development) is performed, followed by fogging color development (W). That is, first, black and white development is performed to form a silver negative image. Subsequently, the remaining unexposed photographic emulsion layer is subjected to color development by applying a fogging method to form a dye positive image together with a silver positive image.

This fogging method includes a method using full-surface exposure and a method using a fogging agent (
Specifically, there are two methods: (1) a method in which color development is performed after the entire surface is exposed; (2) a method in which color development is performed during the entire surface exposure 1. 7> Method of color development after No. Mo bath treatment, and ■
A method of carrying out color development during reduction bath treatment may be mentioned.

In the present invention, a water washing treatment and/or a stabilization treatment are performed after the desilvering treatment.

In addition to tap water, ion exchange water or the like can be used for the washing process.

Moreover, water softeners, bactericidal agents or antifungal agents, surfactants, etc. may be added to these.

The amount of washing water can be set within a wide range depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the washing water temperature, and various other conditions. The pH of the washing water is 4-9, preferably 5-8.

The washing temperature and washing time also vary depending on the characteristics of the color photosensitive material, etc.
20 seconds to 10 minutes at 45°C, preferably 3 to 45°C
A range of 0 seconds to 5 minutes is selected.

Further, a compound having an image stabilizing function is added to the stabilizing liquid used for the stabilizing process. For example, aldehyde compounds such as formalin, and 1
Examples include buffering agents and ammonium compounds for adjusting to ISIp)I. Furthermore, various fungicides, fungicides, surfactants, optical brighteners, hardeners, chelating agents, magnesium and bismuth compounds, and the like can be added.

The processing conditions and the like in this stabilization treatment can be set in the same manner as in the water washing treatment described above.

In the photographic emulsion layer of the light-sensitive material in the present invention, any of silver halide (arsenal, silver iodobromide, silver iodochlorobromide, silver chloride) and silver chloride may be used as the silver halide. Preferred halogen The silver oxide is silver chloride, silver iodobromide, or silver iodochlorobromide containing 3 mol % or less of silver iodide.

Photo 7L The average grain size of the silver halide grains being polished (grain diameter for spherical or approximately spherical grains, grain size for cubic grains in contact, expressed as an average based on projected area) is the grain size The distribution may be narrow or wide.

The particle size is preferably about 0.01 to 5.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or irregular crystal structures such as spherical and plate shapes.
gular) crystal form, or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

Further, it may be a particle in which a mental image is mainly formed on the surface or a particle in which a mental image is mainly formed inside the particle.

The photographic emulsion used in the present invention is P, Glafkide.
Written by Chimie et Physique Photo
ographique (Paul!+1ontel
Publishing, 1967'), G, F, Duffi
Photographic Emulsion C by n
hemistry fThe FocalPress
(1966), V. L. Zelikmane
Making and Coating by T, al.
Photographic Emulsion (The
Focal Press, 1964). That is,
Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method of reacting a soluble silver salt with a soluble halogen salt is a 1 piece 1 hole 1 combination method, or a simultaneous 1 combination method. Either one or a combination thereof may be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, a tardel water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic and A precipitation method (flocculation) using a 11-mer (eg, polystyrene sulfone) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, see, for example, Die G, edited by H. Frleser.
Rundlagen der Photography
schenProzesse mit Silberh
alogeniden (Akademische Ver.
lagsgesllschaft, l 968)
The method described on pages 675-734 can be used.

Color photosensitive materials used in the method of the present invention include color paper, color reversal paper, color negative film for photography, color reversal film, color negative film or color positive film for movies, and transmission type (film).
Alternatively, a known color photosensitive material such as a reflective (paper) direct positive photosensitive material can be used.

As for color paper, commercially available Fuji Color Paper Super FA Paper manufactured by Fuji Photo Film ■, Super HG Paper manufactured by Fuji Photo Film ■, 2001 manufactured by Eatsman Kodak Co., Ltd.
Paper, Koni Color QA Paper manufactured by Konica ■, Agfa Color Paper Type 9 manufactured by Agfa Gewald, etc. may also be mentioned.

As color negative films, Fuji Color Super HRn 100 and Super HG20 manufactured by Fuji Photo Film ■ are available.
0, Super HG400, Super HRII 16
00, Same Ara, Eastman Kodak Koda Color Gold 100, Same Gold 200, Same Gold 40
0, Gold 1600, Efter 25, Efter 1.
00, Efter 1000, etc. can also be mentioned.

<Example> Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Sample 10 of Example 2 of JP-A-63-235940
1 (color negative film), and after exposing it, use an automatic developing machine for color negatives FN manufactured by Fuji Photo Film ■.
Using a modified CP-40B machine, 24 images of 135 size were processed for 5 months at a rate of one image per day according to the following processing steps.

In addition, the above-mentioned automatic developing machine uses parts made of metal materials (roller shafts, bearings, screws, nuts, screws, holding plates, liquid level sensor heads, washers, etc.) in the bleaching tank.
This is a modified machine that has been changed to consist entirely of 5LIS316.

In addition, a pipe made of oxygen-permeable plastic was installed in the circulation section of the bleaching tank, allowing air to be introduced during processing.

Process Processing time Color development 3 minutes 15 seconds Bleach white 2 minutes lO seconds Fixed arrival time: 3 minutes 15 seconds Washing with water (1140 seconds Wed, first (2) 1 minute 00 (less Stability 40 seconds Drying 1 minute 15 seconds Refill amount is 35mm width Next, the composition of the processing liquid Processing temperature 38℃ 38℃ 38℃ 35℃ Replenishment amount 45mε mR 20n+j (2) to (1) Flow piping method.

tank capacity 0j 2 1 P 35℃　　　　30mj 38℃　　　　20m1 55℃ Per 1m length.

Write down.

p 1 (Color developer) Diethylenetriaminepentaacetic acid/1-hydroxyethylitine-1,l-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-ethyl-N (β-hydroxyethyl) ) Amino] Add 2-methylaniline sulfate solution and remove (ε(g) 1.0 3.0 4.0 30.0 1.4 1.5mg 2.4 4.5 1, Oj 10.05 Replenisher (g) 1.1 3.2 4.4 37 .0 0.7 2.8 5.5 1, Oj 10.10 (Bleach solution) 8 solutions, replenisher common Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Ammonium bromide Ammonium nitrate Bleach accelerator (Unit: g) 120.0 10.0 000 10, O O,005 mol (1.4 g) Aqueous ammonia (27%) Add water to 15.0 mj 1.0 °C pH 3 (Fixer) Mother liquor, replenisher Common (unit: g) Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 280 ml aqueous ammonia (27%) 6.0 mj Add water
i, oε pH 6,7 (Washing solution) Common tap water for mother liquor and replenisher.
B) and OH type anion exchange resin (Amberlite IR)
-400) to reduce the concentration of calcium and magnesium ions to 3 mg79 or less, followed by sodium isocyanurate monochloride 20
mg # and 0.15 g/'j of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7%) 2. On+j Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 12 pH 5.0 to 8.0 This is treated as Treatment IA.

In this treatment IA, after 5 months of running treatment, the bleaching solution was removed and the inside of the bleaching tank was visually observed.
Rust (mainly pitting corrosion) had occurred on the members made of S316 and the members that came into contact with the plastic material in the liquid. Specifically, between the roller shaft made of the above material and the vinyl chloride fitted around the roller shaft, the threaded part of the plastic fixing screw made of the above material ÷, the contact surface between the presser plate made of the above material and the plastic, and the presser plate. There was rust on the fixing screws and the contact areas between screws and nuts.

In processing IA, place it in a place that does not interfere with the processing of the photosensitive material in the bleach tank (specifically next to the plastic tank).
A 5US316 rod whose surface had been partially damaged by thermal alteration using arc welding metal melting technology was suspended, and the rest was treated in the same manner.

This is referred to as processing IB.

In addition, in processing IB, 5US316 (
7) Hanging the 5US304 (7) rod instead of the rod,
The rest was treated in the same way.

This is referred to as a processing IC.

In these treatments IB and 1c, when the bleaching baths were observed after 5 months of running, no rust was observed as in treatment IA.

Example 2 Sample P-2 (color paper) described in Example 2 of JP-A No. 63-70857 was used, and after exposure, it was processed using a Fuji Color Paper Processor PP6 manufactured by Fuji Photo Film ■.
Using a modified 00 machine, running processing was carried out for 4 months at a printing rate corresponding to two color negative films per day according to the following processing steps.

The processing machine described above is a modified machine in which all members made of metal materials (roller shafts, tapping screws, gear fixing screws, etc.) in the bleach-fix tank were replaced with ones made of 5US316.

In addition, in the circulation section of the bleach-fix tank, there is a
An air introduction means made of a porous material disclosed in Japanese Patent No. 47 was installed to introduce air during processing.

Color development 38℃ 1 minute 40 seconds 290mj
17j bleach fixing 35℃ 60 seconds 180mj
9j Rinse■ 33-35℃ 20 seconds −
41 Rinse 0 33-35℃ 20 seconds -4j Rinse ■ 33-35℃ 20 seconds 364mff1
4j Drying 70-80°C for 50 seconds *per 1 m2 of photosensitive material (3-tank countercurrent method for rinsing ■-■) The composition of each processing solution is as follows.

"Left" 10E diethylene triamine trichoic acid nitrilotriacetic acid 1-hydroxyethylidene 1,1-diphosphonic acid benzyl alcohol diethylene glycol sulfite potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)- 3-Methyl-4-aminoaniline sulfate hydroxylamine sulfate optical brightener (WHITEX 4 manufactured by Sumitomo Chemical) .0 g 0.5 g 0 g 5.5 g 2.0 g 1.5 g 1.0 g 2, Og 2.0 g 10 mε at 22 m 2.5 g 0 g 7.5 g 2.5 g 2, Og Water In addition, 000mj 000mj pH (25°C) 10.20 10.60 Esako n shame Kyuen Ll! water
400mj
400mff1 ammonium thiosulfate (70%) 80ml 95
mg ammonium sulfite 24 g 3
2 g ethylenediaminetetraacetate iron(III) ammonium 45 g 60
g Disodium ethylenediaminetetraacetate 5g 10g Ammonium bromide 25g 35g Add water 10100O1000mjp
100O℃) 5.0
4.5 vessels] Niyu armpit ion exchange water (3 pp each of calcium and magnesium
m or less) This is referred to as Process 2A.

In this treatment 2A, when the bleach-fix tank after the 4-month running treatment was observed in the same manner as in Example 1, rust had occurred as in the treatment IA of Example 1.

In Process 2A, a 5US316 rod with scratches due to thermal alteration was placed in the bleach-fix tank in the same manner as Process IB of Example 1, and the other processes were carried out in the same manner as Process 2B.

Also, in the same way as the processing IC of Example 1, 5L was placed in the bleach-fix tank.
Process 2C was obtained by installing an IS304 rod and otherwise performing the same process.

In these treatments 2B and 2C, when the bleach-fix tank was observed in the same manner as above after running for 4 months, no rust was observed as in treatment 2A.

<Effects of the Invention> According to the present invention, corrosion, particularly pitting corrosion, of members made of Mo-added stainless steel such as 5US316, which constitutes a treatment tank filled with a treatment solution that carries bleaching ability, can be prevented. Local corrosion can be prevented.

As a result, the service life of the treatment tank can be increased.

Out wish Man Fuji Photo Film Co., Ltd. teenager Reason Man

Claims (1)

[Claims] (1) A method for processing a silver halide color light-sensitive material in which the exposed silver halide color light-sensitive material is subjected to color development processing and then processed with a processing solution having bleaching ability filled in a processing tank, wherein the processing in the processing tank is performed. For the structural members that come into contact with the liquid, C≦0.1%, Cr≧10%, Ni≧2%, Mo≧0.
The treatment tank includes a member made of stainless steel containing 0.8%, and in addition to the member made of stainless steel, stainless steel or Mo A method for processing a silver halide color light-sensitive material, characterized in that a member made of stainless steel that does not substantially contain silver halide is placed in contact with the processing solution.