JPS63182650A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the sticking of stain to the titled material even in case of processing it with the temperance of water by specifying concentrations of a calcium compd. and a magnesium compd. contd. in the replenisher replenished to a washing bath and/or a stabilizing bath to <=5mg/l, respectively. CONSTITUTION:The titled material contg. a cationic high polymer compd. provided on a supporting body is processed with the bath having fixing ability, followed by processing with the washing bath and/or the stabilizing bath which are replenished the replenisher in an amount of 1-50 times the replenisher carried over from the fore bath. In this case, the concentrations of the calcium compd. and the magnesium compd. contd. in the replenisher replenished to the washing bath and/or the stabilizing bath are specified to <=5mg/l respectively. Thus, the sticking of the stain to the titled material is prevented, even in case of continuously processing the photosensitive material having excellent antistatic property with the washing bath or the stabilizing bath which is remarkably reduced the replenishing amount of the replenisher.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application) The present invention relates to a method for processing silver halide photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials). Even if you save a lot of water and treat it,
The present invention relates to an improved processing method that prevents stains from adhering to the photosensitive material.

C) Prior art) In recent years, it has been suggested that the amount of water used in the washing process included in the processing of silver halide photographic light-sensitive materials should be reduced due to environmental conservation, water resource, or cost concerns. . For example, the Journal of the Society on Motion Picture and Television Engineers (Journal of the 5
Ociety of Motion Picture
and Television Engineers)
Volume ≠ Volume 1.24tlr-2! J page [/ri! ! Year! WaterFlow Rates in I Immersion Washing on Motion Picture Film (Month issue)
mmersion-WashingofMotion
Picture Film” Nis・A/l/
M Goldwasser (S, R, Goldwasser
) has proposed a method of reducing the amount of flushing water by making the flushing tank multistage and causing the water to flow countercurrently. This multi-stage countercurrent water washing system has already been implemented in many automatic processors as an effective means for saving water. In particular, the depletion of water resources has become a real problem, and water charges have skyrocketed. Recently, further reductions in the amount of washing water used have been rapidly progressing.

However, it has become clear that various problems arise when the amount of washing water used is reduced and the treatment is carried out continuously. Among them, a major problem that needs to be solved is that when photosensitive materials coated with a cationic polymer compound as an antistatic agent are continuously processed with the amount of washing water replenished drastically reduced, contamination occurs on the surface of the photosensitive materials. This is because the particles adhere to the surface and significantly impair the performance after treatment. Recently, as a means of saving water, methods have begun to be implemented in which after processing in a bath with fixing ability, the washing step is omitted and the process is directly processed in a stable bath containing formalin, etc.; however, in the case of direct processing using such a stable bath The same problem is also evident.

Next, the prevention of static electricity on photosensitive materials will be described. It is very important to prevent static electricity in photosensitive materials. Photosensitive materials that are easily charged can emit light due to static electricity when being wound up in a camera during photography, exposing the emulsion to light and causing significant defects in images. There is.

Therefore, in order to prevent troubles caused by charging of the photosensitive material, an antistatic agent is applied to the pack surface of the color photosensitive material.

Examples of such antistatic agents include various surfactants, polymer compounds, inorganic salts, and conductive metal compounds. 1≠T7.2, the ionene type cationic polymer described in No. 16-7m, JP-A-Sho t! -／jri♂ issue, same 3! The cationic polymer compound represented by the cationic latex described in No. -17t≠- has excellent antistatic performance.

When a photosensitive material is continuously processed using a water washing bath with a reduced amount of replenishment or the above-mentioned stabilizing bath with a reduced amount of replenishment, thiosulfate, silver thiosulfate complex salt, organic Fixing or bleach-fixing bath components (pre-bath components) such as acid iron complex salts accumulate. Furthermore, surfactants, gelatin, etc. are eluted and accumulated from photosensitive materials.

When a photosensitive material coated with a cationic polymer compound is processed in a washing bath or stabilizing bath containing such various deposits, white deposits are formed on the coated surface.

In addition, floating matter called scum is generated in the washing bath or stabilizing bath where photosensitive materials coated with cationic polymer compounds are continuously processed, and this may adhere to the emulsion side or cause damage to the filters of automatic processors. This may cause problems such as clogging in a short period of time.

It has also been found that the formation of such scum is further increased by the growth of microorganisms such as bacteria and mold within the bath.

It has been found that such a phenomenon is particularly remarkable when washing and/or stabilization treatment using hard water is performed.

To avoid such problems, when using a cationic polymer compound, it is necessary to reduce the amount of cationic polymer used, or add it in a layer closer to the support and away from the outermost layer, so that it is not sufficient. In some cases, it has not been possible to provide sufficient antistatic performance, or to sufficiently reduce the amount of replenishment required for washing baths and stabilizing baths during processing.

Note that the technology of using a water-resistant onium compound in the so-called back layer of photosensitive feathers was published in Japanese Patent Application Kokai J/-! 6311! However, the purpose and structure are different from the above-mentioned compounds.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to process a photosensitive material with excellent antistatic performance continuously in a nine-water washing bath or a stabilizing bath while greatly reducing the amount of replenishment. The object of the present invention is to provide a processing method that does not cause stains to adhere to photosensitive materials.

The third object of the present invention is to provide an easy-to-maintain processing method that does not clog the filter provided in the washing bath or stabilizing bath of an automatic developing machine in a short period of time even when the above-mentioned processing is carried out. Our goal is to provide the following. Furthermore, a third object of the present invention is to provide an inexpensive processing method that reduces the amount of replenishment.

Means for Solving Problem C) Such an object of the present invention is to process a silver halide photographic light-sensitive material containing a cationic polymer compound on a support with a bath having fixing ability (preferably immediately), 1 to 10 of the amount brought in from the previous bath per unit area of the photosensitive material.
In a method of treatment with a water washing bath and/or a stabilizing bath that is refilled twice, the concentration of calcium compounds and magnesium compounds in the replenishing solution replenished to the washing bath and/or cough stabilizing bath is J as calcium and magnesium, respectively. −
(2) This was achieved by a method for processing a silver halide photographic material, which is characterized in that / is as follows.

In the present invention, the water washing bath is used to clean the processing liquid components that have adhered to and occluded on the photosensitive material as well as the constituent components of the photosensitive material that are no longer needed during the processing process. The purpose of this bath is to maintain good performance of the material and, if there is a subsequent treatment bath, to maintain the performance of the subsequent bath by reducing the contamination of the preceding bath components.

Therefore, any bath that achieves the above objectives through its cleaning effect falls under the category of the water washing bath of the present invention, regardless of its composition.

Further, the stabilizing bath is a bath to which a compound is added which imparts an image stabilizing effect to the photosensitive material that cannot be obtained with a water washing bath.

An example of such a stabilizing bath for color photosensitive materials is C0LORFJLM by C, TJ, Thomson.
1st edition page, J j (/ri! FOCAL
A bath containing formaldehyde alkalinity regulator and wetting agent is installed in FREssLIM (published by TED).
In addition, U.S. Patent No. 2. The formaldehyde and bisulfite bath described in No. 7 of tμ7.0, No. 3 of the same.
03! , a bath to which soluble salts such as magnesilla and calcium are added as described in 3. /4to, /7t9'r
A bath containing formaldehyde and a polycarboxylic acid as described in JP-A No. 3.3t9,194-ter, a bath containing formaldehyde and a surfactant as described in JP-A No. 3.3t9,194-ter, ammonium sulfite as described in JP-A No. 34-34, etc. A bath to which sulfite was added, a bath to which water-soluble zirconium and polycarboxylic acid were added as described in the Getter rJaai issue, a bath to which a fluorescent brightener was added as described in the same issue ≠ 9-10773, Research Disclosure/ 71≠ri(
There are baths to which an aldehyde compound, diphosphonic acid, and aminopolycarboxylic acid are added, as described in Nov., /937t).

Of course, not all of the baths to which the compounds mentioned in these examples are added are stable baths, but they become stable baths when they exhibit an image stabilizing effect.

In the present invention, the number of washing baths and/or stabilization baths may be single or plural, but in order to achieve the purpose of reducing the amount of replenishment, they are configured with a plurality of tanks, and the last tank is refilled and the flow sequentially flows into the front tank. It is preferable to use a multi-stage countercurrent system.

Hereinafter, a process consisting of one or more water washing baths or stabilization baths will be referred to as a water washing process or a stabilization process, but in the present invention, at least the calcium and magnesium in the last bath of the water washing process or -/O- stabilization process are It is necessary that the concentration of calcium and magnesium compounds in the replenisher solution replenished to the washing bath and/or stabilization bath is maintained below 3.0% as calcium and magnesium, respectively. It is necessary that the amount is reduced to below, preferably less than 3 g/, more preferably less than 1 #g/.

Various known methods can be used to bring calcium and magnesium in the water washing replenisher and/or stable replenisher to the above concentrations, including using ion exchange resin, zeolite, and reverse osmosis treatment equipment alone or in combination. It is preferable. As the ion exchange resin, various cation exchange resins can be used alone or in combination with an anion exchange resin. In addition, a chelate resin 1 that captures metal ions through a chelate reaction (for example, one having an aminopolycarboxylic acid salt at the end) can also be used as one of the ion exchange resins.

As the cation exchange resin, strongly acidic Na-type cation exchange resins and circulating H-type cation/exchange resins are preferred, and a combination of strongly acidic H-type cation exchange resins and strongly basic OH-type anion exchange resins is also a preferred embodiment. It is.

The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinyl inzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such ion exchange resins include Diaion SK-/B or Diaion PK-J/ manufactured by Mitsubishi Chemical Corporation.
, 4, etc. These ion exchange resin substrates are preferably those in which the amount of divinylbenzene charged is φ~/G% with respect to the total amount of monomers charged during production. H
As the anion exchange resin that can be used in combination with the type cation exchange resin, a strongly basic anion exchange resin having a styrene-divinylbenzene copolymer as a base and having a tertiary amine or secondary ammonium group as an exchange group is preferable. An example of such anion exchange resin is the same product name Diaion 5A-10K (manufactured by Mitsubishi Kasei).
Alternatively, Diamondion PA-4A/r can be mentioned.

All known methods can be used to remove calcium and magnesium from water using these ion exchange resins, but preferably the water is passed through a column filled with an ion exchange resin. The water flow rate is /-100 times the resin constitution per hour.
Preferably it is 5 to 30 times.

Zeolite is an insoluble aluminum silicate containing Na
(AtOz 1x-(SiO However, the X-type zeolite is particularly preferred because it has excellent exchangeability for both calcium and magnesium. Examples of such zeolites include zeolites such as Union Ker) Zeolite, Mov+Nila-Sheep I,
INDE ZB-JOO can be given. Zeolite has various particle sizes, but particles larger than 3Q mesh are suitable when packed in a column and brought into contact with washing water -13-.

As the reverse osmosis treatment equipment used in the present invention, any known equipment can be used without limitation, but the area of the reverse osmosis membrane is 3 m
It is desirable to use an ultra-compact device with a working pressure of 2 m2 or less, and a working pressure of 30 h/m2 or less, particularly preferably 2 m2 or less, and 30 kg/m2 or less. When such a compact device is used, the workability is good and a sufficient water saving effect can be obtained. Furthermore, it is also possible to pass activated carbon or a magnetic field.

The reverse osmosis membranes included in the reverse osmosis treatment equipment include cellulose acetate membranes, ethylcellulose polyacrylic acid membranes,
Polyacrylonitrile film, polyvinylene carbonate) I
ll, polyethersulfone membrane, etc. can be used.

In addition, the liquid feeding pressure is usually j -A OKy/m2, but in order to achieve the purpose of the present invention, it is 30 to 9/cfrL.
2 or less is sufficient; however, what is called a low-pressure reverse osmosis device with a pressure of /OKg/cm2 or less can also be used.

-/4t- The structures of reverse osmosis membranes include snoural type and tubular type.
Any of the mold, hollow fiber type, pleated type, and rondo type can be used.

Next, the cationic polymer compound used in the present invention will be described below.

The cationic polymer compound used in the present invention is generally contained in color photosensitive materials as an antistatic agent. At least one of the constituent layers
It is a layer. And in order to obtain favorable antistatic properties,
The cationic polymer compound is used so that the surface resistivity of the pack layer is 7 o 13 Ω or less, more preferably 12 Ω or less, particularly preferably 7 o 11 Ω or less.

These cationic polymer compounds having good antistatic properties are not particularly limited, but for example, JP-A-12-12!3! Same issue! θ-Ta lO Yu No. 3, same! θ−
Tag t72, same guji/2/! No. 23, same! 3-/θ
T//! No., same jJ-//7ko J4 No., same! 3-ta 2
/-! No., times! J-77 Otsu No. 3, same evening Otsu-4 T703 No., same! No. 119.2λλ, U.S. patent, /2t,
4) No. 7, J, Ot2, 711, No. 2. ri7ko,
! No. 37, J, /21. ! The cationic polymer described in No. 10, etc., published by JP-A-Sho! 4)-/J Riwo issue, same t
r-tzyjo issue, same J! -! 71#2, same! j-4
No. 774tt, U.S. Patent J, 07, Hirora No., μ,
Cationic latexes described in No. 07θ, /r, etc. are preferably used. Moreover, as the cationic polymer compound, a non-photosensitive compound is preferable.

The molecular weight of the cationic polymer compound is preferably j'00 to 1 million, more preferably 7θ0-jθ
Ten thousand.

In addition, as the cationic polymer compound, a polymer compound having a quaternary ammonium ion, a pyridinium ion, a phosphonium ion, a sulfonium ion, an amine salt, etc. is preferable, and the quaternary ammonium ion, pyridinium ion, etc. Polymer compounds having the following are preferred.

Specific repeating units constituting the cationic polymer compound are described below.

p-/ P-≠ P-, t H3 １／　♂　− P-r p-i.

1/tarP-// p-/λ P-/J p-/4A p-/, t p-/4 2 l-P-/7 P-/I P-/ri le High cationic properties of the present invention Regarding the method of incorporating the molecular compound into at least seven layers of the backing layer, the cationic polymer compound having a film form can be used as it is without using a binder, or it can be used by mixing it with a binder. good. Further, a cationic polymer compound which cannot form a good film by itself is usually contained in a film using a binder. The binder used in this case may be one having film-forming ability, but examples include proteins such as gelatin and casein, carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, shea cellulose compounds, dextran, agar, sodium alginate, Sugars such as starch derivatives, synthetic polymers such as polyvinyl alcohol, polyvinyl acetate, polyacrylic ester, polymethacrylic ester, polystyrene, polyacrylamide, poly-N-vinylpyrrolidone, polyester, polyvinyl chloride, polyacrylic acid, etc. .

Among these, particularly preferably used binders include gelatin C (lime-treated gelatin, acid-treated gelatin, enzymatically decomposed gelatin, phthalated gelatin, acetyl gelatin, etc.),
These are cellulose acetate, cellulose diacetate, cellulose triacetate, polyvinyl acetate, polyvinyl alcohol, polybutyl acrylate, polyacrylamide, and dextran.

The amount of the cationic polymer compound of the present invention used is 0.00/~10/m2 of the color photosensitive material. However, preferably 0.0/-J'? .

Particularly preferred is 0.02 to 3v. In addition, the ratio (C weight ratio) of the amounts of the cationic polymer compound and the binder used is preferably in the range of z-7oo:o, preferably 10:
riO~/θ020. Particularly preferably 20:Ir0N
:io.

The method of applying the cationic polymer compound of the present invention to the back layer of a color photosensitive material includes water, alcohol 1, etc.
Methanol, ethanol, isopronol, tetrahydrofurfuryl alcohol, benzyl alcohol,
ethylene glycol, methyl cellosolve, etc.), esters (MJ, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, ethyl chloroacetate, methyl propionate, methyl benzoate, diethyl carbonate, co/dimethyl phosphate, etc.), Ketones (e.g. acetone, methyl ethyl ketone, methyl phenyl ketone, cyclohexanone, acetylacetone, etc.), ethers (e.g. diethyl ether, anisole, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether, etc.), hydrocarbons NFIJt, I', benzene, Toluene, xylene, Schiff-λ yo- Rohegisan, octane, chloroform, methylene chloride,
A cationic polymer compound alone or together with a binder is dissolved or dispersed in a solvent such as carbon tetrachloride, amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), acetonitol, dimethyl sulfoxide, etc. to form a back layer. At least a small amount of it should be contained in one layer.

In the present invention, it is preferable that the replenisher to be added to the washing bath or the stabilizing bath be sterilized in advance, thereby further enhancing the effect obtained by reducing calcium and magnesium.

In other words, if such sterilization is carried out, the washing bath,
Invasion of microorganisms such as bacteria and mold into the stable bath is reduced.
The tendency for microorganisms to participate and increase the formation of said scum can be inhibited.

Specific methods for sterilization include the washing replenisher, the stable replenisher itself, or the addition of a compound with a bactericidal effect to the water used to prepare the replenisher, or a filter with a pore size of 0r microns or less. However, due to the reliability of the effect and the synergistic effect with the calcium and magnesium reduction treatment, it is recommended to add compounds with bactericidal effects and filters with pore diameters of o and I microns or less. Filtration is preferred.

Particularly preferred compounds having bactericidal activity are active chlorogen-releasing compounds such as hypochlorous acid, dichloroisocyanuric acid, trichloroisocyanuric acid, and salts thereof. j-Chlorose-methyl-l-isothiazoline-
3-on! Inthiazolone compounds such as -methyl≠-inthiazirin-3-one and benzisothiazolone compounds typified by 2-benzisothiazolin-3-one can also be used. Triazole compounds such as benzotriazole, sulfanilamide, IO,'
Also preferred are organic arsenic compounds such as 10'-oxybisphenoxyarsine, silver ion releasing compounds such as silver nitrate, silver chloride, silver oxide, and the like. You can also use the sterilizing cutting agents described in Hiroshi Horiguchi's ``Chemistry of Antibacterial and Antifungal Agents'' and Sanitation Technology Bulletin ``Sterilization of Microorganisms, Disinfection, and Mildew Release Technology''.

Among the above-mentioned fungicidal and fungicidal agents, active) rogen-releasing compounds and silver ion-releasing compounds are preferred compounds because they have a particularly strong synergistic effect with calcium and magnesium reduction treatments. Specific examples of these compounds include the following.

<Active halogen-releasing compound> l1 Sodium hypochlorite λ, sodium dichloroisocyanurate 3 trichloroincyanuric acid 4t, chloramine Tj, chloramine Bt, dichlorodimethylhydantoin 7.2-bromo-t'-hydroxyacetophenone r , I, 'I-bisbromoacetoxy-2-butene, silver ion-releasing compound>, silver nitrate /7. Silver carbonate 10, silver chloride /1. silver phosphate, silver bromide, silver sulfite, silver fluoride
CoO, silver silicate/3. Silver perchlorate 1. Silver bromate/4t, silver chlorate here. Silver nitrite is, silver acetate 3. Silver iodate lz, silver sulfate λμ
, silver lactate Among the above, sodium hypochlorite, sodium dichloroisocyanurate, and trichloroisocyanuric acid are particularly preferred. The content of sodium hypochlorite is j~/!
It is added as an alkaline aqueous solution. Sodium dichloroinocyanurate and trichloroisocyanuric acid are commercially available in a variety of forms such as powder, granules, tablets, etc., and each can be used as desired depending on the conditions. An example of such a commercially available product is No. Illite Ace G manufactured by Nichichi Kagaku ■.
1 Highlight tOG, No. 1 Light Clean, etc. can be used.

Considering the fact that these compounds have bactericidal effects, it is preferable to add them in larger amounts; however, using excessive amounts will impair the performance of the photosensitive material after processing, so it is better to add them as little as possible. Preferably, the amount of the active halogen-releasing compound to be added is the amount of each compound as a pure product in the amount of water wash replenisher and/or stable replenisher/1. 0.79-100m per
9, preferably 71119 to 5o.
ny, particularly preferably set to 3■ to 30η. In addition, in the case of a silver ion-releasing compound, the silver ion concentration is 0.00j~
It is preferable to adjust to 10Tv, and θ, 0.2~/
1R9 is more preferred. These compounds need to be added to the replenisher solution prior to replenishing the wash bath and/or stabilization bath. Even if these compounds are added directly to the wash bath and/or stabilization bath after they have been refilled, i.e. directly into the wash bath and/or stabilization bath, the carry-over components from the previous bath present in the bath in the case of active halogens, reducing agents such as thiosulfates, sulfites, iron(III) ethylenediaminetetraacetate;
It is deactivated by the action of oxidizing agents such as complex salts, as well as components eluted from photosensitive materials, such as silver salts and gelatin, and silver ions become silver thiosulfate and lose their bactericidal power, so they are not effective. Can not.

Next, a method of carrying out bacterial retention treatment using a filter with a pore size of O0r microns or less will be described.

The pore size of the filter is less than 0.0 microns, preferably less than 0.3 microns, particularly preferably less than 0.3 microns, in order to inhibit bacteria and mold. As the material of the filter, cellulose acetate, ethyl cellulose, polyacrylic acid, polyacrylonitrile, polyvinylene carbonate, etc. can be used, but from the viewpoint of durability, cellulose acetate, and more specifically cellulose triacetate, is preferable. As an example of such a filter, for example, Fuji Micro Filter FCE manufactured by Fuji Photo Film ■
Examples include -17'OW, FCE-22W, FCE-22W cartridges.

Bacteria and mold can be effectively removed by passing through these filters.

In the present invention, the sterilization process does not necessarily have to completely eliminate fungi such as bacteria and mold, but as long as the number of viable bacteria in the washing replenisher after sterilization is io3 or less,
Although the effects of the present invention can be exhibited, it is preferable that
The number of viable bacteria should be 0.02 or less.

In the present invention, it is preferable that the washing bath is placed subsequent to the bath having fixing ability.

Further, the stabilizing bath may be disposed following the bath having fixing ability, or may be disposed as a subsequent bath to the washing bath following the bath having stabilizing ability, but in particular, it may be disposed following the bath having fixing ability. The effect of the present invention is remarkable when the arrangement is made.

The present invention is effective when applied to a washing bath and a stabilizing bath with rice cultivation in the following arrangement, but in particular, the following /, 3,! is preferred.

/, Bath with fixing ability - Washing bath" - Washing bath - Stable bath" 3,
−Water bath”−Stabilizing bath”μ,
- Washing bath - Stable bath - Stable bath Next, we will discuss the amount of replenishment.

The effect of the present invention is that the amount of replenishment to the washing bath and/or stabilization bath is 1 to 1.0% of the amount brought in from the previous bath per unit area of the photographic material to be processed. It is expressed when the number is to, preferably 3
~30 times, particularly preferably 3 to 20 times.

Further, the amount of replenishment of washing water or stabilizing solution is preferably less than 1 m 2 of photosensitive material.

In addition, the light-sensitive material brought in from the pre-bath is usually
m2 equivalent #) 4to -A Oml.

These water washing steps and stabilization steps are preferably performed using a plurality of tanks as described above, and usually 2 to 6 tanks, particularly a Col μ tank is preferable from the viewpoint of the balance between effectiveness, installation area, equipment cost, etc.

In the present invention, the amount brought in from the pre-bath means the volume of the pre-bath that is attached to or occluded by the photosensitive material and mixed into the washing or stabilizing bath, and refers to the volume of the pre-bath that is attached to or occluded by the photosensitive material and mixed into the washing or stabilizing bath. It can be calculated by extracting the pre-bath components by immersion in water and measuring the amount of the pre-bath components in the extract.

Next, the treatment time in the water washing bath is usually 10 seconds to evening, preferably 20 seconds to 3 minutes, particularly preferably 30 seconds to 3 minutes. The treatment time is the same when the water washing bath is omitted and the treatment is performed directly in the stabilizing bath, but when the washing bath is followed by a water washing bath, the treatment time is usually 10 seconds to - minutes, preferably θ seconds to /minute. .

The pH of the washing bath and stabilizing bath largely depends on the pH of the pre-bath that is brought in, but it is usually 7-7, preferably 6-1. It is j.

In addition, if the temperature of the washing bath or stabilizing bath is high, it can reduce the amount of deposits on the photosensitive material, but on the other hand, it can easily cause reticulation and scratches on the emulsion film. ˜≠o′C is preferable, and 33˜jlr0C is particularly preferable.

In addition to the above-mentioned sterilizers, the washing bath uses a sterilizer manufactured by Photographic Science and Engineers (Photog).
rapic 5science and Engine
eers ) Vol, J, Yari (/ri7j) Page
J 5' r-4t/ 3, "Water Quality") Tea Criteria 1Water Quality-
Water softeners such as ethylenediaminetetraacetic acid described in 3 Goo Cr1teria 1'', halogenated phenols to prevent the growth of algae, copper ions, etc. can be added.Furthermore, Hari Search Disclosure, 20 !21 (described in May, 191/1!-
chlorocomethylruderinthiazolin-3-one,
Any compound that can be added to the washing water can also be used in the present invention depending on the purpose.

Compounds known to be added to the above-mentioned stabilizing baths, such as formalin, surfactants, sulfites, polycarboxylic acids, aminopolycarboxylic acids, and fluorescent brighteners, can be optionally added to the stabilizing bath. In addition to this, compounds that can be added to a water washing bath can also be added in the same way. In particular, for a stable bath containing formalin, it is preferable to add the following chelating agent and its salt in order to inhibit the decomposition of formalin by microorganisms.

A-/A-co-J A-gA-terIO-ii A-/2 Ha Summer H203P-C-PO3H3 H These aminocarboxylic acids, aminophosphonic acids, phosphonic acids, phosphonocarboxylic acids, and salts thereof What amount should be included in the washing water or stabilizing solution? X10-5~/x10
-2 mo/lC, preferably -3 to /x10' to jx10-3 mol/l.

In the present invention, overflow liquid generated from the washing bath and/or stabilizing bath upon replenishment can also be introduced into a bath having the fixing ability of the preceding bath.

Introducing such an overflow liquid dilutes the components of the bath with fixing ability, but by adding a small amount of concentrated replenisher to the bath with hand-fixing ability, it is possible to maintain proper bath content. can maintain the concentration of

As a result, it becomes possible to reduce the amount of waste liquid generated during processing.

Conventionally, when introducing an overflow as described above, the amount of dirt adhering to the photosensitive material increased significantly, but as in the present invention, calcium and magnesium in the replenisher of the washing bath and/or stabilizing bath can be reduced. If you do this, you can prevent dirt from sticking.

The present invention can also be effective in reducing the amount of waste liquid by using such overflow liquid.

Next, as examples to which the present invention is applied, there are processing of color light-sensitive materials and processing of black and white light-sensitive materials, and the processing of silver halide color photographic light-sensitive materials, which is preferably used, will be described.

The processing method of the present invention can be applied to various processes for color photographic materials, such as the following.

A6 color development - bleach fixing, washing, drying B, l - washing, bleaching, fixing, washing, drying C0I
- Bleach-fixing, washing, drying, l-1- bleach-fixing, washing, drying, E, I-#- bleach-fixing - washing, drying, F, l, bleach-fixing, washing, drying, G, l
- Bleach, one wash, one stable, one dry HoI - One bleach, one wash, one stable, one dry, l
- Bleach - Bleach-fix - Wash - Stable - Dry - Bleach-fix - Wash - Stable - Dry
1. Fixing - Bleaching - Fixing - Washing - Stabilization - Drying This method can also be applied to the above A to F in which "washing with water" is changed to "stable".

The above treatment bath will be explained below.

Color Development The color developer used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phinidine diamine compounds are preferably used, representative examples of which are 3-methyl-≠-ciminor N, N-diethylaniline, -Methyl-μmamino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-guamino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-guamino-N-ethyl-N
-β-methoxyethylaniline and their salt salts,
Hydrochloride, phosphate or Id, p-)luenesulfone [
K, tetraphenylborate, p-(t-octyl)benzenesulfonate, 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 the aminephenol derivatives include 0-aminophenol, p-aminophenol, guamino-co-methylphenol, co-amino-3-methylphenol, 3-oxy-3-amino-/, and ≠-dimethylbenzene.

In addition, "Photographic Processing Chemistry Three" by F. A. Mason, Focal Press [1996] (L. F. A. Mason)
.

@Photographic Processing
Chemistry', Focal Press)
2.2t ~ Kokota page, U.S. Patent No. ko, /ri J, 0/j
No., Same Ko, J Octopus, JtlA No., JP-A-4J'-tl/
-933, etc. may be used. If necessary, two or more color developing agents may be used in combination.

The color developer contains p 1-1 buffers such as alkali metal carbonates, borates or phosphates; development inhibitors such as bromides, iodides, benzimidazoles, benzothiacinols or mercapto compounds. agent or antifoggant; hydroxylamine, diethylhydroxylamine, triethanolamine, West German patent application (
Preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates, Development accelerators such as 4-thiaoctane-/, I-diol; dye-forming couplers; competitive couplers:
Nucleating agents such as sodium boron hydride; auxiliary developers such as l-phenyl-3-pyrazolidone; tackifiers; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid Acetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and JP-A-Sho! I-/9! Aminopolycarboxylic acids represented by the compounds described in No. Jrllj, l-hydroxyethylidene-i,i'-diphosphonic acid, organic phosphonic acids described in Research Disclosure/1170 (/7 years! months), aminotris C methylene phospho/acid), ethylenediamine-N,N.

A chelating agent such as aminophosphonic acid such as N/, N/-tetramethylenephosphonic acid, phosphonocarboxylic acid, etc. can be contained.

Color developing agents generally have a color developer/l weight of approximately o,
It is used at a concentration of from it to about 30t, more preferably from about /f to about /19 per color developer it. Also,
The pH of the color developing solution is usually 7 or more, and most commonly used at a pH of about 73 to about 73. Furthermore, the amount of replenishment can be reduced by using a replenisher in which the concentration of halides, color developing agents, etc. is adjusted for the color developing solution. For example, it is also possible to use a replenisher containing a large amount of halides.

In the present invention, it is preferable that the above-mentioned benzyl alcohol is not substantially contained as a development accelerator even in the case of color R-par processing. Here, "substantially not containing" means containing no more than 21M9 per ton of color developer, preferably no more than 0.1 ml, and more preferably no content at all. The present invention exhibits better effects when it does not contain benzyl alcohol.

The processing temperature of the color developer of the present invention is preferably 20-4000°C, more preferably 30-0°C. The treatment time is 20 seconds to 70 minutes, preferably 30 seconds to j minutes.

As the bleaching agent used in the bleach solution or bleach-fix solution used in the present invention, a ferric ion complex is a complex of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof. It is. Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Alkali metals include sodium, potassium, lithium, etc. Water-soluble amines include methylamine,
These include alkylamines such as diethylamine, triethylamine, butylamine, ring amines such as cyclohexylamine, cyclic amines such as aniline, m-toluidine, and heterocyclic amines such as pyridine, morpholine, and piperidine.

Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids or their salts include: (1) ethylenediaminetetraacetic acid (2) ethylenediaminetetraacetic acid cinammonium salt (3) ethylenediaminetetraacetic acid diammonium salt (4) Ethylenediaminetetraacetic acid tetraf trimethylammonium) salt (5) Ethylenediaminetetraacetic acid tetrapotassium salt (6) Ethylenediaminetetraacetic acid tetrasodium salt (7) Ethylenediaminetetraacetic acid trisodium salt dat- (8) Diethylenetriaminepentaacetic acid ( 9)
Diethylenetriaminepentaacetic acid pentasodium salt (11ethylenediamine-N-(β-oxyethyl)-
N, N', N'-) ethyl acetic acid α1) Ethylenediamine-N-(β-oxyethyl 1-
N,N',N'-) trisodium acetate salt α2 ethylenediamine-N-Iβ-oxyethyl)-
N,N',N'-1 triammonium acetate salt (2) /, 2-diaminopronononetetraacetic acid Q4) /
, z-diaminopropane tetraacetic acid disodium salt Q5/, J-diaminopronone tetraacetic acid (10ha3-
Diaminoprono ξtetraacetic acid diammonium salt (17) Nitrilotriacetic acid c181 Litrilotriacetic acid trisodium salt α1
Cyclohexanediaminetetraacetic acid cyclohexanediaminetetraacetic acid disodium salt Qυ Iminodiacetic acid @ dihydroxyethylglycine Ethyl etherdiaminetetraacetic acid @ Glycol etherdiaminetetraacetic acid (iii) Ethylenediaminetetrapropionic acid (e) Phenylenediaminetetraacetic acid @ /, 3- Diaminopropanol-N, N.

N',N'-tetramethylenephosphonic acid (c) ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid (c)/, 3-propylenediamine-N,N.

Examples include N',N'-tetramethylenephosphonic acid.

In addition, in the above-mentioned chelating agent, especially (11, (3), (
8), (151% 翰, (goods)) are preferably used.

Ferric ion complex salts may be used in the form of complex salts, or may be used in combination with ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferrous phosphate, etc. A ferric ion complex salt may be formed in solution using a chelating agent such as aminopolycarbo/acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. When used in the form of a complex salt, seven types of A complex salt may be used, or more than one type of complex salt 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 ferrous salts may be used. Furthermore, chelating agents of L type or 2S type or more 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 complexes are preferable, and the amount added is 0.0000000000 in bleaching solutions for color photographic light-sensitive materials such as color negative films. /~1 mol/1. Preferably Oo, 2 to 0.4 tmol/l υ
, and 0.0j to 0.0j in the bleach-fix solution. J-mol/1. Preferably it is θ, /NO, 3 mol/l'''C. In addition, in the bleach solution or bleach-fix solution for color photographic light-sensitive materials for printing such as color paper, it is 0.03 to 0.
．． 3 mol/1. Preferably -≠water is 0.0j to 0.2 mol/l.

Further, a bleach accelerator may be used in the bleaching solution or bleach-fixing solution, if necessary. Specific examples of useful Hiko bleach accelerators include compounds having a mercapto group or disulfide group as described in Research Disclosure A/7/λ (July 1971); JP-A-60-14)0
Thiazolidine derivatives as described in No. 122; Tokko Sho≠yo-rjot, U.S. Patent No. 3,70t, it1
Thiourea derivatives described in West German Patent No. 1. /, 27°7 No. J, Iodides described in JP-A-31-/1,23t; Polyethylene oxides described in West German Patent No. 2.74t♂, 'l-30; -11? Polyamine compound described in No. 36; Other JP-A-Sho μter l/-2
Examples include the compounds described in μ3 Hiro issue and 11-/13 ≠ θ issue, as well as iodine and bromine ions. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat.
Zari 3. Itr No., West German Patent No. 1. ．． 290. , S'/
, No. 2, %[-! Compounds described in No. O-j3-tajtJO are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide C.
Re-logenating agents such as potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, as required
Addition of one or more inorganic acids or organic acids with pH buffering ability such as phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate or guanidine. can do.

The fixing agent used in the bleach-fixing solution or fixing solution of the present invention is:
Known fixing agents, i.e. thiosulfates) Thiosulfates such as IJium, ammonium thiosulfate; Thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylene bisthioglycolic acid, j, J-dithia-/,
! - water-soluble silver halide solubilizers such as thioether compounds such as octanediol and thioureas;
Seven types or a mixture of 28 or more types of these can be used. Also, JP-A-11-/1j3! It is also possible to use a special bleach-fixing solution consisting of a combination of the fixing agent described in ≠ and a large amount of a halide such as potassium iodide. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of the fixing agent equivalent to 11 is preferably 0.3 to 2 moles, and particularly in the processing of color photographic materials for photographing, o, t to
/, 5 mol, and in the processing of color photographic materials for printing, the range is 0.3 to 1 mol.

The pH range of the bleach-fix solution or fix solution in the present invention is 3 to 3.
IO is preferred, and j to ri are particularly preferred. If the pH is lower than this, the desilvering performance will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if the pH is too high, desilvering is delayed and staining is likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, and the like.

The bleach-fixing solution and fixing solution of the present invention contain sulfite (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (e.g., ammonium bisulfite, bisulfite), potassium bisulfite, etc. as preservatives. , etc.), metabisulfite C (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabinitrite, etc.). These compounds are approximately 0.0.2 to 0.02 in terms of sulfite ion.
It is preferable to contain 0.10 mol/, more preferably 0.0 to 0. μ0 mol/l.

-j 3- As a preservative, sulfite is commonly added, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

Examples of the photosensitive material used in the processing method of the present invention include black and white paper, black and white negative film, X-ray photosensitive material,
Examples include photosensitive materials for printing, color paper, color negative film, color reversal film, direct positive color Beno ξ-1 direct positive color film, and reversal color paper.

First, as a color paper, silver chlorobromide having a silver bromide content of lθ molar or higher is used. In addition, in order to obtain an emulsion with sufficient sensitivity without increasing fog, the beautifying silver content should be 20.
Although it is preferable to use a molar coefficient of at least 10 molar coefficient or less, if speed is particularly required, it is possible to use a molar coefficient of 10 or less or j molar coefficient or less.

In particular, an emulsion close to pure silver chloride with a molar ratio of 1 molar or less is preferred because rapid development is possible.

-J-≠- In addition, the photographic emulsion layer of the color negative film used in the present invention contains silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Silver may also be used.

Preferred silver halides are silver iodobromide or silver iodochlorobromide containing less than 30 molar ratios of silver iodide. Particularly preferred is 2. from the λ molar coefficient. It is silver iodobromide containing up to 1000 molar silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.

The grain size of silver halide is 0. The emulsion may be fine particles of less than 10 microns or large particles with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

In addition, as a monodispersed emulsion, silver halide grains with an average direct grain size of about 0.001 microns or more are used, and at least about 1.0 microns of silver halide grains are used. Emulsions in which the weight percent of the average grain is directly within Shihiro 04 are representative. The average particle diameter is about 0.2! ~- It's micron, at least about it! Silver halide grains of at least about 100% by weight or quantity are added to the average grain direct ratio λ.
Emulsions having a θ coefficient within the range can be used in the present invention.

By using tabular grains in the halogenated photographic emulsion used in the present invention, it is possible to improve sensitivity including improvement in color sensitization efficiency by sensitizing dyes, improve the relationship between sensitivity and graininess, improve sharpness, and improve development progress. Improvements in performance, covering power, crossover, etc. can be achieved.

Here, tabular silver halide grains are those whose diameter/thickness ratio is 1 or more, for example, those whose diameter/thickness ratio exceeds t! There are more than r and less than r.

Generally, tabular silver halide grains are tabular with two parallel planes, and therefore the above-mentioned "thickness" is expressed as the distance between the λ parallel planes constituting the tabular silver halide grain.

Regarding the proportion of tabular silver halide grains in the emulsion containing the tabular silver halide grains used,
For the total projected area! It is preferably 0 or more, and more preferably 70'A or more. Especially 904
It is preferable that it is r or more.

The halogen composition of the tabular material is preferably silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride, or silver iodochloride. Silver iodochloride is particularly preferred for use in high-sensitivity photosensitive materials.

one! 7- Silver halide emulsions are usually chemically sensitized.

Chemical sensitization is described by T. H. James,
The Photographic Ink Process, 1st edition, Macmillan Publishing, 1977, (T. H. James.

The Theory of the Photo
graphicProcess, ≠th ed, M
pA can be carried out using activated gelatin as described in p.
g'~io, pHt-r and temperature 1o-ro 0c
sensitizers such as sulfur, selenium, chill layers, gold, platinum, noradium, iridium, or combinations of these sensitizers. Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, and as described in U.S. Pat.
, 117, 7//, 1/-, 21, A, 0/lr, and sulfur-containing compounds or hypo, thiourea-based compounds, rhodanine-based compounds, etc., described in 1/-, 21, A, 0/lr and 57. in the presence of sulfur-containing compounds. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. Chemical sensitizing aids used include azaindene, azapyridazine, azapyrimidine, and other compounds known to suppress fog and increase sensitivity during the chemical sensitization process.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Spectral sensitizing dyes are generally added to chemically sensitized emulsions before coating. U.S. Patent No. g, 4', 2j.

No. 1126 discloses a method of adding it to an emulsion before or during chemical sensitization. In addition, a method of adding a spectral sensitizing dye to the entire emulsion before the formation of silver halide grains is completed is described in U.S. Pat. Chapter 44.11
No. 3.71j, and U.S. Pat. No. 1I, 221. ttt
Disclosed in the issue.

The silver halide photographic emulsion used in this technology may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or to stabilize photographic performance. can.

All of the various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
It is described in the patents listed in RDJA/74FJ, ■-C to G. As the dye-forming coupler, it is important to use a coupler that can be formed by full color development of the three primary colors (i.e., yellow, magenta, and cyan) using the subtractive color process, and a diffusion-resistant,
Specific examples of ≠equivalent or monoequivalent couplers are given in RD/7 Bug 3. In addition to the couplers described in the patents described in Sections 1-C and D, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-piparoylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic j-pyrazolone and pyrazoloazole couplers that have a ballast group.

! - As the pyrazolone coupler, a coupler in which the 3i-position is substituted with an arylamine group or an acylamino group is preferable from the viewpoint of the hue of the coloring dye and the coloring density.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol couplers and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. Couplers that form cyan dyes that are also humidity and temperature fast are preferably used, exemplified by the phenol-nucleated meta-j/- couplers described in U.S. Pat. No. 3,772,002. A phenolic cyan coupler having an alkyl group of ethyl or higher in the 1-position, a co-, and tertiary acylamino-substituted phenolic coupler having a phenylureido group in the co-position and! A phenolic coupler having an acylamino group in the - position, described in European Patent No. 11/B2tA! - Amidonaphthol cyan couplers, etc.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Specific examples of such couplers are described in U.S. Pat. has been done.

Dye-forming couplers and special couplers mentioned above are 21.
It is also possible to form a polymer containing more than 100% of the total number of polymers. Typical examples of polymerized dye-forming couplers are described in US Pat.

Specific examples of polymerized magenta sol are disclosed in US Pat. No. 11. It is described in Jt7,212, etc.

Couplers that release all photographically useful residues upon co-coupling are also preferably used in the present invention. The DIR coupler that releases all of the development inhibitor is the above-mentioned RD/7t4tj,
The couplers described in Sections (1) to (F) and disclosed in the FC patent are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds are given in British Patent No. J, 7゜iao, British Patent No. 2. /J/
, /lr issue. Others, Tokukai Sho AO-/
DIR redonx compound releasing couplers described in I Tatata O et al., European Patent No. 773. Couplers that release dyes that recover color after separation, such as those described in No. zo and zA, can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Patent No. 2, J22.02.
It is stated in issue 7 etc.

Further, the process and effects of the latex dispersion method, and specific examples of the latex for impregnation are described in US Patent No. 1 Tata.

Jtj No., West German Patent Application (OLS) No.! , Tahiro/.

No. 27≠ and No. 2 of the same. Ta≠/, 2iO, etc.

The light-sensitive material produced using the present invention includes, as a color antifogging agent or color mixing inhibitor, no-idroginone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol visiting conductors, ascorbic acid derivatives, colorless couplers, It may also contain sulfonamide phenol derivatives and the like.

Known anti-fading agents can be used in the photosensitive materials that can be used in the present invention. Known anti-fading agents include hydroquinones, o-hydroxychromans, terhydroxycoumarans, spirochromans, p-alcotine phenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methine/ Typical examples include dioxybenzenes, amine phenols, hindered amines, and ether or ester/L/derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds.

In the photosensitive material that can be used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

For example, U.S. Patent No. 3. Benzotriazoles substituted with aryl groups as described in US Patent No. 3,77, etc., US Patent No. 3,2/! .

Examples include benzophenones described in No. 130.

The photosensitive materials that can be used in the present invention are used for various purposes such as coating aids, antistatic properties, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). It may also contain a surfactant.

The photosensitive material that can be used in the present invention may contain a water-soluble strip l#+w in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, steryl dyes, merocyanine dyes, anthraginone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmeth/dyes, and phthalocyanine dyes are used. Dyes are also useful. The oil-soluble dye can also be emulsified by an all-in-water oil droplet dispersion method and added to the hydrophilic colloid layer.

In the photosensitive material that can be used in the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic photosensitive layer or puncture layer. Active halogen compound (2, goudichlor-2-hydroxy-/
, 3. tartriazine) and active vinyl compounds (such as tartriazine) and active vinyl compounds (such as
/, 3-bisvinylsulfonyl-λ-propertool, /
, 2-bisvinylsulfonylacetamidoethane or vinyl polymers having a vinylsulfonyl group in the side chain) are preferable because hydrophilic colloids such as gelatin can harden quickly and stabilize photographic properties.

A variety of exposure means can be used for photosensitive materials. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-fired 7 lash pulses are common. Gas, dye solution, or semiconductor lasers that emit light in the wavelength range from ultraviolet to infrared;
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, fluorescent surfaces (such as CRTs), liquid crystals (LCDs, etc.) emitted from phosphors excited by electron beams, etc.
) and lanthanum-doped lead titanium zirconate (
It is also possible to use an exposure means in which a linear or planar light source is combined with a micro-shutter array using PLZT) or the like. Adjust the spectral distribution used for exposure using color filters as required.

(Examples) The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example/ On a subbed cellulose triacetate film support,
A sample of a multilayer color light-sensitive material having each layer having the composition shown below was prepared.

(Composition of the photosensitive layer) The coating amount is expressed in units of g/m2 of silver for silver halide and colloidal silver, and in g/m2 units for couplers, additives and gelatin. The sensitizing dyes are expressed in moles per 7 moles of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver...0.2 gelatin
...1.3 coupler C-/
... o, ot ultraviolet absorber UV-/ ...
・0. /Same as above UV-2...0.2 Dispersion oil 0il-/...o, oi6 r- Same as above Oi]-2...0.0/Layer λ (intermediate layer) Fine grain silver bromide (average grain Diameter 0.07μ) ...0. /! gelatin
...Φ/, 0 coupler C-2...0.
02 Dispersion oil 0ff-/...0. /Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 molar ratio, diameter/thickness ratio λ, j
, average particle size 0.3μ, internal high AgI type)...Silver 0.4L Gelatin...0.1 Sensitizing dye■
.../, O x 10' sensitizing dye ■
...J, O x 10' sensitizing dye■...
・・・/×10-5 coupler C-J ・・
・o, ot coupler C-Hiroshi ・・・o, ot
Coupler cr...O, O4A Coupler C-1...0.93-t Tar dispersion oil 0il-/...0.03 Same as above
0i1-j...0.0/2nd layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide j molar ratio, diameter/thickness ratio, O
1 Average particle size 0.7 μ, internal high AgI type) ... Silver 0.7 Sensitizing dye I ... / x 10-' Sensitizing dye ■ ... 3 x 10 ' Sensitizing dye ■
...Ixlo-5 coupler C-j
...0.2≠Coupler〇-≠・
...O, Kohiro coupler cr...0.
0≠Coupler C-2...0.0μ Dispersion oil 0il-/...0. /j Same as above
0i1-3...0.0.2 j-th layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mmolar diameter/thickness ratio/,
J, average particle size o, rμ, internal high AgI type)...Silver i,.

Gelatin.../, 0 Sensitizing dye I
...／×10' Sensitizing dye■
...Ex10' sensitizing dye■
.../x10-5 coupler C-1...0.0! Coupler C-7...0. / Dispersion oil 0il-/ ...0.0/ Same as above
0il-2...o, 'or 6th layer (middle layer) Gelatin...1. θ compound cpc
t-A...0.03 Dispersion oil 0i
l-/...0.02 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide 2 molt, diameter/thickness ratio,
j, average particle size 0.3 μ, internal high AgI type) ... silver 0.3 sensitizing dye ■ ... J × 10 'sensitizing dye ■ ... o, 3 × io ' sensitizing dye ■
...Co x 10' gelatin
.../, 0 coupler C-ta ・
・・Oo, 2 coupler C-j ・・0.0
3 coupler C-/...0,0.3 compound Cpd-C...θ, oiλ Dispersion oil Oil...0.2 r-th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (iodobromide emulsion) Silver oxide ≠ Morch, diameter/thickness ratio ≠, O
1 Average particle size o, tμ, internal high AgI type) ...Silver O9≠ Sensitizing dye ■ ...jxIO' Sensitizing dye ■
・・・ko×io 'sensitizing dye■
・・0.3×10′ coupler C-ta
...0.2! Coupler C-/・
...0.03 Coupler C-10...0. θlj Coupler C-J-...o, oi Compound cpci-c...O6θ/Co-dispersed oil 0il-/...0.2 Second layer (third
Green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide t morch, diameter/thickness ratio/, 2
, average particle size i, oμ, internal high AgI type) ... silver 0. Ij gelatin.../, 0 sensitizing dye■
...3. jxlo 'sensitizing dye■
...lgo×io 'Coupler C-/J
... o, oi coupler C-/2 ...
0.03 Coupler C-ta...0.20
Coupler C-/...0.02 Coupler C-/j...0.02 Dispersion oil 0il
-/...-0,20 same as above 0il-2...
・o, or I/O layer (yellow filter single layer) Gelatin...7.2 Yellow colloidal silver...o, or compound cpct-B
...o, i Dispersion oil 0il-i
...0.3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide emulsion, diameter/thickness ratio/, j, average grain size O0 jμ, internal high AgI type ) ...Silver O1≠ Gelatin .../, 0 sensitizing dye ■
... rice l0-4 coupler C-/≠
...O, Ta coupler C-t...
・0.07 dispersion oil 0il-/ ...Ol,
2 First co-layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mole, diameter/thickness ratio ≠,
! , average particle size/, 3μ, internal high A g type I)...Silver o, 4t Gelatin...o, sensitizing dye ■
.../×10 'Coupler C-/4'
...0.2! Dispersion oil 0il-/
...0.07-7 Goo 13th layer (first protective layer) Gelatin ...: o, ir Ultraviolet absorber UV-/ ...o, i Same as above UV-2
...0.2 Dispersion oil 0il-/ ...0.0/Dispersion oil 0il-2...o, o, i 1st layer (1st layer) Fine silver bromide (average particle size 0.07μ) ・ ・ ・ O, j Gelatin ...O1≠! Polymethyl methacrylate particles (diameter/, jtμ)...Oo, 2 Hardener H-/...O6≠n-butyl p-hydroxybenzoate -0,0/ Coformaldehyde scavenger S-/...・ ・ O
,! Formaldehyde scavenger S-2 fist...0. j In addition to the above components, a surfactant was added to each layer as a coating aid.

Next, an antistatic layer having a different composition as shown below was coated on the support opposite to the emulsion layer to prepare sample/-10.

(Inner layer) Cationic polymer compound Compound, coating amount is listed in Table 1 Gelatin o, 2y/rn2 (Outer layer) 5i02 particles with average o, opμm 1jW9/rIL
21-Methylamino-≠-(4A-methylphenyl)aminoanthraquinone 10 da/m 2≠-
((≠-(N,N-diethylamino)-cometerphenyl)imino)-x-(N-phenylamino)carbonyl/,44-naphthoquinoy 10q/rn"Diacetylcellulose 1701v/WL2 gelatin/0.2 Next, the chemical structural formulas or chemical names of the compounds used in this example are shown below; bis(,2-ethelhexyl)C-/('-J C-≠ 17ter-z H3 t-Jro-C-tamol, wt, about xo, oo.

c-i.

14/- C-/I C-/ λ C-/3 α C-/ ≠ ra - C-/J Cpd-A Cpd-B pd-C ra- Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ K 7- H-/ S-/ -T rr- Regarding the sample /-10 prepared as above, the opposite side of the emulsion layer The surface resistance of the side layer (pack layer) was measured. These results are shown in Table 2.

As is clear from Table 2, in samples 3 to IO of the present invention,
The surface resistance value is almost preferable for antistatic purposes/x10
However, the surface resistance value of sample t, which had a small amount of cationic compound added, was slightly larger.

Next, sample 3! After cutting the sample to a JJX width, a standard subject was photographed outdoors, and each sample (300 m) was individually processed using an automatic developing machine (Fuji Color Negative Processor FP-JJO, manufactured by Fuji Photo Film) using the method described below. I processed it like this.

Table 3 Process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes/j seconds JJroC4! ! mI
10L bleach 7 minutes θθ seconds 310C2owl
4AL bleach fixing 3 minutes/j seconds 3t0C3o
rnl IL water wash (2) 1 minute oo seconds Jj'
CJOrnl Hiro stable ao second J
lr'C20rnl 4) L drying 1 minute l
! Second jj0C The replenishment amount is 33 mm wide and 7 m long.Next, write down the composition of the processing solution.

(color developer) mother solution replenisher) diethylenetriaminepentaacetic acid i, o /, //-
Hydroxyethylidene-3,036,21,/-diphosphonic acid sodium sulfite ≠, O≠, ≠potassium carbonate 30.0 37.0 Potassium bromide /, ≠ 0.7 Potassium iodide
1. ! η -Hydroxylamine sulfate
Ko, 4t λ,? ≠-[N-ethyl-N-(β-μ
,,t j,jhydroxyethyl)amino] Add monocomethylaniline sulfate solution /,OL /,0Lp
H10, Oj 10.10 (Bleach solution) Common to mother liquor and replenisher (unit: g) Ferric ethylenediaminetetraacetate /20.0-thalammonium dihydrate Ethylenediaminetetraacetic acid disodium 10.0 Lium Ammonium chloride bromide 100.0 ammonium nitrate /θ,θ bleach accelerator
0.00j mole ammonia water (,z7%
) ts, ovLl add water
1. θpHt, 3 (Bleach-fix solution) Mother liquor @ Replenisher ω Ethylenediaminetetraacetic acid 20.0 -Diferric ammonium dihydrate Ethylenediaminetetraacetic acid dihydrate 3.0 0. ! Sodium salt Sodium sulfite /2.0 20,0-taλ- Ammonium thiosulfate aqueous solution, 2≠0.0d≠oo, o
ml solution (70%) ammonia water (27%) g, od - add water /, OL 1.0L pH 7
,2r,0 (Stable solution) Common to mother solution and replenisher solution (unit: g) Formalin (
37%) Co, Oml polyoxyethylene-p-mono 0.3 nonyl phenyl ether (
Average degree of polymerization 10) Ethylenediaminetetraacetic acid disodium 0.03 Lium salt water added /, 0L pH 1
,0-1,0 The following A and -C were used as the washing liquid.

(Washing liquid A) Mother liquid and replenisher common (Washing liquid B Invention) Mother liquid and replenisher common The above tap water was mixed with H-type strongly acidic cation exchange resin μ0o1nl (Amberphyto IR-/2θB manufactured by Rohm and Haas) and OH
Type anion exchange resin too door l (same amber light IR
Calcium and magnesium ion concentrations were treated as follows by passing water through a mixed bed column packed with 20% sodium isocyanurate dichloride/L and sodium sulfate at a rate of 31/min. o, lsy/l was added.

Calcium ≠, j~/l Magnesium ≠, /da/l (Washing liquid C of the present invention) The above tap water is common to the mother liquor and replenisher solution.
(Type Strongly Acidic Catheo/Replacement Resin 4tOOml (Rohm and Haas An/ζ-Light JR-/20f Rito, O
A mixed bed column packed with 1*00 ml of H-type anion exchange resin (Amberlite IR-daoo) was heated at
．． Calcium and magnesium ion concentrations were treated as described below by passing water at a rate of 0.31%, followed by 2oq/L of sodium incyanurate dichloride and 0.31% of sodium sulfate. /
jf/l was added.

Calcium /, θ■/l Magnesium Q, 3 da/l In the treatment of each sample, all treatment solutions were started from a new solution state.

Table 1 shows the dirt on each sample and the state of floating matter in the washing bath at the end of the 300 m treatment.

As shown in Table 1, in the comparative example, there was significant staining of the sample and occurrence of floating matter in the washing bath, but according to the present invention, these problems are almost eliminated and the washing liquid is The purpose of the present invention can be achieved by greatly reducing the amount of replenishment.

Example - λ.

Example-1, sample 3 and sample 3rd layer, 3rd layer coupler C-J, C-g to C-/l, C-J to C-/7, C-j to C-/ Sample/I by changing equimolar amounts of each
l, /2. Next, sample 3, ≠, /l, /co was photographed as a standard subject outdoors, and 300 m of each sample was processed using an automatic developing machine (Fuji Color Negative Processor,
pp-310 (modified machine) and processed by the method described below.

C-/A-Tar-Table 5 Process Processing time Processing temperature Replenishment amount Tank capacity Color development 2 minutes 30 seconds uooc 10
w1 rLL white fixing 3 minutes 00 seconds uOo
C2oml fL water washing (1) 2o seconds
2L counter-current piping type from 3j0C (2) to (1).

Wash with water (2) 20 seconds Jj'C1Ornl
2L stable 2Q seconds 3j0Ciod
-2L dry go seconds 4j'C Refill amount is 3! IuI width/rn length In the above treatment, all the overflow liquid from water washing (1) accompanying replenishment was introduced into the bleach-fixing bath.

Next, the composition of the treatment liquid will be described.

(Color developer) Mother solution ω Replenisher ω Diethylenetriaminepentaacetic acid 2.0 2.21-Hydroxyethylidene-3,03,2i,i-diphosphonic acid sodium sulfite G, θ! , j Potassium carbonate 30.0 ≠ 2.0 Potassium bromide /, ≠ - Potassium iodide
l, j■ -Hydroxylamine sulfate λ, ≠ 3.0 hiro-[N-ethyl-N-(β hiro,
J' 7.7-Hydroxyethyl)amino]-comethylaniline sulfate solution added /, OL /, 0Lp
H10, oz lo, 2° (bleach-fix solution) Common to mother liquor and replenisher (unit: g) Ferric ethylenediaminetetraacetate TaO0O Ammonium dihydrate Ethylenediaminetetraacetic acid disodium j, Olium salt Sodium sulfite 12.0 Ammonium thiosulfate Aqueous solution, 2tO, θp (7o%) acetic acid, own bleach accelerator, o, oi mol water added, i, oLpHt,.

(Stabilizing solution) Common to mother solution and replenisher solution (unit: g) Formalin (
-77%) Polyoxyethylene-p-mono 0.3 nonyl phenyl ether (average degree of polymerization/(7) ethylenediaminetetraacetic acid) Add 0.01 lium salt water /, 0L pH,
or, θ In addition, the following E and E were used as the washing liquid.

(Washing liquid D) Mother liquid and replenisher common (Washing liquid E, present invention Mother liquid and replenisher common) The above tap water was treated by the method described in Example -/Washing liquid C, and then a micro filter FCE manufactured by Fuji Photo Film ■ was used. -4jW was filtered and used.The calcium and magnesium concentrations of the water are as follows.

Calcium /, ♂η/l Magnesium 0.7my//1 In each treatment in the above method, all treatment liquids are started from a new liquid state, and the stains on each sample at the end of 300m treatment are 1. The increase in stain and the state of floating matter in the washing bath are shown in Table 1.

-1os- In the above table, Stain is the minimum cyan density (red light transmission density) of the sample at the start of processing and at the end of 300m processing.
It shows the change in the measured value of .

The measurement was carried out using an X-Rite JIO type densitometer.

Note that the display of dirt on the sample and floating matter in the washing bath is the same as in Example-1.

As shown in Table 1, according to the present invention, there is no dirt on the sample, there is no floating matter in the washing bath, and there is only a slight stain on the sample, so an excellent effect can be obtained.

Example 3, Example 7, Sample 3, and 1 were carried out in the same manner except that the following treatments were used. As a result, the present invention showed excellent effects almost the same as in Example 1.

-IO'l- Table 7 Process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes l! Second J7. roCll0nl
10L bleach 3 minutes 00 seconds 3710Cj
ynl 10L fixed μ minute 00 seconds, 3
710C201ttl 10L stable (2)
≠j seconds 3J, 00C, tL stable (3)
F, seconds Jj, 00C20m1 [.

Drying 1 minute 20 seconds 11. Q°C The amount of replenishment was per Jjtm width and 7 m length, and all of the over 70 - of the stabilizing solution accompanying replenishment was introduced into the fixing bath.

Next, the composition of the treatment liquid will be described.

(Color developer) Mother solution ω Replenisher ω Diethylenetriaminepentaacetic acid it, Ot, θ Sodium sulfite G, Oa, ≠ Potassium carbonate
30.0 37.0ioz- Potassium Bromide /, 3 θ,? Potassium iodide 7.2-hydroxylamine sulfate 2. θ 2.1 goo [N-ethyl-
Add N-(β4',7!,3-hydroxyethyl)amino]-λ-methylaniline sulfate solution /, OL /, 0Lp
l(10,0010, Oj (bleaching solution) Mother liquor (g) Replenisher ω Ethylenediaminetetraacetic acid 70.0 /20.0 diiron ammonium dihydrate/, 3-diaminopropane 31.θ, 12,0 tetraacetic acid Ferric salt ethylenediaminetetraacetic acid ≠, θ!, O ammonium bromide ioo, otto,.

Ammonium nitrate 30. OjO,0 ammonia water (27%) so, oml, z3. oml
Add water /, OL /, 0L
pHz, z ≠, j (Fixer) Mother solution (g) Replenisher (g) Ethylenediaminetetraacetic acid 0. I O,7 Disodium Salt Sodium Sulfite 7. Or, 0 Sodium bisulfite j, Oj, j Ammonium thiosulfate aqueous solution /70.0 tnl, 200.0 ml liquid (70 sections) Add water /, OL /, 0 L
The following F and G were used as pH 4, '7 +, + stabilizing solutions.

(Stabilizing Solution F) The following stable solution was prepared using tap water containing 3 tw/l of calcium and r/l of magnesium.

Formalin (37ti) 1.2 yo-chloro-2-methyl-4t-5o dainthiazoline-3-oncomethyl-≠-inthiazoline 3.0 3-one surfactant o,ti ethylene glycol i.

Add water (tap water) t, oLpH!
, 0-7.0 (Stabilizing liquid G, present invention) The above-mentioned stable liquid was prepared using water that had been ion-exchanged by the method described in Example 1, Washing liquid C.

Calcium in the ion-exchange treated water was 2.7 W/l, and gnesium was 7 mg/71.

ioi-

Claims (6)

[Claims] (1) After processing a silver halide photographic light-sensitive material containing a cationic polymer compound on the support with a bath having fixing ability, 1 of the amount brought in from the previous bath per unit area of the light-sensitive material
In a method of processing with a washing bath and/or stabilizing bath that replenishes ~50 times, the concentration of calcium compounds and magnesium compounds in the replenishing solution refilled to the washing bath and/or the stabilizing bath is as low as calcium and magnesium. A method for processing a silver halide photographic material, characterized in that the content of each silver halide photographic material is reduced to 5 mg/l or less. (2) The treatment method according to claim 1, wherein the concentration of calcium compounds and magnesium compounds is reduced by the following method (a) and/or (b). (a) A method of bringing the water used for replenishment into contact with an ion exchange resin. (b) A method of passing water used for replenishment through a reverse osmosis membrane. (3) The processing method according to claim 1, wherein the bath having fixing ability is a bleach-fixing bath. (4) The treatment method according to claim 1, wherein the replenisher and/or the water used for the replenisher is sterilized by at least one method described in (c) and (d) below. (c) Addition of a compound with bactericidal action (d) Filtration through a filter with a pore size of 0.8 microns or less (5) The washing bath or the stabilizing bath is composed of two or more tanks, and the overflow liquid generated by replenishing the last tank sequentially flows into the front tank, which is a countercurrent replenishment system.Claim 1 Treatment method described in section. (6) The processing method according to claim 1 or 3, characterized in that an overflow liquid generated during replenishment is introduced from the washing bath and/or the stabilizing bath into a bath having fixing ability.