JPS62134646A - Storage pack for photographic processing liquid - Google Patents

Abstract

PURPOSE:To obtain a storage pack which preserves stably a photographic processing liquid and does not require complicated dissolving works and capable of constitute a waste liquid recovery system free from failure, by arranging a flexible synthetic resin film having a prescribed property so that this film faces the surface of a partitioning film which separates a processing liquid supply chamber and a waste liquid chamber from each other in the photographic processing liquid storage pack. CONSTITUTION:A photographic processing liquid storage pack 1 consists of a flexible bag body, and the inside is divided into a photographic processing liquid supply chamber 2 and a waste liquid chamber 3 by a partitioning wall 1A. The edge of a square flexible film F2 forming the partitioning wall 1A is sealed along the edge of a square flexible film F1 having a through hole for an aperture 4 and an aperture 5 by a seal S. In such a case, liquid absorbing and expanding materials 6 are interposed on demand. The aperture 4 of the film F2 pierces the through hole of the film F1 and is sealed in this state by the seal S to form the waste liquid chamber 3. Next, a flexible film F3 forming the supply chamber 2 is sealed by the seal S. Films F1 and F2 consist of a flexible synthetic resin film having <=20ml/m<2>/24hr oxygen permeability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improved photographic σ8 processing agent composition storage pack. More specifically, it relates to a container for storing a compounded photographic processing agent composition, which has a long service life even when containing an unnecessary photographic processing solution, and which facilitates the disposal of waste liquid. This relates to a liquid storage pack.

Many of the photographic processing liquids used when exposing photographs to produce phenomena have redox properties and are generally susceptible to air oxidation.

For example, since developing solutions and color developing solutions are easily oxidized by air, sulfite is added as a preservative to help warm up the degree of oxidation. Also, to prevent the fixing agent, sodium thiosulfate, from decomposing due to air oxidation in the fixing solution or bleach-fixing solution and releasing sulfuric acid, causing a serious accident, sulfite is added to prevent air oxidation. Furthermore, in waterless cleaning stabilizers, the anti-piping agent easily deteriorates due to air oxidation.
This is often prevented by adding sulfite to the same tower. Even if these treatment solutions are prevented from air oxidation using sulfites as described above, they cannot be used in conventional kit containers such as polyethylene bottles or polyethylene film bags (flexible containers called by trade names such as Shorey Bag). However, if the treatment liquid is prepared and kept at the point of use, it will not withstand storage for more than two weeks and will deteriorate due to oxidation. It was supplied in a treatment composition called a pre-mixed kit, which was dissolved in water and used in a short period of time.

[Problem that the invention seeks to solve]

Therefore, at each current location, one processing solution must be dissolved using a plurality of sachets, which is a troublesome task.

Generally, each sachet cannot be immersed in the next sachet until it is completely dissolved, and the patient must wait while stirring for several minutes or even tens of minutes. However, it required a considerable amount of manpower. In particular, as simple automatic processing machines and processing machines for minilabs and copymanon-like distributed processing become available, it is easy for complete amateurs to misunderstand the names and distinctions of complex kits packaged in many containers. A number of problems have begun to occur in fabrics due to dissolution that seriously impede photographic performance, and this problem is becoming more and more apparent as the work shifts from specialized phenomenon processing workers to camera store clerks.

Furthermore, as processing becomes waterless, many automatic processing machines have come on the market that eliminate the need for drain pipes and allow the overflow of each processing solution to be collected in a dedicated waste tank. This is very desirable in terms of pollution prevention, but when the waste liquid tank is full, a buzzer goes off.Although safety measures have been taken, I accidentally turn off the alarm buzzer when the waste liquid tank is full. There have been many cases where people forget to replace the fluid and the waste fluid overflows, staining the floor and leading to serious accidents.

Therefore, in the era of decentralized photographic processing, users need a highly amateurish processing solution supply that eliminates the troublesome and easy-to-make mistake-prone kit dissolution work that consists of complicated packages, and allows them to work with peace of mind without having to worry about waste solution management. It can be said that there is a strong demand for a storage pack for photographic processing solutions that is both a system and has a high shelf life for processing solutions.

Therefore, the first object of the present invention is to provide a storage pack for a photographic processing solution that has high storage stability;
Second, it does not require complicated disassembly work. Third, it provides a storage pack for photographic processing liquid that can be assembled with a waste liquid recovery system that is completely error-free.

[Means for solving problems]

As a result of extensive studies, the present inventor has found that in a flexible pack for storing a photographic processing solution for a silver halide photographic light-sensitive material, the pack has at least two compartments separated by a diaphragm,
One of the compartments is a supply chamber for photographic processing solution, and the other is a waste solution chamber, and at least the membrane forming the self-recording photographic processing solution supply chamber and the membrane on the surface facing the front μ diaphragm is oxygen permeable. The volume is 20ml! /m'/24t (r or less), and is made of a flexible synthetic resin film having a diameter of less than r, and at least one side of the photographic processing solution supply chamber is covered with waste liquid collected in a waste liquid chamber. The inventors have discovered that the above object (technical problem) can be achieved by a liquid storage pack, and have arrived at the present invention.

In a preferred embodiment of the present invention, (1) the storage pack is composed of at least three flexible synthetic resin films, at least one of which is a diaphragm, and constitutes a photographic processing solution supply chamber. (2) One entire surface of the diaphragm is a photographic processing solution supply chamber, and the other entire surface is a waste liquid chamber. (3) The surface facing the diaphragm constituting the photographic processing solution supply chamber is composed of at least 25 flexible synthetic resin films, and at least 611 of the layers excluding the innermost layer are made of EVAL, aluminum foil, etc. (4) The diaphragm is made of a flexible synthetic resin film with an oxygen permeability of 20 mQ/m"/24 Hr or less; (5) The diaphragm is made of a flexible synthetic resin film of at least 25 At least one layer excluding the outermost stone is made of EVAL, aluminum foil, or aluminum vapor-deposited synthetic resin film.

By the way, Japanese Patent Application Publication Nos. 55-55942 and 56-131
No. 155, No. 58-52065, and Utility Model Publication No. 1982-94
Japanese Patent No. 754 discloses a technique in which one pack is divided into two by a diaphragm. According to these technologies, the processing solution supply pack and waste solution storage pack can be provided in one pack, which certainly reduces the amount of acid in the space, but it is not possible to maintain the storage stability of the photographic processing solution. .

Embodiments of the present invention will be described below with reference to the accompanying drawings.

1 and 2 are cross-sectional views showing one embodiment of the present invention, and FIG. 1 shows a photographic processing solution stored in a supply chamber;
Fig. 2 shows a state in which waste liquid is stored in the waste liquid chamber, and Fig. 2 shows a state in which waste liquid is collected in the waste liquid chamber.

In FIGS. 1 and 2, l is a storage pack, and the storage pack l is a flexible bag made of resin. It is divided into two parts: 3. Reference numeral 4 designates an opening provided in the supply chamber 2 for photographic processing liquid, and 5 designates an opening provided in the waste liquid chamber 3.

The details of the structure of the embodiment shown in FIGS. 1 and 2 are as follows.

That is, from the manufacturing example, first, along the edge of the rectangular flexible film Fl having the through hole for the opening 4 and the opening 5,
The edges of the rectangular flexible film F2 forming the diaphragm IA are sealed S. At this time, a liquid-absorbing and swelling substance 6 is interposed as necessary. What is the opening 4 in the rectangular flexible film F2?
It is sealed S while penetrating the through hole 1. As a result of the above, a waste liquid chamber 3 is formed in which a liquid-absorbing and expanding substance 6 is provided as required. Then the flexible film F forming the supply chamber 2
3 is sealed S. In addition, it is preferable that the openings 4 and 5 have screws in order to attach a lid.

In the present invention, as the photographic waste liquid stored in the waste liquid chamber 3, for example, the ratio ff11. Photographic processing solutions such as o1 or higher black and white developer, color developer, fixer, bleach-fixer, bleaching solution, stabilizer, stop solution, image stabilizer, rinsing solution, water-washing substitute stabilizer, etc. after photographic material processing. There may be a mixture of one or more of these liquids, but if necessary, the liquid may be drained for reuse.

On the other hand, the photographic processing liquid stored in the supply chamber 2 is the various photographic processing liquids themselves.

Below, among these photographic processing solutions, the photographic processing solutions particularly preferably used in the present invention include a black and white developer, a color developing solution, a fixing solution, a bleach-fixing solution, a bleaching solution, and a water-washing substitute stabilizing solution. It is particularly preferable to apply to processing liquids containing preservatives such as sulfites and hydroxyamines that are easily oxidized by air, developing agents, thiosulfates, anti-high agents, etc., and especially applicable to processing liquids containing sulfites. It is preferable to
.

The black-and-white developer uses at least one black-and-white developing agent selected from hydroquinones, 1-phenol-corbyrazolitons, and paraaminophenols.

Examples of hydroquinones include T, tl, and James.
s by r The Theory of The P
oLographic Process (1977)
Compounds described on pages 100 to 311 of "" can be used, specifically hydroquinone, methylhydroquinone, 2.3-dimethylhydroquinone, 2.5-
Dimethylhydroquinone, 2,3゜5-trimethylhydroquinone, tetramethylhydroquinone, 2.6-
Dimethylhydroquinone, methoxyhydroquinone, 2
．． 5-dimethoxyhydroquinone, 2-chlorohydroquinone, 2,3-dichlorohydroquinone, 2,5-
Dichlorohydroquinone, 2,6-dichlorohydroquinone, aminohydroquinone, bromohydroquinone,
Hydroxyhydroquinone, t-butylhydroquinone, phenylhydroquinone, Z-methyl-3-chlorohydroquinone, hydroquinone monosulfonic acid, and the like are used. The amount of hydroquinone used is 0.1 to 2.
00g/text is preferred, more preferably 1-100g/
It is particularly preferably 2 to SOg/fL.

Specific examples of l-phenyl-3-pyrazolidones include:
l-phenyl-3-pyrazolidone and British patent 943.9
No. 28, t, oq'x, zat, U.S. Patent No. 2.21
19) No. 67, same: l, 241,967 and same, 4
Compounds 1 having substituents at the 2-position, 4-position and/or 5-position of the 3-pyrazolidone ring as described in No. 5 Co., No. 109, etc. 1 For example, 4-hydroxymethyl-4-methyl-1-
Phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, 4-methyl-
1-phenyl-3-pyrazolidone, 4,4-dimethyl-
1-phenyl-3-hyrazolidone, 2-morpholinomethyl-3-pyrazolidone, 2-(+,2.3-tetrahydroquinolylmethyl)-1-phenyl-3-pyrazolidone, 2-piperadimethyl-1 -Phenyl-3-pyrazolidone, 2-hydroxymethyl-1-phenyl-3
-pyrazolidone, 2-hydroxymethyl-4-methyl-
1-phenyl-cobyrazolitone, 4,4-dimethyl-
2-Hydroxymethyl-1-phenyl-]-pyrazolidone, 4-chloromethyl-2-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-morpholinomethyl-4.4-dimethyl-l-phenyl -3-pyrazolidone, 2-(methyl-β-hydroxyethyl)aminomethyl-4,4-dimethyl-1-phenyluropyrazolinone, 2-(di-β-hydroxyethyl)aminomethyl-4.4 -Dimethyl-1-phenyl-3-pyrazolidone, 5-methyl-■-phenyl-3-pyrazolidone, etc. are used, and among these, 1-phenyluropyrazolitone and a compound having a substituent at the 4-position of the 3-pyrazolidone ring are particularly preferably used.

Examples of para-aminophenols include T. H.

r The Theory of T by James
he PotographicProcess(197
Is it possible to use the compounds described on pages 311 to 15 of 7th Year)?Specifically, baraminophenol, N
-Methyl-baraminophenol, p-β-hydroxyaminophenol, ρ-α-aminoethylaminophenol, p-sulfamethylaminophenol, p-hydroxyphenylglycine, 4-amino-Z-chlorophenol, 4-amino -3-chlorophenol, 4-aminophenol-2-sulfonate, 4-aminophenol-3-sulfonate, N-methylto(β-sul)oamidoethyl)-p-aminophenol, N-pencyl-p- Aminophenol, N-methyl-p-aminophenol-2-sulfonic acid, 2,6-cyclop-
Aminophenol, tomethyl-baraminophenol, etc. can be used. The amount of the l-7 enyl-cobylazolidones and/or paraaminophenols used is 0.01 to
l mouth Og/vertical preferably, more preferably 0.05 to 5
0 g/l, particularly preferably 0.1 to 10 g/l.

In addition to the hydroquinones, l-phenyl-pyrazolitones, and/or para-aminophenols, the black-and-white developer contains various components that are normally added to black-and-white developers, such as carbonates, boric acid, and boric acid. Buffers such as salts, phosphates, alkanolamines, and silicates, alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal sulfites, alkaline total bisulfites, and bisulfites of aldehydes and ketone compounds. Preservatives such as adducts, alkali total thiocyanate, polyalkylene oxide compounds, sodium thiosulfate, ammonium, phosphonium, or sulfonium type onium compounds and polyionium compounds, and those described in JP-A-57-63530. development accelerators such as thioether compounds,
Alkali metal halides, antifoggants such as benzotriazole, benzothiazole, tetrazole, thiazole, phosphates such as polyphosphates, nitrilotriacetic acid, 1
, 3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, aminopolycarboxylic acids such as hydroxyethyliminodiacetic acid, oxycarboxylic acids such as citric acid and gluconic acid, and organic acids such as l-hydroxyethylidene-1,1-diphosphonic acid. acids, aminopolyphosphonic acid such as aminotri(methylenephosphonic acid), chelating agents such as polyhydroxy compounds such as 1,2-dihydroxybenzene-3,5-disulfonic acid, and ethylene glycol, diethylene glycol, polyethylene glycols, and their It is possible to decide what to contain, such as thickening agents such as esters.

The pH of the black and white developer of the present invention is preferably 8.5 to 11.5, more preferably 9.0 to 11.0. The treatment temperature is preferably 10 to 60'C, more preferably 20'C.
~50°C.

The color developing agent used in the color developing solution is preferably an aromatic primary amine color developing agent, including various types widely used in various color photographic processes. Since these compounds are more stable than in the free state, they are generally used in the form of salts, such as hydrochlorides or sulfates. These compounds are also generally used at a concentration of about 0.1 g to about 3 fJg per color developer, preferably from about tg to about 15 g per color developer.

Useful aromatic primary amine color developers are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl group and phenyl group may be substituted with any substituents, such as N, N-diethyl-p-phenylenediamine hydrochloride, N-ethyl-N-propylparaphenylenecyamine QmkF, N,N-dimethyl-p-phenylenecyamine hydrochloride, 2-amino-5-(N-ethyl- N-dodecylamino)-toluene, N-ethyl-N-
β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, 4-amino-13-methyl-N-
Ethyl-N-β-hydroxyethylaniline sulfate, 4
-Amino-3-methyl-N,N-diethylaniline sulfate, 4-aminoto(β-methoxyethyl)-N-ethyl-3-methylaniline-11-)-luenesulfonate, N,N-diethyl-3- (β-methanesulfonamidoethyl)-4-aminoaniline sulfate and the like can be mentioned.

The effective color developing agent used in the present invention is a para-phenylene diamine color developing agent having at least one water-soluble group (wood-philic group) on the amino group. Examples include the following compounds, but the present invention is not limited thereto.

In addition, the above-mentioned water-soluble groups include -(CH2)n-CH,011, -(CHz)--NH3O2-(C)+2)--CI+
3,-((:+(,),-0-(C1+,) ne-e
ll,.

-(C1,C)120). C-11□1.1 (and.

is an integer greater than or equal to 0), -CO group, -3o group, and 11 group.

NH2 NH2 NH2 (4) 02H, O□) I40CH.

(5) O, H, 03H, Soyu HNH2 NH2 NH2 NH2 l-I2 N.H.

(2) C2H5 H2 NH2 A coloring agent particularly useful in the present invention is -(OH2) n 0H20H as a substituent on the amino group.

-(CHz)rn-NH8O2-(OHz)n-
CH3, (CH2)mO-(C!Hz)1 cH,l
It is a compound having each group of (OH2CH20)nOmH2m+1, and the specific compound is (υ
r (2) + (3) , (4) , (6) and (7
) to be buried. However, m and n are integers greater than or equal to 0 and 'jb
υ.

Preferably it is O-5.

Particularly preferable compounds among these compounds are the compounds shown in the specific examples (1), (3), and (4), and among these, the compounds shown in (1) and (3) are particularly preferable. It is particularly preferably used.

The color developing solution may contain known developing components in addition to the aromatic primary amine color developing agent. For example, preservatives include alkali total sulfites, alkali gold Ji1 bisulfites, bisulfite adducts of aldehydes and ketone compounds, water-soluble salts of hydroxylamine, such as sulfates, ti! These include Slu and phosphate. As alkaline agents, buffering agents, etc., sodium hydroxide, silicate, sodium carbonate, potassium metaborate, boric acid, phosphorus salt tolerance, etc. are added singly or in combination. Furthermore, disodium hydrogen phosphate, sodium bicarbonate, etc. may also be used due to pharmaceutical needs or for the purpose of increasing ionic strength.

In addition, it is also possible to add inorganic or organic antifogging agents as necessary, and typical examples of these compounds include inorganic halide compounds such as potassium bromide and potassium iodide, as well as U.S. Patent No. 2,496. , 6-nitrobenzimidazole described in No. 2,497.917 and No. 2.656.271, mercaptobenzimidazole, mercaptobenzoxazole, including 0-phenylenediamine. , thiouracil, 5-methylbenzotosoazole,
Alternatively, mention may be made of the heterocyclic compounds described in Japanese Patent Publication No. 46-41675.

In addition to these various ingredients, there are also
A development inhibitor disclosed in US Pat. No. 45-6149 and US Pat. No. 3,295,976 and a development accelerator may also be added if necessary. Among these development accelerators, there are various pyridium compounds represented by U.S. Pat. No. 2,648,604, U.S. Pat. Cationic pigments such as safranin.

Neutral salts such as thallium nitrate, U.S. Patent 2,533,99
No. 0, same 2. S:It, 8:12, 2,950,9
No. 70, No. 2.577.127 and Special Publication No. 1977-1995
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc. described in No. 04, Japanese Patent Publication No. 44'
The organic solvents and organic amines described in No.-9509, such as ethanolamine, ethylenediamine, jetanolamine, and triethanolamine, are included. Also, US Patent 2,30
In addition to pencil alcohol and phenethyl alcohol described in No. 4,925, acetylene glycol, methyl ethyl ketone, cyclohexane, thioethers, pyridine, ammonia, hydrazine, and amines are also effective development accelerators. In addition, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin,
Other compounds described in Japanese Patent Publication Nos. 47-33378 and 44-9509 can also be used as organic solvents to increase the solubility of the developing agent.

Also for color developer. Various chelating agents can be included as water softeners and heavy metal sequestrants. Such chelating agents include polyphosphoric acid'i! i phosphates, aminopolycarboxylic acids such as nitosoroacetic acid, 1,3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylimino-acetic acid, oxycarboxylic acids such as citric acid and gluconic acid, 1-hydroxyethylidene- The organic acid of 1,1-diphosphonic lv rod, aminotri(
Methylenephosphonic acid) Kasa's aminopolyphosphophone M, 1
．． Examples include polyhydroxy compounds such as 2-dihydroxybenzene-3,5-disulfone.

Additionally, auxiliary developers may be used with the developing agent. These auxiliary developers include 1 such as N-methyl-p-aminophenol sulfate (methol), phenidone, N,N-diethyl-p-aminophenol 1
′! ! The acid salt N,N,N,N-tetramethyl-p-phenylenecyamine Nmk12G is known, and the amount added is usually 0.01g to 1. Og/l is preferable, and in addition, if necessary, competitive couplers such as citradinic acid, tin chelate compounds such as N,N,N-trimethylenephosphonic acid tin, tin citrate, and tar as fogging agents are used.
Borohydride compounds such as t-butylamine borane, colored couplers, development-inhibited release couplers (so-called DIR couplers), or development inhibitor-releasing compounds can also be added.

The color developing agent may be used in p118 to I4, more preferably in p1! 9.5 to 14, particularly preferably 91111.5 to I3.5. The temperature of the treatment is preferably 10-60°C, more preferably 20-60°C.
The temperature is 50°C.

In the present invention, compounds preferably used in the water washing alternative stabilizer have a chelate stability constant of 8 or 8 for iron ions.
The above-mentioned chelating agents can be mentioned, and these are preferably used to achieve the object of the present invention.

What is the chelate stability constant here? 1. ,G,5ill
Written by A, E, Marte l l, '
5tability Cor+5tanLs o
r 14 etal-ion Colplexes'',
The Chemical 5ociety, Lon
don (1964), S., Chaberck-A.E.
, by MarLell, “OrganicSeques”
tering Agents”, Wiley (195
9) etc. means a generally known constant.

Examples of chelating agents having a chelate stability constant of 8 or more for iron ions that are preferably used in the water washing alternative stabilizer of the present invention include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. can be mentioned. Note that the above-mentioned iron ion means :52 iron ion (F%+).

Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds: ethylenediaminethiolthohydroxyphenyl Acetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexane Diaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenecyaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, ■-hydroxyethylidene-1,1-diphosphonic acid, 1. l-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-)-licarboxylic acid, ■-hydroxy-1-phosphonopropane-1,2,3-)-licarboxylic acid, catechol-3, 5-diphosphonic acid, sodium pyrophosphate.

Examples include sodium tetrapolyphosphate and sodium hexametaphosphate, and particularly preferred are diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, and especially l-hydroxyethylidene. -1,1
-diphosphonic acid is most preferably used.

The amount of the above-mentioned chelating agent used is 0.00% per tU of water washing alternative stabilizer.
01-50g is preferable, more preferably 0.05-2
It is in the range of 0g.

Furthermore, as a compound to be added to the water washing substitute stabilizing solution of the present invention,
Ammonium compounds are particularly preferred.

These are supplied by ammonium salts of various inorganic compounds, specifically ammonium hydroxide, ammonium bromide, iRM ammonium, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, fluoride. Ammonium, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium fluoride,
Ammonium hydrogen sulfate, ff1M ammonium, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, lauric tricarboxylic ammonium, ammonium benanoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, formic acid Ammonium, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium tartarate, ammonium thiosulfate, ammonium sulfite,
Ammonium ethylenecyaminetetraacetate, ferric ammonium ethylenecyaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, succinic acid These include ammonium, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, and 2,4.6-dolinyl-lophenol ammonium. Among these ammonium compounds, ammonium thiosulfate is particularly preferred since it achieves the effects of the present invention.

The state of addition of ammonium compounds is 1. Ox 10-' or more
F2 is preferred, more preferably stable Ml intersection is 0.0
The range is 0.01 to 5.0 mol, more preferably 0.0 mol.
The range is 0.02 to 1.0 mol.

Further, it is desirable that the water washing substitute stabilizing solution in the present invention contains sulfite to the extent that grouperia does not occur.

In the present invention, the sulfite contained in the water washing alternative stabilizing solution may be any organic or inorganic substance as long as it releases sulfite ions, and preferably an inorganic salt.
Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and pytrosulfide, and cartaraldehyde. Bis modified Vi, acid sodium, succinic acid aldehyde bis bead, sodium sulfite, etc. can be mentioned.

The above sulfite should be at least 10X in the water washing substitute stabilizing solution.
It is preferable that the amount is added to be 10-' mol/l, more preferably 5 x 10-' mol/l
, 7H is added so that ox to 'mol/cross.

The water washing substitute stabilizer used in the present invention is:

Preferably, it contains an anti-high agent, which further improves sulfurization prevention and image preservability.

As an anti-piping agent, for example, inthiazoline type.

Benzimidazole-based, benzisothiazoline-based, thiabendazole-based, phenol-based, organic halogen-substituted compounds, mercapto-based compounds, benzoic acid and its derivatives, etc. can be used, but isothiazoline-based, benzintiazoline-based, thiabendazole-based , phenolic,
Examples include training for cheap and q training. Particularly preferred are isothiazoline, pentwinthiazoline, and thiabendazole.

Specific compounds will be listed below, but the invention is not limited to these.

[Exemplary compounds] (1) 2-methyl-4-thiazolin-3-one (2
) 5-chloro-2-methyl-4-isothiazoline-3-
(3) 2-Methyl-5-phenyl-4-inthiazolin-3-one (4) 4-bromo-5-chloro-2-methyl-4-isothiazolin-rone (5) 2-hydroxymethyl-4 -Inchiazoline-3
-one (6) 2-(2-ethoxyethyl)-4-inchazoline-one (7) 2-(-methyl-carbamoyl)-4-isothiazolin-3-one (8) 5-bromomethyl-2-( N-dichlorophenyl-carbamoyl)-4-inthiazolin-3-one (9) 5-chloro-2-(2-phenylethyl)-4-
Inthiazolin-3-one (10) 4-Methyl-2-(3,4-dichlorophenyl)-4-itziazolin-3-one (II) 1.2-benzisothiazolin-3-one (12) 2-(2- Bromoethyl)-1,2-benzisothiazolin-3-one (11) 2-Methyl-L,2-benzisothiazolin-3-one (14) 2-ethyl-5-nitro-1,2-benzisothiazolin-3- On (!S) 2-pencyl-1,2-benzisothiazolin-3-one (16) 5-chloro-1,2-benzisothiazolin-3-one (17) Hydroxy Yasukuchi, aromatic acid (18) Saia Bentazole These exemplary compounds are described in U.S. Patent No. 2,767.
No. 172, No. 2,767.173, No. 2,767
, No. 174, No. 2.870,015, British Patent No. 848
, No. 130, French Patent No. 1,555,416 I
The synthesis method and examples of its application to other fields are described in the JJ specifications and the like. There are also reprints such as Top Sight Co00, Top Sight 600 (manufactured by Permake Asia Co., Ltd.), Fine Sight J-700 (manufactured by Tokyo Fine Chemical Co., Ltd.), and Proxel GXL (1, C).
, made by one company).

The amount of the above compound used is 0.01 per liter of water washing substitute stabilizer.
-SDg is preferred, more preferably 0.05-20g
It is to add.

In the present invention, the pl+ of the water washing () stabilizer is 3.0 to 9.
．． The range of pl+ is preferably 5, and it is further preferable to adjust the pl+ to 3.5 to 9.0 for the purpose of the present invention, which is the sedimentation prevention IF.

Furthermore, other compounds that can be added to the water-washing alternative stabilizing solution in case 11 include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.).

pl+buffer (phosphoric acid, borate, hydrochloric acid, sulfuric acid, etc.) or surfactant, preservative, Bi, Mg, In,
Ni.

Hebun, Sn, Ti, 7. Is there a metal salt, etc. of r':g?The amount of these compounds added is necessary to maintain the PL+ of the water washing alternative stabilizer according to the present invention, and to prevent the stability of color photographic images during storage and the occurrence of precipitation. Any compound may be used in any combination as long as it does not cause any adverse effects.

Any bleaching agent may be used as the bleaching agent used in the doorway or t=self-fixing solution of the present invention, such as red blood salt, iron chloride (British Patent No. 7:15,881, Japanese Patent Publication No. 1983-1986).
44424 (described in each publication), sulfur (described in German patents 2 and 1)
41,199), hydrogen peroxide (Japanese Patent Publication No. 1983-
11617 and 58-11618), organic ferric complex salts such as ethylenediaminetetraacetic acid ferric complex salts may be used.

Particularly preferred examples include ferric complex salts of organic acids shown below.

(1) diethylenetriaminepentaacetic acid (2) diethylenetriaminepentamethylphosphonic acid (3) cyclohexanecyaminetetraacetic acid (4) ethylenediaminetetraacetic acid (5) methyliminodiacetic acid (6) probyliminodiacetic acid (7) butyliminodiacetic acid (8) cyclohexanediaminetetramethylene Phosphonic acid (9) Triethylenetetraminehexaacetic acid (10) Triethylenetetramine hexamethylenephosphonic acid (11) Glycol ethercyamine tetraacetic acid (12) Glycol ethercyamine tetramethylenephosphonic acid (+3) 1,2-diamino Propane tetraacetic acid (111) 1
．． 2-diaminopropane tetramethylenephosphonic acid (+5) l, 3-diaminopropan-2-ol tetraacetic acid (+6) 1,1-diaminopropane-2-ol tetramethylenephosphonic acid (17) ethylenecyamine thiorthohydride Roxyphenylacetic acid (18) Ethylenecyaminecyorthohydroxyphenylmethylenephosphonic acid (I9) Ethylenecyaminetetramethylenephosphonic acid (20
) Tohytroxyethyliminoni M: Acid Ferric complex salts of organic acids are free acids (hydrogen salts), sodium salts, potassium salts, lithium'! ! The alkali metal salts of 3 or ammonium salts, or water-soluble amine salts such as triethanolamine salts, preferably potassium salts.

Sodium salts and ammonium salts are used. At least one type of these ferric complex salts may be used, or two or more types may be used in combination. Its usage can be selected arbitrarily, and it may or may not be selected depending on the ffi rM and silver halide set a9 of the photosensitive material to be processed, and it generally has a high oxidizing power, so it has a lower oxidizing power than other aminopolycarboxylate salts. For example, the working solution can be used in an amount of 12690.01 mol or more, preferably 0.05 to 0.6 mol. In addition, in the replenisher, it is desirable to use it in a highly concentrated form with the highest solubility in order to achieve low concentration and low replenishment.

The bleach and bleach-fix solutions may be used with a plIO of 2 to 9.5, preferably 4 to 9, more preferably 5.5 to 8.
5 is used. The treatment temperature is 80° C. or lower, preferably 55° C. or lower, and most preferably 45° C. or lower to suppress evaporation.

The bleaching solution may contain various additives along with the organic acid ferric complex salt as a bleaching agent as described above. As additives, it is particularly desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like.

Also, the pH of borates, g-acids, acetates, carbonates, phosphates, etc.
Buffers, solubilizers such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, alkylamines, polyethylene oxides, etc. can be added to ordinary bleaching solutions. Those known in the art can be added as appropriate.

The bleaching stone solution is made up of a composition in which a small amount of a halogen compound such as potassium bromide is added.

Or, conversely, a bleach-fix solution with a composition containing a large amount of a halogen compound such as potassium bromide or ammonium bromide, or a special composition containing a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide. You can also use a bleach-fix solution or the like.

In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. may also be used.

The silver halide fixing agent to be included in the bleach-fix solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as those used in normal fixing treatments.

For example, potassium thiosulfate, sodium thiosulfate.

Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanine lv salts such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, bulk thio powder, thioethers, and high concentrations of bromide and iodide. These fixing agents have a content of 5 g/1 or more, preferably 5 g/1
It can be used in an amount that can dissolve 0 g/l or more, more preferably 70 g/l or more.

The bleach-fixing solution contains boric acid, borax, sodium hydroxide, and potassium hydroxide, as in the case of the above-mentioned bleaching solution.

It is possible to contain pl+buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium subcarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. Also hydroxyamine, hydrazine, sulfite, isomeric bisulfite Mtl! ,
Preservatives such as aldehyde 1- and east sulfite adducts of ketone compounds, organic chelates such as acetylacetone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, polycarboxylic acid, dicarboxylic acid, and aminopolycarboxylic acid or stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amine T, other additives, and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide. I can do it.

When the fixing solution used in the present invention is a processing solution or a fixing solution, the fixing solution may be used as a fixing agent such as, for example, thioic acid #11!
(Anthrate described in JP-A-57-18543585435 (British Patent No. 565,135, JP-A-54-137)
143), halides (Japanese Patent Application Laid-Open No. 52-1
30639), 1,000-onychill (described in Belgian Patent No. 626970), Thio bulk powder (British Patent No. 1.
189,416) etc.).

In addition to these fixers, the fixer contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, Rm potassium, sodium bicarbonate, potassium bicarbonate, acetic acid, as in the white fixer mentioned above. pH consisting of various salts such as sodium acetate, ammonium hydroxide, etc. [A buffer agent can be contained alone or in combination of two or more kinds. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifoaming agents can be contained. Also hydroxyamines, hydrazine, sulfites, isomeric bisulfites.

Preservatives such as bisulfite adducts of aldehydes and ketone compounds; organic chelating agents such as acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, boccarboxylic acids, dicarboxylic acids, and aminopolycarboxylic acids; Alcohol, nitric acid! ! ! A stabilizer such as, a solubilizer such as an alkanolamine, a stain preventive agent such as an organic amine, other additives, and an organic solvent such as methanol, dimethylformamide, dimethyl sulfoxide, etc. may be appropriately contained.

The photographic processing solution used in Unreleased '51 may be a processing solution for directly processing photosensitive materials, and may include replenishment solutions used for replenishment and preparation of these processing solutions. Parts may be prepared by concentrating part or all of the composition.

In the present invention, oxygen permeation is -20 min/rn'/2
A flexible synthetic resin film of 411r or less is used, and the amount of oxygen permeation can be measured by a conventionally known method.

The oxygen permeation rate of the present invention is 2[1”C165% under 1 atm.
It shows the measured value of relative humidity.

Next, oxygen permeability i120ml/m2 used in the present invention
A flexible synthetic resin film having a thickness of /m''/24Hr or less will be explained.

Oxygen passage fik of the invention 20m12/m2/24
Flexible synthetic resin film of Hr or less is 15 (polymer)
It may be a resin film or a laminated (polymer) resin film of two or more. Examples of polymer resin films that meet the conditions of the present invention include (1) polyethylene terephthalate (PET) with a thickness of 0.1 mm or more, and (2) acrylonitrile butanoene with a thickness of 0.3 mm or more. (3) hydrochloric acid rubber having a thickness of 0.1 mm or more, and the like. Among them, polyethylene terephthalate is well-known for its alkali resistance and acid resistance, and therefore can be suitably used in the present invention.

Next, examples of laminated polymer resin films that meet the conditions of the present invention include (4) PET/polyvinyl alcohol/ethylene copolymer (EVAL)/polyethylene (PE), (5)
Nobu (medium polypropylene (OPP)/EVAL/PE
, (6) unstretched polypropylene (CP P )/EVAL/PE, (7) nylon (N)/aluminum foil (Ae)/
PE, (8) PET/AQ/PE, (
9) Cellophane/PE/AI2/PE, (to)AI
2/Paper/PE, (11) PET/PE/Af2/PE1
(12) N/PE/AQ/PE, (13) Paper/PE/A
Q/PE, (14) PET/A12/PET/polypropylene (PP), (15) PET/, l! /PET/High-density polyethylene (HDPE), (18) PET
/AQ/PE/Low density polyethylene (LDPE), (1
7) EVAL/PP1 (11ri PET/AQ/PP, (
19) Paper/AQ/PE1 (20) PE/PVDC:ll
-tonylon/PE/ethyl vinyl acetate polyethylene condensate (EVA), (21) PE/PV
D C: +-t N/PE, (22) EVA/PE/aluminum vapor-deposited nylon/PE/EVA1 (23) aluminum vapor-deposited nylon/N/PE/EVA, (24) OPP/PVDC
1-t N/PE, (25) PE/PV DC coat N/PE, (26) OPP/Eva-
Le/L D P E, (27) O P
/ Enkil/CP P, (28) PET/Eval/L D P E.

(29) ON (stretched nylon)/EVAL/LDPE
, (30) CN (unstretched nylon)/EVAL/LD
There are PE and the like, among which the above (20) to (30) are preferably used.

The thickness of these films varies depending on the type, but
Preferably 0-5 μm to 500 μm 1 Especially preferably 1
A film with a diameter of μm to 200 μm is preferably used.

A supply chamber 2 shown in FIG. 1 is filled with a photographic processing solution.

From this state, the processing liquid is supplied through the opening 4 to an automatic developing machine (not shown).

The waste liquid from the automatic developing machine is sent into the waste liquid chamber 2 through the opening 5. At this time, as the waste liquid is absorbed into the waste liquid chamber 3, it wets or soaks the partition 11alA and eliminates air permeation, thereby preventing oxidation of the photographic processing liquid in the supply chamber 2 and causing storage deterioration. As the liquid in the supply chamber 2 decreases, the state gradually approaches the state shown in FIG. 2.

Although one embodiment of the present invention has been described above, the embodiments of the present invention are not limited thereto.

For example, the storage tank 1 is not limited to the illustrated form, but may be of any other form as long as it is divided into two or more parts. Specifically, it may be of the form shown in FIG. 3. That is, the same reference numerals in the figure as in FIGS. 1 and 2 indicate corresponding member names. The embodiment shown in FIG.
4'. In this case, another flexible film F4 may be used during manufacturing. Note that the opening 4
' can also be made to protrude toward the opening 5 side in the same way as the opening 4. Note that it is preferable to provide the liquid-absorbing and swelling substance 6, for example, it may be placed on the diaphragm IA,
It may be fixed to the diaphragm IA or to the inner wall (IF) of the storage tank l. It is also preferable that the gap alA is stretchable (by expansion of the liquid-absorbing and expansible material 6), such as a stretchable or flexible synthetic resin sheet or film (including one made of stone) or a rubber sheet. (Natural rubber or synthetic rubber may be used, but chemically resistant rubber) whose oxygen permeability is within the range of the present invention can be particularly preferably used.

In addition, it is preferable to use the flexible synthetic resin film according to the present invention for the membrane constituting the waste liquid chamber 3 as well.

[Example] The invention will now be illustrated by examples.

Example 1 Prepare 7A of color developer replenisher with the following formulation, prepare two storage packs each of size 5 of 6 [class 6] with different synthetic resins as shown in Figure 1, and store one of the storage packs. The pack contains 4 colors of color developer replenisher prepared according to the following formulation in the processing solution supply chamber.
In case 1, color developer waste solution 11 was put in the waste solution chamber, or in the other storage pack, only 5 volumes of color developer replenisher solution was put in the processing solution supply chamber, but no color developer replenisher solution was put in the waste solution chamber.

Next, these stored bars were stored in a thermostat at 50°C for two weeks, and the reduction rate of sulfite ions in the color developer replenisher was measured.

In addition, a diaphragm and a processing liquid supply chamber formed opposite to the diaphragm are provided.
The layer structure and oxygen permeation amount of 12 (F3) are shown in Table 1, but the membrane (Fl) that forms the waste liquid chamber facing the diaphragm is made of LDPE of 50 l, and the oxygen permeation h°C is 2700 si.
/ m' / 2411r was there. The results are shown in Table 1.

[Color developer replenisher] Benzyl alcohol 18m diethylene glycol 10m fluorescent brightener (Chippanol SFP (Ciba Geigi tA) 2g hydroxylamine sulfate 4g potassium carbonate 25g potassium sulfite (
50% aqueous solution) 6mM potassium hydroxide
2.3g in water
It should be one sentence.

As is clear from the results in Table 1, the oxygen permeation rate of F3 is 20
T! ;L/rn'/2411r or less, and when there is waste liquid in the waste liquid chamber, the rate of decrease of sulfite ions in the color developer is extremely low, especially the amount of oxygen permeation through the diaphragm is 2.
It can be seen that the rate of decrease is lower than that at 0m viewing/m''/2411r.

Example 2 An experiment was conducted in the same manner as in Example 1, except that a bleach-fixing replenisher having the following formulation was used instead of the color developing replenisher.
The sample was stored in a thermostat at 0°C for one week, and the reduction rate of sulfite ions was measured.

[Bleach-fix replenisher] Iron ammonium ethylenediaminetetraacetate 75g Ammonium sulfite 10g Ammonium thiosulfate 10g Aqueous ammonia (28%)
The mixture was washed with water for 10+s to give a uniform finish, and the pH was adjusted to 6.5 with acetic acid and aqueous ammonia.

The results are shown in Table 2. Sample No. I in S1 Table 2]~2
4 corresponds to sample Nos. 1 to 12 shown in Table 1 of Example 1.

Table 2 As is clear from Table 2, it can be seen that the bleach-fixing replenisher has the same tendency as the color developing replenisher.

Example 3 Storage bulk membrane (F3) similar to that used in Example 1
The color developer replenisher used in Example 1 was poured into the processing solution supply chamber of the storage pack whose film (Fl) was changed as shown in Table 3, and the opening of the processing solution supply chamber was filled with color vapor. Connect it to the bellows pump of the automatic developing machine, connect the color developer replenisher to the color developer tank, connect the opening of the waste liquid chamber to the overflow pipe from the color developer tank, and connect the color developer replenisher to the overflow pipe. It was made to flow into the market. Adjust the processing amount of color paper so that about 2,001 cubic centimeters of color developer replenisher is replenished into the color developer tank per day, and after 24-hour running processing, add the color developer replenisher in the processing solution supply chamber of the storage pack. The sulfite ions in the sample were measured, and the reduction rate of sulfite ions was determined. The results are shown in Table 3.

As is clear from Table 3, when a storage pack in which the oxygen permeation rate of the membrane (F3) and membrane (Fl) is 20 m1/rn'/2411r or less is used, the reduction rate of sulfite ions is extremely low.

Margin below

[Brief explanation of drawings]

1 and 2 are cross-sectional views showing one embodiment of the present invention, and FIG. 1 shows a photographic processing solution stored in a supply chamber;
FIG. 2 shows the state before the waste liquid is stored in the waste liquid chamber, and FIG. 2 shows the state after the waste liquid is collected in the waste liquid chamber. FIG. 3 is a sectional view showing another embodiment of the present invention. l: Storage tank IA: Diaphragm 2: Supply chamber 3: Waste liquid chamber 4: Opening 5: Opening Fl-F4: Flexible synthetic resin film or sheet Patent applicant: Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Sakaguchi Nobuaki (and 1 other person) Figure 1 Figure 2 Figure 1A 2 1: Storage tank 1A: Diaphragm 2: Supply chamber 3; Waste liquid chamber 4: Opening 5: Opening PI to F4: Flexible synthetic resin film or sheet Figure 3

Claims (6)

[Claims] (1) A flexible pack for storing a photographic processing solution for a silver halide photographic light-sensitive material, the pack having at least two compartments separated by a diaphragm, one of which supplies the photographic processing solution. and the other is a waste solution chamber, and at least the membrane forming the photographic processing solution supply chamber and the membrane on the surface facing the diaphragm has an oxygen permeation rate of 20 ml/m.
A housing for a photographic processing solution, characterized in that it is made of a flexible synthetic resin film that lasts 2/24 hours or less, and at least one side of the photographic processing solution supply chamber is covered with the waste solution collected in the waste solution chamber. pack. (2) The storage pack is composed of at least three flexible synthetic resin films, at least one of which is a diaphragm, and the opposing surface of the diaphragm constituting the photographic processing solution supply chamber is air-filled. 2. A storage pack for photographic processing liquid according to claim 1, characterized in that the pack is made of a flexible synthetic resin film that comes into contact with the photographic processing liquid. (3) A storage pack for photographic processing liquid according to claim 1 or 2, characterized in that one entire surface of the diaphragm is a photographic processing liquid supply chamber, and the other entire surface is a waste liquid chamber. . (4) The surface facing the diaphragm that constitutes the photographic processing solution supply chamber is
Claim 1: It is composed of at least two layers of flexible synthetic resin film, and at least one of the layers excluding the innermost layer is composed of EVAL, aluminum foil, or aluminum vapor-deposited synthetic resin film. A storage pack for a photographic processing solution according to any one of items 1 to 3. (5) Oxygen permeation rate of the diaphragm is 20ml/m^2/24Hr
A photographic processing liquid storage pack according to any one of claims 1 to 4, characterized in that it is made of the following flexible synthetic resin film. (6) The diaphragm is composed of at least 25 flexible synthetic resin films, and at least one layer excluding the outermost layer is EVAL, aluminum foil, or aluminum vapor-deposited synthetic resin film. A photographic processing liquid storage pack according to any one of items 1 to 5.