JPH03276153A - Container for photographic processing solution - Google Patents

Abstract

PURPOSE:To stabilize a solvent even after long-term preservation, to prevent the deformation of the container and to facilitate the throwing away or reuse of the container by using the container consisting of a packaging material which is formed by laminating at least a flexible resin layer on a paper board and has a gas barrier property. CONSTITUTION:The container which houses the development processing agent of silver halide photosensitive materials therein is formed of the packaging material which is formed by laminating at least the flexible resin layer on the paper board and has the gas barrier property. For example, the packaging material consisting of a liquid side/PE/K-nylon/PE/Al/PE/flat paper board/PE/ outer side is used as the container for the developing soln. part agent. The container 1 which seals the respectively different part liquids into the containers 5, 6, 7 is used.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a packaging material that can replace a container for a processing solution for silver halide photographic light-sensitive materials, and particularly relates to a container mainly made of paper. .

<Prior Art> Conventionally, packaging materials and containers for development processing solutions for silver halide photographic materials (hereinafter generally referred to as photosensitive materials) include:
For example, they are mainly made of fairly hard plastic, such as polyethylene bottles.

These hard materials are easy to transfer and do not leave any residue (and are easy to handle) when using a mixing mixer (commonly known as a "chemical mixer") for processing solution that is attached to an automatic processing machine. This is because there is little chemical interaction with the liquid agent stored inside.

On the other hand, a soft container has the disadvantage that it is difficult to perform liquid transfer operations because its shape changes.

Incidentally, these plastic wastes have recently become a major social problem from the standpoint of environmental conservation. More specifically, there is a demand for materials that are easier to disassemble, easier to incinerate (easier to assemble or disassemble and transport, and easier to store).

Although it is not technically impossible to recycle and reuse polyethylene containers, it is not realistic to reuse them due to the high transportation costs involved in recovering them and the maintenance and management costs required for reuse.

Conventionally, flexible plastic materials with a multilayer structure have been used as packaging materials for containers for milk, juice, etc., and these materials are made of nylon/polyethylene under the trade name "Toy Bag". Or, ethylene-
It is also used as a packaging material for developing processing solutions, such as the product name ``Cubitainer'' made from vinyl alcohol/low-density polyethylene (LDPE) and the product name ``Sholly Bag'' made from polyethylene bags.

However, these multilayered plastic packaging materials are flexible and easily deformed, making them difficult to use when using the chemical mixer mentioned above. It is necessary to use auxiliary materials to prevent deformation.

Furthermore, these are heat-resistant and difficult to dispose of, and when storing large quantities of liquid at 5ρ and 10°C, they must be placed in even stronger cardboard boxes to provide strength.

On the other hand, containers for alcohol, milk, juice, etc. are made of polyethylene.
Multilayer containers such as paper/polyethylene have also been used.

However, in systems such as photographic processing solutions, which have extremely high salt concentrations (and also contain organic solvents, the solution permeates through the solution, and in the case of developing solutions, the slow permeation of minute amounts of oxygen causes However, since it inherently has the property of being easily oxidized, it cannot be put into practical use.

On the other hand, in addition to the problem of plastic waste caused by packaging materials as described above, development processing waste liquid is also a major problem in terms of environmental conservation, and there is a need to reduce the amount of waste liquid by reducing the amount of replenisher.

For this reason, from the era of handling large amounts of processing liquid as in the past,
We are moving into an era in which smaller amounts of processing liquid are handled.

Furthermore, the trend of the times is to simplify the development process for silver halide photographic materials.

The greatest advantage of silver halide photographic systems is that the image quality is extremely high.

On the other hand, its biggest drawback is that it is a wet process and the development process is complicated.

Therefore, the biggest challenge for this image forming system is to simplify the development process, which is its biggest drawback, while maintaining high image quality.

Therefore, anyone can easily process the process, and
What is desired is a system that is easy to clean up afterwards.

<Problems to be Solved by the Invention> Therefore, the first object of the present invention is to provide a solution for producing a developing solution for a silver halide photographic material and for a long period of time (storage) until it is used in the form of a kit. Another object of the present invention is to provide a container using a stable packaging material.

A second object is to provide a container that can maintain its shape without deformation even when it is filled with a developing treatment solution.

Third, the packaging material that makes up the container can be easily folded or crushed before and after use, making it a space-saving container that is particularly convenient for disposal or reuse. Our goal is to provide the following.

Furthermore, the fourth object is to provide a container that can be easily disposed of after use, such as by being incinerated.

Means to solve problems〉 Such objects are achieved by the invention described below.

(1) A container for storing a development processing solution for silver halide photographic light-sensitive materials inside, characterized by being made of a packaging material having gas barrier properties, including a paperboard laminated with at least a flexible resin layer. Photographic processing liquid container.

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

In the present invention, the paper that is the main material of the packaging material weighs 200
~800g/m2, preferably 3oo~700g/m
” paperboard.

Of course, inside the paperboard, the steps are processed corrugated paperboard,
This includes so-called corrugated cardboard such as the laminate.

Use of such paperboard provides a certain degree of rigidity and ensures shape retention.

Furthermore, it can be folded after use.

At least one flexible resin layer is laminated on such paperboard.

The above synthetic resin materials include polyethylene (high pressure method,
(low pressure method may be used) Polypropylene (either unstretched or stretched) Polyvinyl chloride, polyvinyl acetate, nylon (stretched or unstretched) Polyvinylidene chloride, polystyrene, polycarbonate, vinylon, EVAL,
Polyethylene terephthalate (PET) and other polyesters, hydrochloric acid rubber, acrylonitrile butadiene copolymer, epoxy-phosphoric acid resin (JP-A-63-63037
The polymer described in JP-A-57-32952 may be any of the polymers described in JP-A-57-32952.

These films are usually laminated and bonded together, but may also be applied as a coating layer.

Furthermore, it is more preferable to use various gas barrier films, such as using aluminum foil or aluminum-deposited synthetic resin between the above synthetic resin films.

In addition, the total oxygen permeability of these laminated films is 50 mA
/m”/24hr/atm or less (at 20℃65%RH)
, more preferably 30 mj/m2/24hr/atm
It is preferable that it is below.

The total thickness of these laminated films is preferably 1 to 2000 layers, more preferably 10 to 1000 layers, and even more preferably 50 to 1000 layers.

The above synthetic resin film may be a single layer (polymer) resin film, or may be a laminated (polymer) resin film of two or more layers.

Examples of one-layer 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; (2) acrylonitrile butadiene copolymer with a thickness of 0.3 mm or more; (3) Examples include hydrochloric acid rubber having a thickness of 0.1 mm or more, among which polyethylene terephthalate is excellent in alkali resistance and acid resistance, and therefore can be suitably used in the present invention.

Next, laminated polymer resin films that meet the conditions of the present invention include, for example: (4) PET/polyvinyl alcohol/ethylene copolymer (EVAL)/polyethylene (PE) (5) Oriented polypropylene (OPP)/EVAL /PE
, (6) Unoriented polypropylene (CPP)/EVAL/P
E.

(7) Nylon (N)/Aluminum foil (A℃)/P-E
% (8) PET/Aβ/PE, (9) Cellophane/PE/A℃/PE, (10AJ2/
Paper/PE, (11PET/PE/Aβ/PE, (12N/PE/Aβ/PE, (13 paper/PE/Aβ/PE, (14PET/Aj2/PET/Polypropylene (pp
) (15) PET/AJ2/PET/High-density polyethylene (HDPE) (16) PET/Aβ/PE/Low-density polyethylene (
LDPE) (17) EVAL/PP.

(18) PET/Aβ/PP, (19) Paper/AI2/PE.

(20) PE/PVDC: l-tonylon/PE/ethyl vinyl acetate polyethylene condensate (EVA) (21) PE/PVDC coat N/PE, (22) EV
A/PE/Fulumi vapor-deposited nylon/PE/EVA1 (23) Aluminum vapor-deposited nylon/N/P E/EVA.

(24) OPP/PVDC: I-TN/PE, (25)
PE/PVDC Co) N/PE, (26) OPP/EVAL/LDPE, (27) OPP/EVAL/CPP, (28) PET/EVAL/LDPE, (29) ON
(Stretched nylon)/EVAL/LDPE.

(30) CN (unstretched nylon)/EVAL/LDP
Among them, the above (20) to (30) are preferably used.

More specifically, as for the composition of the packaging material, if the side that comes into contact with the processing liquid is the inner surface, then in order from the inner surface: PE/mainly paperboard/PE/A fl/epoxy.
Phosphoric acid resin layer/Polyester resin layer/PE, PE/Nylon/PE or adhesive/Aρ/PE/
Paperboard/PE, PE/vinylon/PE or adhesive/Aρ/PE/paperboard/PE, PE/vinylidene chloride/PE or adhesive/Aβ/P
E/Paperboard/PE, PE/Polyester/PE or adhesive/AI2/PE
/Paperboard/PE, Polypropylene/Nylon/Polypropylene/Aρ
/Polypropylene/Paperboard/Polypropylene, etc.

Regarding the amount of replenisher for the processing solution sealed in the container of the packaging material of the present invention, it is difficult to package a large amount of processing solution due to the nature of the packaging material, so the smaller the amount, the more effective it is.

In other words, the amount of replenisher is 20 to 500 mj per m2 of sensitive material.
, preferably 25 to 400rnR1, more preferably 2
It is 5-35o1.

Here, the amount of replenishment liquid is calculated by the amount of concentrated liquid + water for dilution, or the working liquid to be replenished (working 5ol).
tion ready to use).

Further, the maximum size of these packaging units is preferably 10β, more preferably 8β or less.

At this time, the shape can be maintained during use.

The container of the present invention can take various shapes depending on the purpose, but it is preferably bottle-shaped and equipped with a sufficiently airtight cap.

Alternatively, it may be in the form of a collapsible container or the like.

As for the airtightness of the cap, it is preferable to use a method such as attaching a sheet of an inert elastic material to the inside of the cap and press-fitting it.

In addition, the outside of the container may be wrapped in a flexible bag and the opening of the bag may be sufficiently sealed.

As the cap material, the above-mentioned materials, ebonite, etc. can be used.

Furthermore, it is more effective to heat-seal a polyethylene film laminated with aluminum foil or the like to the mouth of the container and place the aforementioned cap on top of it.

The cap may be removable or pierceable.

Specific examples of container forms using the packaging material of the present invention are shown in Figures 1-
It is shown in Figure 3.

The container 1 shown in FIG. 1 is made from the packaging material 2 of the present invention.
It is shaped like a pot with a rectangular cross section and has a sloped roof-like guard 15 at the top, and this guard 15 is provided with an opening 3 used as an inlet or an outlet.

This mouth part 3 is usually provided with a cap, and the liquid agent inside is sealed.

The container 1 shown in FIG. 2 also has a pot-shaped main body 11 with a rectangular cross section.
An inspector 15 having a mouth portion 3 is integrated slightly below the upper end of the device.

At this time, the inspector 15 also has the function of reinforcing the main body 11.

The container 1 shown in FIG. 3 is also pot-shaped with a rectangular cross section, and has a mouth 3 at its upper end.

The examples shown in Figures 1 to 3 are for relatively small volumes; however, if the capacity is larger than this, a reinforcing material may be provided inside the container to enhance the shape retention function. is preferred.

The reinforcing material is also formed from the above-mentioned packaging material, but in addition to this, resin layer materials that are inert to the liquid agent and other than the above-mentioned paperboard and aluminum foil, such as polyethylene, nylon, polyethylene terephthalate, EVAL, etc., may be used singly or in combination. It may also be used as

Examples in which reinforcing materials are provided are shown in FIGS. 4 to 8.

The example shown in FIG. 4 is an example in which a reinforcing material is provided in the container 1 which is almost the same as that shown in FIG. Reinforcement material 4
This is an example in which 1.43 was glued.

In this case, reinforcing materials 45, 47 are also bonded between the guard 15 at the top of the container 1 and the main body 11, and the guard 15 near the mouth 3 between these reinforcing members 45, 47 is shaped upward in a frustum shape. These are formed so as to protrude from the sides, thereby enhancing the shape retention function in the vicinity of the mouth.

Further, in the example shown in FIG. 5, reinforcing members 41 and 43 are provided between the side walls of the main body 11 of the container 1 at approximately the center thereof.

In these examples, the shape retention ability of the bottom side of the container 1 is high, which is advantageous especially when the container 1 is installed upside down in a liquid preparation mixer.

Furthermore, in the example shown in FIG. 6, the reinforcing members 41, 43 are formed integrally with external reinforcing members 45, 47 between the upper side walls of the main body 11 of the container 1.

In addition, in the example shown in FIG. 7, the positions of the inspectors 15 in the compartments on both sides of the container 1 in the example shown in FIG.
It is located at the upper end of the main body 11 to increase the capacity of the container.

Furthermore, in the example shown in FIG. 8, a plurality of reinforcing members 41
．． 42, 43, and 44.

In these examples, the shape retention ability of the upper part of the container 1 is high, so that it is advantageous when the container 1 is installed in a liquid preparation mixer at the position shown in the figure.

The above are examples of containers that enclose a single processing liquid or one of a plurality of processing liquid parts.

When the processing liquid is divided into multiple parts, these containers may be integrated into a kit.

For example, as shown in FIG. 9, the container 1 may be formed by integrating containers 5, 6, and 7 each containing three different types of processing liquid parts.

Alternatively, as shown in Figure 10, a separate container 5.6
．． 7 may be integrated with a fastener 8 such as a belt-like band.

Such a container 1 or a container in which they are integrated is set in a liquid preparation mixer as a development processing liquid kit, and the sealed liquid is diluted with water while stirring to prepare a working liquid.

Also, Japanese Patent Application Laid-open No. 177132/1983, Japanese Patent Application No. 1-273
As described in No. 304, each stock solution sealed in the container of the present invention and water are mixed and diluted at a predetermined ratio immediately before the photosensitive material is processed in the processing tank of the automatic processing machine. It is also possible to use a method of replenishing according to the situation.

Furthermore, Japanese Patent Application Nos. 1-129388 and 1-268
As described in No. 814, after first mixing the stock solution and diluting it with water, as the sensitive material is further processed, the once diluted processing solution is mixed and diluted with water and replenished. It is also possible to apply it to Among the processing solutions prepared from these photographic processing solutions, the photographic processing solutions particularly preferably used in the present invention include black and white developer, color developer, fixer, bleach-fixer, bleaching solution, and water washing alternative stabilizing solution. It is preferable to apply it to processing liquids containing preservatives such as sulfites and hydroxyamines that are easily oxidized in the air, thiosulfate developing agents, anti-piping agents, etc., especially processing liquids containing sulfites. It is preferable to apply it to

The black and white developer contains hydroquinones, 1-phenol-
At least one black and white developing agent selected from 3-pyrazolidones and para-aminophenols is used.

Examples of hydroquinones include T and H.

rThe Theory of Th by James
e PotographicProcess (197
Compounds described on pages 300 to 311 of ``7th Year)'' can be used, but specifically, hydroquinone, methylhydroquinone, 2,3-dimethylhydroquinone,
2゜5-dimethylhydroquinone, 2,3.5-thonomethylhydroquinone, tetramethylhydroquinone, 2
．． 5-dimethylhydroquinone, methoxyhydroquinone, 2.5-dimethoxyhydroquinone, 2-chlorohydroquinone, 2.3-dichlorohydroquinone, 2,
5-dichlorohydroquinone, 2,6-dichlorohydroquinone, aminohydroquinone, bromohydroquinone, hydroxyhydroquinone, t-butylhydroquinone, phenylhydroquinone, 2-methyl-3-chlorohydroquinone, hydroquinone monosulfonic acid, and the like are used. The amount of hydroquinone used is 0.
．． 1 to 200 gel is preferable, more preferably 1 to 200 gel
100 gel, particularly preferably 2-50 g#
It is.

Specific examples of 1-phenyl-3-pyrazolidones include:
1-phenyl-3-pyrazolidone and British patent 943,9
No. 28, No. 1,093,281, U.S. Patent No. 2,289
, No. 367, No. 3.241,967 and No. 3,45.
Compounds having substituents at the 2-position, 4-position and/or 5-position of the 3-pyrazolidone ring as described in No. 3.109 etc., such as 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-pyrazolidone, 2- Morpholinomethyl-1-phenyl-3-pyrazolidone, 2- (1
, 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-3-pyrazolidone, 4.4
-dimethyl-2-hydroxymethyl-1-phenyl-3
-pyrazolidone, 4-chloromethyl-2-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone,
l-morpholinomethyl-4,4-dimethyl-1-phenyl-3-pyrazolidone, 2-(methyl-β-hydroxyethyl)aminomethyl-4,4-dimethyl-1-phenyl-3-pyrazolidone, 2-( di-β-hydroxyethyl)aminomethyl-4,4-dimethyl-1-phenyl-3-pyrazolidone, 5-methyl-1-phenyl-3-
Pyrazolidone and the like are used, and among these, 1-phenyl-3-pyrazolidone 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, J
rThe Theory of The by ames
Potographic Process (1977
Compounds described on pages 311 to 315 of 2013) can be used, but specifically, baraminophenol,
N-methyl-para-aminophenol, p-β-hydroxyaminophenol 1, p-α-aminoethylaminophenol 1, p-sulfamethylaminophenol, p
-Hydroxyphenylglycine, 4-amino-2-chlorophenol, 4-amino-3-tritetraphenol, 4
-Aminephenol-2-sulfonate, 4-aminophenol-3-sulfonate, N-methyl-N-(β
-sulfoamidoethyl)-p-aminophenol, N
-benzyl-p-aminophenol, N-methyl-p-
Amine phenol-2-sulfonic acid, 2,6-dichloro-p-aminophenol, 3-methyl-para-aminophenol, etc. can be used. The amount of the 1-phenyl-3-pyrazolidones and/or para-aminophenols used is preferably 0.01 to 100 g/j, more preferably 0.05 to 50 g/j, particularly preferably 0.1
~10g/j.

In addition to the hydroquinones, 1-phenyl-3-pyrazolidones, and/or para-aminophenols, the black-and-white developer contains various components that are usually added to black-and-white developers, such as carbonates, sulfuric acid, and sulfuric acid. Buffers such as salts, phosphates, alkanolamines, silicates, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
Preservatives such as bisulfite adducts of aldehydes and ketone compounds, alkali metal thiocyanates, polyalkylene oxide compounds, sodium thiosulfate, ammonium, phosphonium, or sulfonium-type onium compounds and polyionium compounds, and JP-A-57-63530 Development accelerators such as thioether compounds, hardeners such as geltaraldehyde or its bisulfite adducts, antifogging agents such as alkali metal halides, benzotriazole, benzothiazole, tetrazole, thiazole, etc. agents, phosphates such as polyphosphates, aminopolycarboxylic acids such as nitrilotriacetic acid, 1,3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, and oxycarboxylic acids such as citric acid and gluconic acid. , 1-hydroxyethylidene-1
, organic acids such as 1-diphosphonic acid, aminopolyphosphonic acids such as aminotono(methylenephosphonic acid), chelating agents such as polyhydroxy compounds such as 1,2-dihydroxybenzene-3°5-disulfonic acid, and ethylene glycol, diethylene glycol. , polyethylene glycols, esters thereof, and other thickening agents may optionally be included.

The pH of the black and white developer of the present invention is preferably 8.5 to 12.0, more preferably 9.0 to 11.5. 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, and includes various types that are widely used in various color photographic processes. These compounds are more stable than their free states;
Generally used in salt form, such as hydrochloride or sulfate. In addition, these compounds are generally used in a color developer at 1°C.
It is used at a concentration of from about 0.1 to about 30 g per degree Celsius, preferably from about 1 to about 15 g per degree Celsius of color developer.

A useful aromatic primary amine color developer is N.

It is an N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Examples include N,N-diethyl-p
-phenylenediamine hydrochloride, N-ethyl-N-propylbaraphenylenediamine hydrochloride, N,N-dimethyl-
p-phenylenediamine hydrochloride, 2-amino-5(N-
Ethyl-N-dodecylamino) to toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-
4-aminoaniline sulfate, 4-amino-3-methyl-
N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-methyl-N, N-diethylaniline sulfate, 4-amino-N-(β-methoxyethyl)-N
-ethyl-3-methylaniline-p-toluenesulfonate, N,N-diethyl-3-(β-methanesulfonamidoethyl)-4-aminoaniline sulfate, and the like.

The effective color developing agent used in the present invention is a para-phenylenediamine color developing agent having at least one water-soluble group (hydrophilic group) on the amino group, and typical examples of these color developing agents include: , the following compounds, but the present invention is not limited thereto.

In addition, the above-mentioned water-soluble groups include: 1 GHz) I, 1-CHzOH.

-(CHz)1.1-NH5Oz-(CH2)rl-C
H-5-(CHz)m-0-(CHz)n-CHs, -
(CHzCH20)nCmHzm++ (m and n are integers of 0 or more) COOH group, -3O, H group, etc. are mentioned as preferable ones.

(1) 02H5C2H4NH3O□CH.

\/ (2) (3) (4) (7) (5) (8) (6) (9) NI'I2 (10) (13) Ni+2 (11) (14) (l 2) N1'12 pieces Particularly useful color developing agents for the invention include -(CH2) n-CH20H1-(CHz) as a substituent on the amino group.
--NH3O□-(CH2)n-CHz, -(C)+2
) m-0-(CH2)n-CHa, -(CH2CH20
) nCmH2, fi. 1, and specific examples include (1) and (2) of the specific examples above.
), (3), (4), (6) and (7). However, m and n are integers of 0 or more, preferably 0 to 5.

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

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

In addition, it is also possible to add inorganic or organic antifoggants 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. 2.495. , 5-nitropencyimiguzole described in No. 2,497,917 and No. 2,656,271, mercaptobenzimidazole, mercapto, including 0-phenylenediamine. Benzoxazole, thiouracil, 5-methylbenzotriazole, 5-nitroindazole or Japanese Patent Publication No. 46-4167
Examples include the heterocyclic compound described in No. 5.

In addition to these various components, development inhibitors disclosed in Japanese Patent Publications Sho-Borrow No. 19039, No. 45-6149, and U.S. Pat.

Among these development accelerators are U.S. Pat.
No. 04, No. 3,671,247, Special Publication No. 44-950
Various pyridium compounds represented by No. 3, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, and U.S. Patent No. 2.
No. 533,990, No. 2,531,832, No. 2,9
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers described in Japanese Patent Publication No. 50,970, Japanese Patent Publication No. 2,577゜127 and Japanese Patent Publication No. 44-9504, organic solvents and organic amines described in Japanese Patent Publication No. 44-9509, Includes ethanolamine, ethylenediamine, jetanolamine, triethanolamine, etc. In addition to benzyl alcohol and phenethyl alcohol described in U.S. Pat. No. 2,304,925, 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, and other stocks may be added.
The compound described in No. 4-9509 can be used as an organic solvent to increase the solubility of the developing agent.

The color developing solution can also contain various chelating agents as water softeners and heavy metal sequestering agents. Such chelating agents include phosphates such as polyphosphates, nitrilotriacetic acid, 1,3-diaminopropanoltetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid and hydroxyethyliminodiacetic acid, oxycarboxylic acids such as citric acid and gluconic acid, 1-hydroxyethylidene-
Examples include organic acids such as 1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid), and polyhydroxy compounds such as 1,2-dihydroxybenzene-3,5-disulfonic acid.

Additionally, auxiliary developers can be used with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminephenol sulfate (methol), phenidone, N,N-diethyl-p-aminophenol hydrochloride, N,N,N,N-tetramethyl-p- Phenyldiamine hydrochloride and the like are known, and the amount added thereof is usually preferably 0.01 g to 1, Og/j. In addition, if necessary, competitive couplers such as citradinic acid,
N as a fogging agent.

Tin chelate compounds such as N,N-trimethylenephosphonic acid tin and tin citrate; borohydride compounds such as tert-butylamine borane; colored couplers; development-inhibited release couplers (so-called CIR couplers)
Alternatively, a development inhibitor-releasing compound or the like may be added.

The color developing agent can be used at a pH of 8 to 14, more preferably at a pH of 9.5 to 14, and particularly preferably at a pH of 9.5 to 14.
HII, used in 5-13.5. The temperature of the treatment is 1
The temperature is preferably 0 to 60°C, more preferably 20 to 50°C.

As the bleaching agent used in the bleaching or bleach-fixing solution of the present invention, any bleaching agent can be used, such as red blood salt, iron chloride (British Patent No. 736.881, Japanese Patent Publication No.
44424) Persulfuric acid (German patent 2,14)
1,199) Hydrogen peroxide (Special Publication No. 1,198-1)
1617 and No. 58-11618), organic ferric complex salts such as ethylenediaminetetraacetic acid ferric complex salts are used.

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

(1) Diethylenetriaminepentaacetic acid (2) Diethylenetriaminepentamethylphosphonic acid (3) Cyclohexanediaminetetraacetic acid (4) Ethylenediaminetetraacetic acid (5) Methyliminodiacetic acid (6) Probyliminodiacetic acid (7) Butyliminodiacetic acid (8) Cyclohexanediaminetetramethylenephosphonic acid Acid (9) Triethylenetetraminehexaacetic acid (10) l-lyethylenetetraminehexamethylenephosphonic acid (11) Glycol ether diamine tetraacetic acid (12) Glycol ether diamine tetramethylene phosphonic acid (13) 1,2-Diaminopropane tetraacetic acid ( 14)
1.2-Diaminopropane tetramethylenephosphonic acid (15) 1.3-Diaminopropan-2-ol tetraacetic acid (16) 1.3-Diaminopropane-2-ol tetramethylenephosphonic acid (17) Ethylenediamine diorthohydroxyphenyl Vinegar (18) Ethylenediamine diorthohydroxyphenyl methylene phosphonic acid (19) Ethylene diamine tetramethylene phosphonic acid (20) N-hydroxyethyliminodiacetic acid Ferric complex salt of organic acid is free acid (hydrogen salt), sodium salt ,
Alkali metal salts such as potassium salts and lithium salts, or ammonium salts or water-soluble amine salts such as triethanolamine salts are used, but potassium salts, sodium salts and ammonium salts are preferably used.
At least one of these ferric complex salts may be used, but
Two or more types can also be used in combination. The amount used can be arbitrarily selected and must be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is generally used at a lower concentration than other aminopolycarboxylate salts because of its high oxidizing power. can. For example, 0201 per ε of working liquid
It can be used in a mole or more, preferably 0.05 to 0.6 mole.

Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

The bleach and bleach-fix solutions can be used at a pH of 0.2 to 9.5, preferably 4 to 9, more preferably 5.5 to 8.
Used in 5. The treatment temperature is used at 80° C. or lower, preferably 55° C. or lower, most preferably 45° C. or lower to suppress evaporation.

The bleaching solution can contain various additives together 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, pH buffering agents such as sulfates, oxalates, acetates, carbonates, and phosphates, solubilizing agents such as triethanolamine, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, etc. Those known to be added to ordinary bleaching solutions, such as acids, alkylamines, and polyethylene oxides, can be added as appropriate.

Bleach-fix solutions include bleach-fix solutions that contain a small amount of halogen compounds such as potassium bromide, or conversely, bleach-fix solutions that contain a large amount of halogen compounds such as potassium bromide and ammonium bromide. Further, a special bleach-fixing solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide can also be used.

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. can also be used.

Silver halide fixing agents to be included in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanate such as ammonium thiocyanate, thiourea, thioether, high concentration bromide, iodide, etc. These fixing agents can be used in an amount that can dissolve 5 g/j or more, preferably 50 g/j or more, more preferably 70 g/j or more.

As in the case of the above bleaching solution, the bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
pH buffering agents consisting of various salts such as acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. Also, preservatives such as hydroxyamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, and polycarboxylic acids. , organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, solubilizers such as alkasolamines, stain inhibitors such as organic amines, other additives, methanol, dimethylformamide, etc. ,
An organic solvent such as dimethyl sulfoxide can be appropriately contained.

When the processing liquid having fixing ability used in the present invention is a fixing liquid, the fixing liquid may be used as a fixing agent such as thiosulfate (described in Japanese Patent Application Laid-open No. 57-185435), thiocyanate (described in British Patent No. 565). No. 135, JP-A-54-13714
No. 3 (described in each publication) Halides (Japanese Patent Application Laid-open No. 52-130
639) Thioether (Belgium patent 6)
26970) Thiourea (British Patent No. 1, 18)
9,416) etc. can be used. In addition to these fixing agents, the fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, pH buffering agents consisting of various salts such as sodium acetate and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained. Also, preservatives such as hydroxyamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, and polycarboxylic acids. , organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, and other additives such as residual color improvers,
An organic solvent such as methanol, dimethylformamide, dimethyl sulfoxide, etc. can be appropriately contained.

The photographic processing liquid used in the present invention may be a processing liquid for directly processing a photosensitive material. It may also be a part agent in which part or all of the replenisher used for replenishment and the composition used for preparing these processing solutions are concentrated.

When enclosing these liquid agents, it is preferable to purge the inside of the container with an inert gas.

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

Example 1 Milk "LΩ" [1j2 of purified water, 5 g of potassium bromide, 25.6 g of gelatin, 0 thioether) 1 (CH□) 2S (CH2) 2S (CH
2) 5% water solution of 20H? ! Add 2.5mε, 66℃
An aqueous solution of 8.33 g of silver nitrate, 5.94 g of potassium bromide, and 0.0 g of potassium iodide were added to the solution maintained at 0.25 g while stirring.
An aqueous solution containing 726 g was added over 45 seconds using the double jet method.

Then, after adding 2.9 g of potassium bromide, 8 g of silver nitrate
．． An aqueous solution containing 33 g was added over 24 minutes, and then 0.1 mg of thiourea dioxide having the following structure was added.

After that, 20ml of 25% ammonia solution! , 50% ammonium nitrate 10+nj was added and the mixture was physically aged for 20 minutes, followed by neutralization by adding 240 mR of IN sulfuric acid.

Subsequently, an aqueous solution containing 153.34 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide was heated to a potential pAg of 8.
It was added over 40 minutes by a controlled double jet method while maintaining the temperature at 2.

At this time, the flow rate at the end of addition is the flow rate at the start of addition 9
It accelerated to double.

15ml of 2N potassium thiocyanate solution after completion of addition! and then add 45 ml of 1% potassium iodide aqueous solution to 3
Added over 0 seconds.

After this, the temperature was lowered to 35°C, soluble salts were removed by the sedimentation method, and then the temperature was raised to 40°C, and 76 g of gelatin, 76 mg of Proxel, and 760 m of phenoxyethanol were added.
The pH of the emulsion was adjusted to 6.50 and the pAg to 8.20 using sodium hydroxide and potassium bromide.

After raising the temperature to 56°C, 186 mg of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene
was added, and 10 minutes later, a sensitizing dye with the following structure was added to 520
mg was added.

In the resulting emulsion, 99.5% of the total projected area of all grains consisted of grains with an aspect ratio of 3 or more, and the average projected area diameter of all grains with an aspect ratio of 2 or more was 1.4.
'8gm, standard deviation 25.6%, average particle thickness 0
．． 195s+, the aspect ratio was 7.6, and the total iodine content was 3.2 mol% based on the amount of gold and silver.

1. To the above emulsion, the following chemicals were added in the following amounts per mole of silver halide to prepare a coating solution.

・Polymer latex (poly(ethyl acrylate/MEC lyric acid: copolymerization ratio 97/3) 25.0g ・Hardening agent (1,2
-bis(vinylsulfonylacetamido)ethane
3.0g・2.6-bis(hydroxyamino)
-4-gelamino-1,3,5-triazine 0 mg ・Sodium polyacrylate (average molecular weight 41,000) 4.0 g ・Potassium polystyrene sulfonate (average molecular weight 600,000) 1.0 g ・Polyacrylamide (average Molecular weight 45,000) 24g! A polyethylene terephthalate base having a thickness of 175 cm and colored with JLJI blue was prepared by providing an undercoat layer on both sides of the base in the amount shown below.

・Gelatin 84mg/m2 ・Polymer below 60B/m2 ・Dye below 17mg/m2 Coat the above coating solution on both sides of the support at the same time as the surface protective layer coating solution with the following composition. The amount of silver coated was 1 per side.
．． It was 85g/m2. The surface protective layer was prepared so that each component was coated in the following amounts.

Togelatin 1.15g/m2 Polyacrylamide (average molecular weight 45,000) 0.25g/m2・Sodium polyacrylate (average molecular weight 400,000) 0.02g/m2・p
- Sodium salt of t-octylphenoxy diglyceryl butyl sulfonate 0.02 g/m2 ・Poly(degree of polymerization 10) oxyethylecetyl ether
0.035g/m2・Poly(polymerization degree 1
0) Oxyethylene-poly(degree of polymerization 3) oxyglycerylnyl-octylphenoxy ether 0.01 g/m2 4-hydroxy-6-methyl 1,3,3a.

7-Chitrazaindene 0.0155g/+n2
・2-chlorohydroquinone 0.154 g/m2
・CaFl? 5O3K O,003
g/m2・Polymethyl methacrylate (average particle size 3-5p) 0.025 g/m
2. Poly (methyl methacrylate/methacrylate) (copolymerization ratio 7:3 average particle size 2.5 p) 0.020 g/
m2 In this way, a photosensitive material with a coating film swelling percentage of 230% was prepared.

Preparation of concentrated solution (Developer) Part A Potassium hydroxide Potassium sulfite Sodium sulfite Potassium carbonate Diethylene glycol diethylene triamine Pentaacetic acid 1-(N,N-diethylamine)ethyl-5-mercaptotetrazole Hydroquinone Add water. 30g 30g 55g 0g 5g 80g 0g 0.75g 50g 125mj Part B Diethylene glycol 3-3° ~ dithiobishydrocinnamic acid glacial acetic acid 5-nitroindazole 1-phenyl-3-pyrazolidone thioglycerin Add water artC geltaraldehyde (50wt/wt%) Sodium bromide Sodium metabisulfite water added 25g 1.5g 102.6g 3.75g 34.5g 4.5+nj 50mA 50g 5g 05g 50mJ <Fixer> Ammonium thiosulfate (70wt/voe%) ) 200m
j Ethylenediaminetetraacetic acid disodium trihydrate 0.03g Sodium sulfite 15g Boric acid
4g 1-(N,N-dimethylamino)-ethyl-5-mercaptotitrazole 1g tartaric acid
3.2g glacial acetic acid
45g sodium hydroxide 15
g Sulfuric acid (36N) 3.9 g Aluminum sulfate 10 g Add water
400m1! pH 4,68 11 盈且Il The above developer concentrate was filled into the following containers for each part. This container is one in which the containers of Parts A, B, and C are connected together by the container itself or other packaging material.

Further, the above fixer concentrate was also filled into the same type of container.

The processing liquid in such a container was turned upside down and inserted into the perforating blade of the processing liquid stock tank attached to the side of the automatic processing machine, and the cap was broken and filled.

These developing solutions and fixing solutions were filled in the developing tank and fixing tank of an automatic processor in the following proportions using metering pumps installed in the automatic processor, respectively. Every time 8 sheets of light-sensitive material were processed in terms of cut-out size, the processing agent stock solution and water were mixed and replenished into the tank of the automatic processing machine in this proportion.

Developer I Fixer xcr>+R formation An automatic processor with the following configuration was used.

Fill the washing tank with tap water, and add Na to the bottom of the tank.
20 / B t O3 / S 102 (1076
Two bags containing 200 g of a silver sustained release agent containing 1.7 wt% of Ag wrapped in nonwoven fabric were submerged in a soluble glass consisting of 5,725 wt% of Ag.

Liquid amount Temperature Path length Process time fixation
15j 32°C541mm 11. ．． Wash with water for 7 seconds 1] 17℃ 305mm
j, 7 seconds running water squeeze 6.6 seconds dry 58℃ 368mm
8.0 seconds total 1827
The photosensitive material A was exposed to X-rays, and the photosensitive material A was exposed to X-rays, using the above-mentioned automatic processor and each processing solution mixed in the above-mentioned proportions, and the cut-out size (10 x 12 inches) was obtained using the above-mentioned process time. ) Developing was performed while replenishing 25 mε of developer and 25 mj of fixer per sheet.

Washing water is supplied at a flow rate of 5 ρ per minute by opening a solenoid valve in synchronization with the time when the photosensitive material is being processed (approximately 0.5 ρ/1 four-cut cut) - automatically at the end of the day's work. The solenoid valve opens and all the water in the tank is drained.The average number of sheets processed per day is about 200 sheets of cut-size size.

A packaging material having the following structure was obtained using paperboard with a weight of 500 g/m2.

[Liquid] PE layer with one nylon/PE/shoulder/P'E/flat paperboard/PE [Outside] In this case, first, according to the description in Japanese Patent No. 510861, PE is extruded onto one side of the paperboard at a low temperature to form an extrusion coating film. By forming the paper, curl-free paper was obtained.

On the other hand, a PE layer was also formed on the outer surface of the paper by lamination.

In a separate process, a PE layer was formed on the outer surface of the K-nylon by the method described in Japanese Patent No. 510861, and a layer of A was further formed on the inner surface of the nylon via PEIII.

A packaging material was produced by bonding the paper thus formed and the Ai layer via PE.

The lamination thickness of the paper liquid is 200p, and the outer lamination thickness is 50p.
It was a door.

In addition, the oxygen permeability at 25°C and 65%RH is 2 +++
j/m2/24hr/atm or less.

A container shown in FIG. 9 was made from such packaging material.

The capacities of containers 5.6.7 are 4.6°C and 0.8°C, respectively.
The temperature was set at 3° C. and 0.8:M2, and parts solutions A, B, and C were respectively sealed in this container 5.6.7.

Container ■ According to Container I, a packaging material with the following structure was produced, and a container with the same structure was produced.

[Liquid] PE/AI! /PE/flat paperboard/PE [
Outside] The thickness of the liquid material and the outside layer are as follows:
180 habit and 60tjJIl oxygen permeability is 3.5m!
/m2/24hr/atm or less.

1...” Product name: EVA/LDP used in Cubitener
E (thickness 0.43n+m) containers of three sizes (same as container ■) were filled with each parts liquid A, B, and C, and packaged in a cardboard box.

The container itself will deform, so if it is not packaged in a cardboard box,
It cannot be set in the correct position on the automatic processing machine.

An integrated container having three types of containers having the same capacity as container I was produced by molding high-density polyethylene (thickness: 0.6 mm).

The results using these containers I-TV are shown in the table below.

Easy to transfer liquid from container Disposal of container ■ Completely easy to incinerate and crush ■
Complete, easily incinerated, crushable, with residual liquid
A flame-retardant cardboard box is also required and must be separated for disposal.
This shows that even packaging materials mainly made of paper can contain a sufficient amount of liquid agent.

In addition, in container (2), pinballing and cracking were likely to occur in the two AI layers, and the liquid sometimes oozed out.

<Effects> According to the present invention, firstly, a container is provided in which the developing processing solution for silver halide photographic materials is kept stable even when stored for a long period of time from when it is manufactured until it is used in a kit state. will be realized.

Second, a container is realized that can maintain its shape without deforming even if it is filled with a developing treatment solution.

Third, the packaging material that makes up the container can be easily folded or crushed before and after use, making it a space-saving container that is particularly convenient for disposal or reuse. will be realized.

Furthermore, fourthly, it can be easily disposed of after use, for example by being incinerated.

[Brief explanation of drawings]

Figures 1, 2, 3 and 10 are, respectively,
FIG. 1 is a front view showing an example of a photographic processing liquid container of the present invention. FIG. 4 is a perspective view showing another example of the photographic processing liquid container of the present invention. FIG. 5, FIG. 6, FIG. 7, FIG. 8, and FIG. 9 are longitudinal cross-sectional views showing further different examples of the photographic processing liquid container of the present invention. Explanation of symbols 1... Container

Claims (1)

[Claims] (1) A container for storing a development processing solution for silver halide photographic light-sensitive materials inside, characterized by being made of a packaging material having gas barrier properties, including a paperboard laminated with at least a flexible resin layer. Photographic processing liquid container.