JP2001350243A - Container for photographic processing agent and method for preserving photographic processing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preserving a photographic processing agent and a container for the photographic processing agent excellent in performance as a gas barrier and not containing a compound which causes the generation of dioxins. SOLUTION: The container comprises a multilayer film with at least one polyvinyl alcohol resin layer, at least one polyethylene layer on the inside of the polyvinyl alcohol resin layer brought into contact with a photographic processing agent and at least one polyolefin resin layer or nylon layer on the outside of the polyvinyl alcohol resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a container for a photographic processing agent and a storage method, and more particularly to a flexible container excellent in the preservability of a liquid processing agent, environmentally friendly and excellent in disposal. And a method for preserving a photographic processing agent.

[0002]

2. Description of the Related Art Photographic processing agents are often supplied as liquids in the form of concentrates or part liquids in both the monochrome and color fields. Since these photographic processing agents are liable to be deteriorated when exposed to air, they are stored and distributed in containers made of a chemical resistant material having excellent gas barrier properties. In particular, in recent years, flexible type containers that are easy to dispose after use are often used. As a material which satisfies these conditions and is often used for a flexible container for a photographic processing agent, there is a composite film in which a vinylidene chloride-coated nylon (K-NY) and a polyethylene (PE) film are combined.

[0003]

However, KN used as a barrier layer in this composite film is
It is known that a y-film has a vinylidene chloride layer and generates a harmful gas which causes dioxin generation during incineration. For this reason, some chloride-free materials have been proposed as substitutes for K-Ny. For example, there is a film on which an inorganic substance such as silicon oxide is deposited,
This film is not suitable for use as a container for a liquid photographic processing agent because the film has low adhesion strength to a vapor-deposited layer and, when formed into a composite film, has particularly poor physical strength such as impact strength. Further, as another alternative material, a composite film using an ethylene-vinyl alcohol copolymer resin (EvOH) film has been proposed. This composite film is superior to a composite film using a film on which an inorganic substance such as silicon oxide is vapor-deposited in terms of gas barrier properties, but has been unsatisfactory in that it is somewhat expensive.

[0004] Accordingly, an object of the present invention is to provide a container for a photographic processing agent which is less expensive and which has more excellent gas barrier properties without containing a compound which causes dioxin, and an excellent photographic processing agent using this container. To provide a preservation method.

[0005]

In order to achieve the above object, the present invention comprises at least one polyvinyl alcohol resin layer and at least one polyethylene layer inside the polyvinyl alcohol resin layer in contact with a photographic processing agent. Have
It is characterized by comprising a multilayer film having at least one polyolefin-based resin layer or nylon layer outside the polyvinyl alcohol resin layer.

In particular, when the structure of the multilayer film is in contact with the photographic processing agent when viewed from the polyvinyl alcohol resin layer,
The present invention is more effective when a linear low-density polyethylene (LLDPE) layer is provided, and the outer layer is composed of three layers having any one of a nylon layer, an LLDPE layer, and a polypropylene layer. In addition, by using a container for a photographic processing agent composed of such a multilayer film having a three-layer structure,
It has been found that the piercing suitability of the container is also improved.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Container 1 for a photographic processing agent of the present invention
Is at least one polyvinyl alcohol resin layer 2
And at least one polyethylene layer 3 on the inner side of the polyvinyl alcohol resin layer 2 in contact with the photographic processing agent,
At least one layer outside the polyvinyl alcohol resin layer 2
It is formed of a multilayer film 5 having a polyolefin resin layer or a nylon layer 4. The polyvinyl alcohol resin layer 2 may be a film made of a single material of polyvinyl alcohol, or may be a film made of a polyvinyl alcohol resin into which an inorganic substance is kneaded for improving moisture resistance.

In a preferred embodiment of the multilayer film 5 used in the container of the present invention, a polyvinyl alcohol resin layer is provided with a polyolefin resin layer on both sides, or a polyvinyl alcohol resin layer is provided with a nylon layer on the outer side. A layer configuration in which a polyolefin-based resin layer is provided on the inner side (hereinafter, sometimes referred to as a liquid contact side) in contact with a photographic processing agent can be given.

As the polyolefin resin used in the present invention, polyethylene (PE) or polypropylene can be preferably used. Specific examples of polyethylene include LLDPE (linear low density polyethylene) and LDPE (low density polyethylene). Specific examples of polypropylene include CPP
(Unstretched polypropylene), OPP (stretched polypropylene) and the like.

It is preferable to use LLDPE on the liquid contact side of the container of the present invention in view of chemical resistance and strength. The film used on the outside of the polyvinyl alcohol resin layer 2 can be selected from the above-mentioned materials in accordance with the purpose of use of the container and used in combination. For example, OP
P is a preferable material because the bag-made container has appropriate hardness and is easy to handle, and nylon is preferable because the bag-made container has excellent strength. In particular, in the case of the present container, since the polyvinyl alcohol layer 2 is used as a barrier material, OPP is preferable from the viewpoint of moisture resistance.

The multi-layer film 5 is manufactured by a known method such as a method of bonding the film with a resin obtained by melting a resin such as an adhesive or PE or a method of slitting and extruding a plurality of resins. be able to.

The container 1 of the present invention is a flexible type container such as a three-sided sealed bag, a four-sided sealed bag, a pillow bag, a gusset bag or a self-standing container called a standing pouch, or a container having a multi-layer structure represented by a back-in box. Can be used in various general shapes. The capacity is not particularly limited, and can be widely used as a container for a photographic processing agent in a form suitable for each size from a small size of 50 ml to a large size of 20 L. For example, when used in a medium-sized or larger size exceeding 1 L, a strength suitable for enclosing a large volume of liquid can be obtained by adopting a form called a water pillow type having a multiple bag structure. When used in a water pillow type, for example, a multilayer film using a polyolefin-based resin such as LLDPE on both sides of a polyvinyl alcohol resin is used for the outer film, and a single-layer film of LLDPE is used inside (liquid contact side). A heavy bag configuration can be used.

Recently, there has been proposed a method in which a tube 6 or the like is pierced into a container of a photographic processing agent and connected to a replenishing device of an automatic developing machine to suck out a processing solution directly from the container and replenish the container. According to this method, there is no need for the preparation of a solution for diluting and dissolving the treatment agent, and the treatment agent can be replenished almost without contact with air, so that the treatment agent is stable. Although it is a preferred method in terms of excellent properties, containers that can be used, even when piercing a tube or the like,
It is limited to containers made of a piercing-suitable material that does not allow air to enter from that part or cause liquid leakage. In the case of the container of the present invention, by using a polymer film having a low tensile strength for at least one of the other layers combined with the polyvinyl alcohol resin, a container having piercing suitability that can be used in this piercing method replenishing method is obtained. be able to. Specifically, at least one layer on both sides of the polyvinyl alcohol resin layer is used in combination with a relatively thick film having a relatively large thickness of 60 μm or more and a small tensile strength, for example, LLDPE, unstretched nylon, or unstretched polypropylene. By doing so, it is possible to give excellent piercing suitability.

For the polyvinyl alcohol resin layer 2,
When only one side is combined with each layer of LLDPE, unstretched nylon or unstretched polypropylene having low tensile strength, piercing suitability can be obtained, but in the case of only one side, the tube 6 pierced into the container 1 tends to come off. There is. This problem does not occur if the tube tip is a polymer material such as soft vinyl chloride (PVC). However, if the tube tip is made of metal so that it can be easily pierced into the container, only one side is used. Are easy to cause an accident that the tube comes off and leaks. By providing a polymer film layer having low tensile strength on both sides of the polyvinyl alcohol resin layer 2 as described above, such an accident can be reliably prevented from occurring.

The container 1 of the present invention is made of a halogenated material such as a processing agent for a monochrome light-sensitive material, a processing agent for a plate making film, a processing agent for an X-ray light-sensitive material, a processing agent for a color film and a color photographic paper, and a processing agent for a reversal film. Any processing agent for a silver photographic light-sensitive material can be used regardless of the composition.

Hereinafter, the main ones of these treating agents will be outlined, but the present invention is not limited to these. Developers for graphic arts photosensitive materials and black-and-white photosensitive materials are dihydroxybenzene-based developing agents, 1-phenyl-3-pyrazolidone-based or p-aminophenol-based developing agents, preservatives such as reductones, sulfites, alkaline agents, PH buffer materials such as carbonates or phosphates, halides such as NaBr and KBr as development inhibitors, glycol-based organic solvents, organic development inhibitors such as benzotriazole derivatives and indazol derivatives, and heterocyclic compounds having a mercapto group. It may contain a silver sludge inhibitor, and may further contain a color tone agent, a surfactant, an antifoaming agent, a water quality regulator, a hardener, an amino compound, and the like, if necessary.

The fixer for graphic arts light-sensitive materials and black-and-white light-sensitive materials contains a preserving agent such as thiosulfate or sulfite, a pH buffer such as acetic acid or boric acid as a fixing agent,
Hardening agents such as aluminum salts, organic acids as aluminum precipitation inhibitors, may also contain a pH adjuster such as sulfuric acid,
Further, if necessary, a fixing accelerator and a water quality adjusting agent may be contained.

The stabilizer for the graphic arts light-sensitive material and the black-and-white light-sensitive material is a mercapto compound, a sulfite,
Water quality regulator, pH buffer, may contain a pH regulator,
It may further contain a thiosulfate, a lithium salt, a magnesium salt or the like as necessary.

The color developing solution for color light-sensitive materials is p-
It may contain a phenylenediamine-based color developing agent, a hydroxylamine-based preservative, a sulfite-based preservative, a halide development inhibitor, a pH buffering agent such as a carbonate, and an alkaline agent. Agents, surfactants, water quality regulators, amino compounds, defoamers.

The bleaching agent for a color light-sensitive material includes a bleaching agent such as an aminopolycarboxylic acid-based iron complex, a bromide, a nitrate,
It may contain a pH adjuster, and if necessary, may further contain a bleaching accelerator, a pH buffer such as acetic acid or an organic acid, and a water quality adjuster.

The bleach-fixing agent for color light-sensitive materials includes a bleaching agent such as an aminopolycarboxylic acid-based iron complex, a fixing agent such as thiosulfate, a preservative such as sulfite, and a pH buffer such as acetic acid or an organic acid. And a pH adjusting agent, and may further contain a bleaching accelerator and a water quality adjusting agent as necessary.

The fixing agent for color light-sensitive materials may contain a thiosulfate-based fixing agent, a preservative such as a sulfite, a pH buffer such as acetic acid or an organic acid, and a pH adjuster. In addition, a fixing accelerator and a water quality adjusting agent may be included.

The stabilizing solution for a color light-sensitive material may be a fungicide or a bactericide, a water quality regulator, a pH of acetic acid or an organic acid or the like.
It may contain a buffer, a pH adjuster, and a surfactant, and may further contain an organic acid-based hardener as needed.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the present invention is limited thereto. The performance of the containers used in the examples was examined by the following test methods.

[Preservation test] The photographic processing agent described in each example was put in each test container, sealed, and left under the conditions described in each example. The degree of subsequent coloring and (b) the degree of deterioration due to standing were confirmed, and the effect of each container on the stability of the photographic processing agent was examined.

(A) Degree of coloring after standing: The degree of coloring of the contents after standing was visually evaluated according to the following criteria. Evaluation of coloring of liquid ○: No change compared to before leaving. Δ: Slight coloring is observed, but there is no practical problem. X: Liquid coloring is remarkable and the commercial value is impaired.

(B) Degree of deterioration due to standing: According to the photographic processing agent used in each of the examples, the content of each component suitable for confirming the deterioration of the composition before and after standing was determined. The compound was analyzed to determine the residual ratio of the compound.

[Drop test] A test sample prepared by putting the photographic processing agent described in each example in each test container and sealing it is put in a cardboard box, and the drop point is set to the bottom surface according to JIS Z0202 and the height is set to 80 cm. Then, the container was dropped five times in succession, and the state of bag breakage of the container was examined. Evaluation of drop test ○: No damage. ×: One or more of the five were damaged.

[Vibration Test] A test sample prepared by putting the photographic processing agent described in each example into each test container and sealing the container was placed in a cardboard box, accelerating at 0.75 G according to JIS Z0200, and having a frequency of: A test was performed under the conditions of sweeping 5 to 50 Hz and vibration time: 40 minutes each for vertical and horizontal directions, and the pinhole generation state of the container was examined. Evaluation of vibration test ：: No pinhole. ×: Pinholes occurred.

Example 1 The performance of a small-capacity container was examined by performing the following tests. In a flexible container 1 (single bag) having a capacity of 500 ml in a three-side seal type prepared using the multilayer film 5 having the constitution shown in Table 1, 250 ml of the main drug part solution of the color developing solution for a color negative film shown below is placed, and heat-sealed. A test sample was prepared by sealing to prevent liquid leakage.

Color developing solution Main part solution CD-4 400 g Sodium bisulfite 4 g Add water to adjust to 1000 ml pH value 50% -Adjust to pH 1.0 using sulfuric acid CD-4: N-ethyl-N- ( β-hydroxyethyl) -3-methyl-4-aminoaniline sulfate

[0032]

[Table 1] K-Ny: Nylon coated with vinylidene chloride LLDPE: Linear low density polyethylene K-PET: Polyethylene terephthalate coated with vinylidene chloride OPP: Stretched polypropylene PVA: Polyvinyl alcohol Ny: Nylon

These test samples were subjected to 50 ° C., 75% R
H was left in a constant temperature bath for 800 hours, and the stability of the contents of each container was compared by measuring the coloring of the liquid after standing and the residual ratio of the color developing agent (CD-4). The residual ratio of the color developing agent was determined by measuring the amount of CD-4 in each sample before and after standing in a thermostat using high-speed chromatography. Further, the above-mentioned drop test and vibration test were performed to examine the strength of each container 1 when the photographic processing agent was enclosed. Table 2 shows these results.

[0034]

[Table 2]

From these results, it can be seen that when stored using the container 1 of the present invention, the stability of the photographic processing agent is extremely excellent. Further, it can be seen that the container 1 of the present invention is excellent in strength as well as the conventional one.

Example 2 The performance of a large-capacity double bag container was examined by performing the following tests. Four-sided seal type 3000 manufactured using the multilayer film 5 having the configuration shown in Table 3.
Water pillow type flexible container 1 (double bag) with ml capacity
Then, 2000 ml of a concentrated stock solution of a color developing solution for one part of color paper shown below was placed therein, and a cap was closed to prevent liquid leakage, thereby obtaining a test sample.

Color developing solution Diethylenetriaminepentaacetic acid 3.5 g Triethanolamine 30.0 g N, N-diethylhydroxylamine 15.0 g Fluorescent whitening agent (Kayahole manufactured by Nippon Kayaku) 25.0 g CD-3 35.0 g Potassium carbonate 60.0 g Potassium chloride 1.5 g Adjusted to 1000 ml by adding water pH value Adjusted to pH 13.5 using KOH CD-3: N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl -4-aminoaniline sulfate

[0038]

[Table 3] K-Ny: Nylon coated with vinylidene chloride LLDPE: Linear low density polyethylene K-PET: Polyethylene terephthalate coated with vinylidene chloride Ny: Nylon PE: Polyethylene PVA: Polyvinyl alcohol OPP: Stretched polypropylene

In the same manner as in Example 1, these test samples were left in a thermostat at 50 ° C. and 75% RH for 800 hours.
The color of the liquid after standing and the residual ratio of N, N-diethylhydroxylamine (DEHA) were measured to determine the stability of the contents of each container 1. The residual ratio of DEHA was calculated by measuring the amount of DEHA in each sample before and after standing in a thermostat using gas chromatography. Further, the above-mentioned drop test and vibration test were performed to examine the strength of each container when the photographic processing agent was enclosed. Table 4 shows these results.

[0040]

[Table 4]

From these results, it can be seen that when stored using the container 1 of the present invention, the stability of the photographic processing agent is extremely excellent. Further, it can be seen that the container 1 of the present invention has the same excellent strength as a conventional one even when a large-capacity photographic processing agent is enclosed as a water pillow type container.

Example 3 The performance of a large-capacity double bag container with respect to a monochrome developer was examined by performing the following tests.
A developer for a photosensitive material for plate making shown below was placed in a water-pillow-type flexible container (double bag) having a capacity of 10 L, which is a four-sided seal type, manufactured using a multilayer film having the same configuration as the containers F and H of Example 2. 10 L of the concentrated undiluted solution was added, and the cap was closed to prevent liquid leakage, and used as a test sample.

Developer Diethylenetriaminepentaacetic acid 3.0 g Potassium sulfite 135.0 g Potassium bromide 7.5 g Potassium carbonate 120.0 g Diethylene glycol 100.0 g 5-Methylbenzotriazole 0.45 g Dimezone S 3.0 g Hydroquinone 60.0 g 1- Phenyl-5-mercaptotetrazole 0.06 g Add water to adjust to 1000 ml pH value Adjust to pH 10.6 using KOH

These test samples were left to stand naturally for one year, after which the solution was colored and hydroquinone (H
The residual ratio of Q) was measured to determine the stability of the contents. The residual ratio of hydroquinone was calculated by measuring the amount of hydroquinone in each sample before and after standing using an ultraviolet spectrophotometer. Table 5 shows these results.

[0045]

[Table 5]

From these results, it can be seen that when stored using the container 1 of the present invention, the stability of the monochrome developing solution is very excellent.

Example 4 The performance of the piercing container 1 was examined by performing the following tests. In a flexible container 1 (single bag) having a capacity of 500 ml for a three-sided seal type produced using the multilayer film 5 having the constitution shown in Table 6, 250 ml of a main part solution of a color developing solution for a color negative film shown below is provided.
, And sealed by heat sealing to prevent liquid leakage to obtain a test sample.

Color developing solution Main solution part solution CD-4 400 g Sodium bisulfite 4 g Add water to adjust to 1000 ml pH value 50% -Adjust to pH 1.0 using sulfuric acid

[0049]

[Table 6] K-PET: Polyethylene terephthalate coated with vinylidene chloride LLDPE: Linear low-density polyethylene LDPE: Low-density polyethylene PET: Polyethylene terephthalate PVA: Polyvinyl alcohol PE: Polyethylene CPP: Undrawn polypropylene

These test samples were subjected to 50 ° C., 75% R
H was left in a constant temperature bath for 800 hours, and the coloring of the liquid after standing and the residual ratio of the color developing agent (CD-4) were measured to determine the stability of the contents of each container. The residual ratio of the color developing agent was calculated by measuring the amount of CD-4 in each sample before and after standing in a thermostat using high performance liquid chromatography.
Further, the above-mentioned drop test and vibration test were performed to examine the strength of each container 1 when the photographic processing agent was enclosed. In addition, in this example, the piercing property was tested by performing the following piercing test for each test sample. Table 7 shows these results.

[Puncture Test] Polyvinyl chloride (PV
C) and a metal-made piercing rod 6 having a sharp tip with an outer diameter of 6 mm are prepared, and these piercing rods are pierced into each test sample. After standing for 1 hour, if the entire container of each test sample was lightly pressed by hand and no liquid leakage occurred, the container was further strongly pressed to see if there was any liquid leakage. Furthermore, the sample which did not cause liquid leakage when pressed by hand was suspended for one month with the pierced portion facing down to check for liquid leakage.

Evaluation of piercing test ○: No liquid leakage. ×: Leakage in hanging test. XX: Leakage due to strong pressing. ×××: Press lightly to leak.

[0053]

[Table 7]

From these results, it can be seen that the container of the present invention is excellent in the preservability and strength of the photographic processing agent and the piercing suitability without using a film which causes the generation of dioxin. Particularly, the containers O and P in which PVA is sanded on both sides with LLDPE or CPP have excellent piercing suitability regardless of the material of the piercing rod.

[0055]

As described above, claims 1 and 2 of the present invention.
According to the present invention, it is possible to provide a container for stably storing a photographic processing agent for a long period of time without using a material containing a compound causing dioxin or an expensive material. In addition, by using a container composed of a multilayer film having a polymer film layer having a small tensile strength on both sides of the polyvinyl alcohol resin layer, the suitability for piercing the container is improved, and a liquid leakage accident due to a tube coming off is improved. Can be prevented.

According to the third aspect of the present invention, in addition to the above, there is an advantage that the bag-made container has an appropriate hardness and is easy to handle. In addition, according to the fourth aspect, there is another advantage that piercing suitability can be obtained. In addition, according to the fifth aspect, chemical resistance and strength can be obtained, and piercing suitability can be obtained.

Further, according to claim 6 of the present invention, it is possible to provide a storage method which is excellent in gas barrier performance and can withstand long-term storage of a photographic processing agent.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a use state of an embodiment of the present invention.

FIG. 2 is an explanatory view of a longitudinal cutaway of a main part of an embodiment of the present invention.

FIG. 3 is an explanatory view of a longitudinal cutaway of a main part of another embodiment of the present invention.

[Explanation of symbols]

 Reference Signs List 1 container 2 polyvinyl alcohol resin layer 3 polyethylene layer 4 polyolefin resin layer 5 multilayer film 6 tube

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinichiro Nakai 1-7-1 Uchisaiwaicho, Chiyoda-ku, Tokyo Rengo Co., Ltd. (72) Inventor Seiichi Yamagishi 6-2 Asahi, Yoshikawa-shi, Saitama Chugai Photographic Chemicals Co., Ltd. In-house F term (reference) 2H016 AA00

Claims (6)

[Claims] 1. A polyvinyl alcohol resin layer comprising: at least one polyvinyl alcohol resin layer; and at least one polyethylene layer inside the polyvinyl alcohol resin layer in contact with a photographic processing agent.
A container for a photographic processing agent, comprising a multilayer film having at least one polyolefin resin layer or nylon layer outside the polyvinyl alcohol resin layer. 2. The container for a photographic processing agent according to claim 1, wherein the polyolefin resin layer located outside the polyvinyl alcohol resin layer is also made of polyethylene. 3. The container for a photographic processing agent according to claim 1, wherein the polyolefin resin layer located outside the polyvinyl alcohol resin layer is a stretched polypropylene. 4. The container for a photographic processing agent according to claim 1, wherein the polyolefin-based resin layer located outside the polyvinyl alcohol resin layer is an unstretched polypropylene. 5. The container for a photographic processing agent according to claim 1, wherein the polyethylene is linear low density polyethylene (LLDPE). 6. At least one polyvinyl alcohol resin layer, and at least one polyethylene layer inside the polyvinyl alcohol resin layer in contact with a photographic processing agent,
Storing a photographic processing agent in a photographic processing material container comprising a multilayer film having at least one polyolefin resin layer or a nylon layer outside the polyvinyl alcohol resin layer. Method.