JPH05170945A - Packaging bag - Google Patents

Abstract

PURPOSE:To provide a packaging bag usable even at very low temperatures, excellent in resistance to cold and heat, suitable for blood preservation and transportation etc., consisting of a polyamide resin made up of specific recurring unit. CONSTITUTION:The objective packaging bag consisting of a polyimide resin made up of recurring unit of formula I (X is direct bond, 1-10C divalent hydrocarbon, hexafluorinated isopropylidene, carbonyl, thio or sulfonyl; R is >=2C aliphatic group, alicyclic group, monocyclic aromatic group, condensed polycyclic aromatic group, etc.). The polyimide resin can be obtained by reaction between a compound of formula II and a compound of formula III.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a packaging bag obtained from a polyimide film or sheet having cold resistance and heat resistance. Especially, liquid nitrogen temperature obtained by heat-sealing polyimide film or sheet -196 ° C
Regarding the packaging bag that can be used even at low temperature, -1
The present invention relates to a packaging bag particularly useful as a packaging bag for storing or transporting blood for storing blood or one component in blood at a low temperature of 70 to -196 ° C.

[0002]

2. Description of the Related Art Packaging bags that have been used for carrying or storing various articles have been used for practical purposes by using a cloth, a film or a sheet and adhering and stitching them into a shape adapted to the usage form. There is. In such a packaging bag, various materials are used depending on diversification of usage modes and usage targets. Particularly in recent years, materials that can be used in a wide temperature range are required due to the development of distribution means, transportation technology, long-term storage technology, storage technology, medical technology, and the like. On the other hand, various polymer materials, particularly polymer materials having excellent heat resistance, have been developed, and attempts have been made to apply these materials according to their respective performances. Among them,
It is also found to be applied to packaging bags.

On the other hand, the storage and transportation of the articles should be carried out in an extremely low temperature environment for the purpose of ensuring the stability of the quality of the articles, or avoiding spoilage when the articles are especially organic substances. There is. A packaging bag made of a so-called cold-resistant material that can be applied even under such an environment has been developed. For example, regarding the preservation of blood, the rapid freezing method in liquid nitrogen (-196 ° C) has been attracting attention, and the slow-freezing method (liquefied nitrogen -80 to -90 ° C storage, soft vinyl chloride container has been conventionally used. ), The recovery rate of erythrocytes and the quality of thawed erythrocytes to be collected are good, and the storage period is greatly extended. As the container for quick-freezing storage, a conventional container made of vinyl chloride or polypropylene does not have resistance to a low temperature of -196 ° C, and even a slight impact causes cracking and cannot be used.

On the other hand, as a resin having good low-temperature resistance,

[Chemical 3] Although a polyimide resin having a basic skeleton represented by (Dupont: trade name Kapton) is known, it has no clear glass transition temperature and is difficult to process into a packaging bag because it is not thermoplastic. there were. Therefore, in order to obtain a packaging bag using such a polyimide resin, a method in which a binder resin layer is laminated with a thermoplastic resin layer such as polyethylene or vinyl acetate and used as a laminate (Japanese Patent Publication No. Sho 60-22942). ) Is known, but it is not satisfactory in terms of interfacial adhesive strength, binder resin adhesive strength, and low-temperature resistance property of the binder resin.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-resistant or cold-resistant packaging bag that can be used even at a high temperature to an extremely low temperature, for example, a liquid nitrogen temperature of -196 ° C.

[0006]

Means for Solving the Problems As a result of various studies on the above-mentioned packaging bag material, the present inventors heat-seal the film sheet of the polyimide into a bag shape by using a specific polyimide. It is possible that the packaging bag obtained by heat sealing has a wide temperature range, that is, at high temperature, of course, at low temperature, especially liquid nitrogen temperature -196 ° C.
It has been found that cracks and bag breakage do not occur even when used at such a low temperature, and the present invention has been completed.

That is, the packaging bag of the present invention has the general formula (1)

[Chemical 4] (In the formula, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms,
Hexafluorinated isopropylidene group, carbonyl group,
A thio group or a sulfonyl group, and R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or an aromatic group directly or as a bridge member A tetravalent group selected from the group consisting of non-condensed polycyclic aromatic groups interconnected with each other by a heat-sealing bag or polyimide film having a repeating unit represented by It is a packaging bag.

The packaging bag of the present invention is easy to prepare, and can be obtained by simply heat-sealing a polyimide film or sheet into a desired bag shape. The obtained packaging bag of the present invention does not cause cracks even at extremely low temperatures and can be used as a blood storage or transportation packaging bag that can store blood or one component in blood, and can also store other frozen articles. It is extremely useful as a packaging bag for transportation.

The above polyimide has the general formula (3)

[Chemical 5] (Wherein, X has the same meaning as in the case of the general formula (1)), and an etherdiamine represented by the general formula (4)

[Chemical 6] (In the formula, R has the same meaning as in the case of the general formula (1)) A polyimide obtained by reacting with one or more tetracarboxylic dianhydrides.

The polyimide used in the present invention is characterized in that a diamine having an ether bond is used as a raw material. Specifically, for example, JP-A-61-143478 and JP-A-62-6
8817, 62-86021, U.S. Pat. No. 48,473,495 and the like, and the thermoplastic polyimides produced by these methods can all be used in the present invention. Among them, the preferable polyimide can be produced using the following raw materials. That is, 4,4 '-[bis (3-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy) phenyl] methane 1,1-bis [4- (3-aminophenoxy) phenyl] as etherdiamine Ethane 1,2-bis [4- (3-aminophenoxy) phenyl] ethane 2,2-bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis [4- (3-aminophenoxy) phenyl ] Butane 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane bis [4- (3-aminophenoxy) phenyl] ketone bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, The ether diamine selected from these is used alone or in combination of two or more.

As the tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, pyromellitic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride. 1,2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride,
2,3,6,7-anthracene tetracarboxylic dianhydride, 1,
2,7,8-phenanthrenetetracarboxylic dianhydride, etc.,
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3',
4,4'-benzophenone tetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenone tetracarboxylic dianhydride,
2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl)
Ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4 , 4 '-(p-phenylenedioxy) diphthalic acid dianhydride, 4,4'-(m-phenylenedioxy) diphthalic acid dianhydride p-phenyleneoxydi (4-phthalic acid) dianhydride A single compound selected from these compounds or a mixture of two or more compounds is used.

The method for producing a polyimide by reacting these diamine compounds and tetracarboxylic dianhydride is not particularly limited, and various methods including a known method for producing a polyimide can be applied. For example, the polyimide used in the present invention can be generally produced by the following method. That is, diamine compound and tetracarboxylic acid dianhydride are dissolved in an organic solvent, polymerization is initiated to generate polyamic acid, and then reaction is performed at a temperature of 100 ° C or higher to generate reaction water accompanying imide cyclization. The polyimide corresponding to the raw material monomer can be produced by imidization while removing the so-called, so-called thermal imidization, or dehydration-imidization using a dehydrating agent such as acetic acid, so-called chemical imidization.

In particular, in order to obtain a packaging bag with stable quality, (1) a method in which a diamine compound and a tetracarboxylic acid dianhydride are separately dissolved in a phenolic solvent, and these solutions are mixed and polymerized, (2) When dissolving the tetracarboxylic acid dianhydride in a phenolic solvent, a method in which an organic base is present in the phenolic solvent, or (3)
It is more preferable to devise a method of reacting the diamine compound and the tetracarboxylic dianhydride in a phenol solvent in the presence of an organic base. Further, as the phenolic solvent used in such a method, phenol,
Examples include m-cresol, o-cresol, p-cresol, cresylic acid, ethylphenol, isopropylphenol, tert-butylphenol, xylenol, chlorophenol, dichlorophenol, phenylphenol and the like. These phenolic solvents may be used alone or in combination of two or more.

When a monomer solution or a polyamic acid solution is prepared by these methods, for example, triethylamine, tributylamine, tripentylamine, N, N-
Dimethylaniline, N, N-diethylaniline, pyridine, α-picoline, β-picoline, γ-picoline, 2,4
An organic base such as -lutidine, 2,6-lutidine, quinoline or isoquinoline, preferably pyridine or γ-picoline is allowed to coexist. The amount of the organic base to be coexisted varies depending on the type of the monomer and the type of the phenol solvent, but is usually 0.1 to 0.1 mol per 1 mol of the tetracarboxylic dianhydride.
The molar amount is 10 times, preferably 1.0 to 3.0 times.

Further, in order to produce a polyimide suitable for the present invention, there is no problem even if a monoamine, a dicarboxylic acid anhydride or the like is allowed to coexist as a polymer terminal blocking agent during polymerization. Typical dicarboxylic acid anhydrides used include:
For example, phthalic anhydride, 2,3-benzophenone dicarboxylic acid anhydride, 3,4-benzophenone dicarboxylic acid anhydride,
2,3-dicarboxyphenyl phenyl ether anhydride,
3,4-dicarboxyphenyl phenyl ether anhydride,
2,3-biphenyldicarboxylic acid anhydride, 3,4-biphenyldicarboxylic acid anhydride, 2,3-dicarboxyphenylphenyl sulfone anhydride, 3,4-dicarboxyphenylphenyl sulfone anhydride, 2,3-dicarboxy Phenylphenyl sulfide anhydride, 3,4-dicarboxyphenyl phenyl sulfide anhydride, 1,2-naphthalene dicarboxylic acid anhydride, 2,3-naphthalene dicarboxylic acid anhydride, 1,
Examples thereof include 8-naphthalenedicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, and 1,9-anthracene dicarboxylic acid anhydride.

Representative monoamine compounds include, for example, aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,4-xylidine, 2,5-xylidine, 2,6. -Xylidine, 3,4-xylidine, 3,5-xylidine, o-chloroaniline, m
-Chloroaniline, p-chloroaniline, o-bromoaniline, m-bromoaniline, p-bromoaniline, o
-Nitroaniline, m-nitroaniline, p-nitroaniline, o-aminophenol, m-aminophenol, p-aminophenol, o-anisidine, m-anisidine, p-anisidine, o-phenetidine, m-phenetidine, p -Phenetidine, o-aminobenzaldehyde, m-aminobenzaldehyde, p-aminobenzaldehyde, o-aminobenzotrifluoride, m-aminobenzotrifluoride, p-aminobenzotrifluoride, o-aminobenzonitrile, m- Aminobenzonitrile, p-aminobenzonitrile, 2-aminobiphenyl, 3-aminobiphenyl, 4-aminobiphenyl, 2-aminophenylphenyl ether, 3-aminophenylphenyl ether, 4-aminophenylphenyl ether, 2-ami Benzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-aminophenylphenyl sulfide, 3-aminophenylphenyl sulfide, 4-aminophenylphenyl sulfide, 2-aminophenylphenyl sulfone, 3-aminophenylphenyl sulfone, 4-amino Phenylphenyl sulfone, α-naphthylamine, β-naphthylamine, 1-amino-2-naphthol, 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-
1-naphthol, 5-amino-2-naphthol, 7-amino-2-naphthol, 8-amino-1-naphthol,
8-amino-2-naphthol, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene and the like can be mentioned.

The reaction temperature in producing the polyamic acid solution is usually 100 ° C. or lower, preferably 60 ° C. or lower. The reaction pressure is not particularly limited and it can be carried out at normal pressure. The reaction time varies depending on the type of solvent and the reaction temperature, and usually 4 to 24 hours is sufficient. After producing the polyamic acid solution, the obtained polyamic acid solution is heated to a temperature of 100 ° C. or higher to produce the corresponding polyimide while removing the reaction water generated by the imide cyclization. The imide cyclization temperature is 100 ° C or higher, preferably 150 ° C or higher.

The logarithmic viscosity of the polyimide of the present invention obtained by the above is usually 0.35 to 0.65 dl / g, preferably 0.40 to 0.
It is in the range of 60 dl / g. When the logarithmic viscosity exceeds the above range and is 0.35 or less, mechanical properties and durability are insufficient, and when it is 0.60 or more, moldability is deteriorated and film forming becomes difficult. This logarithmic viscosity is parachlorophenol /
Concentration 0.5g / 100 in a mixed solvent of phenol (90/10 weight ratio)
It is dissolved by heating in ml of solvent and then cooled to 35 ° C for measurement.

In order to produce the packaging bag of the present invention, the above polyimide resin is formed into a film or sheet by a known method. The packaging bag of the present invention can be obtained by stacking polyimide resin films or sheets obtained by molding and heat-sealing them into a desired bag shape.
The film or sheet can be obtained by various methods, and the following methods can be given as typical preferable methods. Of course, the film or sheet used in the present invention is not limited to the one obtained by the following method. For example, in the following method for producing a film, polyimide is heated and melted by a well-known melt extruder, extruded from a die having a slit-shaped nozzle to be formed into a film, and static electricity is imparted to this, and a glass transition of a polymer is made. Temperature (Tg) -50 to Tg-15 ℃ It is cooled and solidified by a chill roll with a surface temperature in the range, and it is transported to the normal temperature with tension without contacting the roll etc. Is sent.

The melt viscosity of the polyimide used is often in the range of 500 to 100,000 poise at the molding temperature. With a melt viscosity of this level, there is no tensile strength due to the elasticity of the molten state, it is possible to make uniform contact with the cooling roll, the flowability in the molten state is good, and the film breaks when pulled by the cooling roll. There is no problem such as.

For the molten film, for example, Japanese Patent Publication No. 37
-6124, a wire or knife edge is used as an electrode, and the potential gradient near the electrode is at least 30 kV.
By applying a positive or negative DC electric field such that / cm, a corona discharge or blow discharge occurs in the vicinity of the electrode, gas molecules in the atmosphere (generally in air) are ionized, and a general method of giving static electricity to the film Then, apply static electricity. As a specific method, for example, the diameter is 0.05 to 0.5 m
A method of applying a positive or negative DC voltage of 5 to 30 kV to a tungsten wire of m 3 can be mentioned.

The cooling roll used in this method is, for example, a roll having a surface layer of metal, ceramic, etc.
It can be heated by passing a heating medium such as oil, water, or a low melting point inorganic substance inside. The surface temperature is preferably in the range of [Tg] −50 to [Tg] −15 ° C., based on the glass transition temperature of the polyimide used (hereinafter referred to as [Tg]).
Within this temperature range, the film can be obtained without deforming the film, generating wrinkles and, in some cases, causing no troubles during molding such as winding around a cooling roll.

Further, in the method for producing a polyimide sheet, the polyimide can be formed into a sheet by a well-known melt extrusion molding technique and apparatus. The sheet can be obtained by heating and melting the polyimide, extruding it into a sheet form with a die such as a circular die or a flat die, and cooling it. Usually, when producing a polyimide sheet by melt extrusion, the water content of the polyimide used may slightly affect the characteristics of the sheet,
When the water content is 0.5 to 1%, the appearance and extrudability of the sheet may cause particular problems.
By controlling to 0 ppm or less, it is possible to stably obtain a sheet having an excellent surface state.

The water content of the polyimide used is generally controlled at a temperature of 100 ° C. or higher at which the polyimide does not melt, usually 250 ° C. or lower for 3 to 24 hours. Further, it is effective to replace the atmosphere with air, nitrogen, etc., and the treatment may be further performed under reduced pressure. However, any method may be used as long as it can reduce the water content. The melt extrusion temperature varies depending on the polymer structure, but is usually in the range of 300 to 450 ° C. Preferably 3
It is in the range of 50 to 430 ° C. If the temperature is less than 300 ° C, the resin is difficult to melt and cannot be extruded in many cases, and even if the resin can be extruded, the fluidity of the molten resin is extremely reduced, and it is difficult to form the resin into a sheet by taking it. Absent. Further, if the temperature exceeds 450 ° C., the decomposition of the resin proceeds, and the appearance of the sheet is impaired due to air bubbles, die lines, decomposed residue, etc., which is not preferable.

The packaging bag of the present invention is made in various shapes according to the purpose of use. For example, as a container for storing or transporting blood, the polyimide sheet or film of the present invention, a tube-shaped or belly-shaped spout member obtained by separately molding, heat the member for injection port to an appropriate location. It can be sealed and adhered, and the sheet or film can be shaped into a desired shape, and heat-sealed at necessary portions to form a packaging bag.

The heat sealing method is a hot bar sealer,
Any method such as a high frequency sealer or an ultrasonic sealer may be used. The thickness of the film or sheet used for the packaging bag of the present invention is 0.025 to 0.2 mm, preferably 0.05 to 0.15 mm. If it is less than 0.025 mm, the mechanical strength of the packaging bag is insufficient, and if it exceeds 0.2 mm, the thermal conductivity is poor and the time for freezing or thawing becomes long, resulting in poor workability. The polyimide resin packaging bag may be coated with a metal foil such as aluminum or stainless steel for the purpose of improving strength and heat conductivity.

[0027]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 4,4′-bis (3-aminophenoxy) biphenyl was placed in a reaction vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
Charge 3.68 kg (10 mol) and 25 kg of N, N-dimethylacetamide, and under a nitrogen atmosphere, pyromellitic dianhydride 2.1
4 kg (9.80 mol) was added in portions while paying attention to the rise in the solution temperature, 59 g (0.4 mol) of phthalic anhydride was added, and the mixture was stirred at room temperature for about 20 hours, followed by 303 g (3 mol) of triethylamine and 306 g ( (3 mol) acetic anhydride was added over about 50 minutes and then stirred for about 2 hours. 20 kg of methanol was charged into this solution, and the polyimide powder was filtered off at 30 ° C. The obtained polyimide powder was washed with methanol and acetone and then dried at 300 ° C. for 8 hours in a nitrogen atmosphere to obtain about 5 kg of polyimide powder. The melt viscosity of the obtained polyimide was measured using a high-lower flow tester (CFT-500 manufactured by Shimadzu Corp.), and the apparent shear rate was 200 sec ⁻¹ and the apparent viscosity at 400 ° C. was 5500 poise. The obtained polyimide powder was dried at 180 ° C. for 24 hours, melted at 410 ° C. with a 25 mm vent type extruder, extruded from a nozzle having a diameter of 2 mm, and naturally cooled to obtain a strand of about 1.8 mm. This was cut into about 3 mm in the longitudinal direction to obtain pellets.
The melt viscosity of this polyimide resin pellet is 400 ℃, 200
It was 5600 poise at a shear rate of ^-1 sec. Also,
The glass transition temperature was 248 ° C as determined by the DSC method (heating rate 4 ° C / min.). The polyimide pellets were placed in a hot air dryer and dried at 180 ° C for 24 hours. This is fed to a 40 mm extruder, heated and melted at 400 ° C, extruded from a slit die with a width of 500 mm (gap 1 mm), and cooled with a 400 mm diameter cooling roll (
It was collected at a surface temperature of 220 ° C) at 3 m / min. At this time, a tungsten wire with a diameter of 0.2 mm was stretched 15 mm away from the point where the film and the cooling roll were in contact with each other in the direction perpendicular to the surface of the film, and both ends were fixed with insulators. Electrode KFV-30-10) to the electrode +
A voltage of 10 kV was applied. The molten film was evenly adhered to the cooling roll. The angle at which the film was in contact with the cooling roll was about 100 °, which was peeled off from the rear with a tension of 5 kgf, and naturally cooled without contacting the roll for about 2 m and wound up. The film temperature immediately before winding was about 60 ° C, and there was no scratch on the film surface. The 50 μm-thick film obtained as described above was stacked on two sheets, and the length was 250 mm and the width was 150 mm, and the periphery was formed so as to form a packaging bag having an inlet for contents in the center of its short side. With a Fuji Impulse T-130 heat sealer,
Heat sealing was performed under the conditions of a sealing temperature of 300 ° C., a pressure of 10 kg / cm ² , and a sealing time of 2 seconds. The sealing property, oxygen barrier property, cold resistance, cold sheet cycle test, etc. of the prepared packaging bag were measured, and all were good.

Examples 2 to 6 Films were prepared in the same manner as in Example 1 using polyimides 2 to 6 shown in Table 1 (Table 1), and packaging bags were manufactured using the films. In all cases, the heat sealability was good. The various properties of the obtained film were good.

[Table 1]

Claims (3)

[Claims] 1. A compound represented by the general formula (1): (In the formula, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms,
Hexafluorinated isopropylidene group, carbonyl group,
A thio group or a sulfonyl group, and R has 2 carbon atoms
The above-mentioned aliphatic groups, cycloaliphatic groups, monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a crosslinking member. Which represents a tetravalent group selected from the group consisting of) and a packaging bag made of a polyimide resin having a repeating unit represented by the formula: 2. The general formula (1): (In the formula, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms,
Hexafluorinated isopropylidene group, carbonyl group,
A thio group or a sulfonyl group, and R has 2 carbon atoms
The above-mentioned aliphatic groups, cycloaliphatic groups, monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups in which the aromatic groups are connected to each other directly or by a crosslinking member. A cold- and heat-resistant packaging bag obtained by heat-sealing a polyimide sheet or film having a repeating unit represented by the formula (4) selected from the group consisting of 3. The packaging bag according to claim 2, wherein the packaging bag is for blood storage or transportation.