JPS6025448B2 - Thin structure for medical or food use - Google Patents

Description

[Detailed description of the invention] TECHNICAL FIELD The present invention relates to a thin film structure for medical use or for food and drink.

More specifically, the present invention relates to a thin-film structure for medical use or food/drink use made of a transparent and soft polyester/polyether copolymer having a specific composition. Conventionally, plasticized polyvinyl chloride, rubber, polyurethane, and the like have been widely used as materials for thin structures such as tubes, bottles, and containers for medical or drinking purposes.

However, rubber or polyurethane is inherently susceptible to the effects of light or oxygen, and tends to gradually lose its strength or elasticity during use. Since it is often subjected to oxide sterilization, there is a high risk of deterioration occurring under such conditions. Furthermore, plasticized polypynyl chloride does not have particularly sufficient elasticity, and is not necessarily satisfactory as a material for thin-sheet structures.

Furthermore, since the plasticized polypinyl chloride generally contains a large amount of plasticizer, it has the disadvantage that the plasticizer leaches out during use, especially when used as a material for medical purposes or food and drink. This is a problem because many of them contain plasticizers whose toxicity to the human body has recently become a problem. Furthermore, vinyl chloride has the problem of residual vinyl chloride monomer, and toxicity of vinyl chloride monomer to the human body has recently become a problem. The present invention provides a thin sheet structure for medical or food use using a new material that does not have the disadvantages of conventional materials, is transparent, flexible, elastic, and can be melt-molded.

That is, the present invention uses terphthalic acid as a dicarboxylic acid component, and uses tetramethylene glycol, ethylene glycol, and polyoxyalkylene glycol with a molecular weight of 500 to 2000 and a ratio of carbon atoms to oxygen atoms of 2 to 4.5 as glycol components. It is a copolymer, and the polyoxyalkylene glycol is copolymerized in a proportion of 50 to 85% by weight of the copolymer and the ethylene glycol is copolymerized in a proportion of 10 to 50% by mole based on the sum of ethylene glycol and tetramethylene glycol. The present invention relates to a thin sheet structure for medical or food use made by melt-molding a polyester/polyether copolymer.

The material used in the present invention is a polyester-polyether copolymer consisting essentially of intramolecular linear ether ester units and ester units.

In the copolymer, the intramolecular linear ether ester units form soft segments, and the ester units form hard segments. The component forming the soft segment is a polyoxyalkylene glycol having a molecular weight of 500 to 2000 and a ratio of carbon atoms to oxygen atoms of 2 to 4.5, and the amount thereof is 50 to 4.5 in the copolymer.
Preferably it is 85% by weight, especially 50-75% by weight.

If the amount of polyoxyalkylene glycol is less than 5% by weight, flexibility will be insufficient, which is not preferred. If it exceeds 85% by weight, the copolymer becomes extremely soft, has poor moldability, and exhibits tackiness, which is undesirable. Examples of the poly(oxyalkylene) glycol having an average molecular weight of 500 to 2,000 and a ratio of carbon atoms to oxygen atoms of 2 to 4.5 include poly(oxytetramethylene) glycol and poly(oxypropylene).
Examples include glycol, poly(oxyethylene) glycol, poly(oxyhexamethylene) glycol, and the like.

These poly(oxyalkylene) glycols may be composed of a single component or may be a copolymer of two or more components. An example of a typical copolymerized polyoxyalkylene glycol is an ethylene oxide/propylene oxide copolymer. In addition, poly(
Oxyalkylene) glycols may be used alone or in combination of two or more thereof. The components forming the hard segment of the polyester/polyether copolymer are tetramethylene glycol and ethylene glycol.

Ethylene glycol is 10 to 50 mol%, especially 20 to 45 mol% of the sum of ethylene glycol and tetramethylene glycol.
It is preferable that The proportion of ethylene glycol is 1
If it is less than 0 mol%, transparency will not be sufficiently developed, which is not preferable, and if it exceeds 50 mol%, the molded product will develop stickiness after melt molding, and the molded product will not be able to form a tubular shape. In such cases, when the tubular body is wound up after melt-forming, the tubular body tends to be set in the rolled shape, which is not preferable. Furthermore, when it exceeds 50 mol%, there is a significant drawback that devitrification occurs during high temperature steam sterilization treatment or ethylene oxide sterilization treatment of molded products. The polyester/polyether copolymer may be copolymerized with a trifunctional or more polyfunctional compound such as bentaerythritol for the purpose of various modifications.

The polyester-polyether copolymer used in the present invention includes: (i) terephthalic acid and/or its ester-forming derivative, (o) tetramethylene glycol and/or its ester-forming derivative, (i) ethylene glycol and/or ester-forming derivatives thereof, 8
In the resulting polymer, B is Overall 50-85
% by weight, and the weight is 10 to 10% to the sum of the raw thorns
It is obtained by melt polymerization in a proportion of 50 mol%.

Examples of the ester-forming derivatives of the component {i' include lower alkyl esters (eg, methyl ester) and aryl esters (eg, phenyl ester) of terephthalic acid. Further, examples of the ester-forming derivatives of the components 'Rho', '1' and '8' include monocarboxylic acid esters of each glycol (eg, mo-, di-acetate), and the like. As the polymerization method, a conventional polyester manufacturing method can be adopted. The polymerization reaction temperature is from the melting point of the reaction product to 270
A temperature range of 0.degree. C. is preferable; if the temperature is too high than 270 qo, the product will deteriorate significantly, which is not preferable.

Suitable catalysts for use in melt polymerizations include tetrabutyl titanate, tetramethyl titanate, tetraethylene titanate, tetrapropyl titanate, di-n-butyl-tin-laurate, di-butyl-tin-oxide, dibutyl-tin-sebacinoate, zinc acetate and antimony oxide, magnesium acetate and antimony oxide,
Examples include zinc acetate and germanium oxide, magnesium acetate and germanium oxide, lead monoxide, lead dioxide, magnesium oxide, and zinc oxide.

Among them, preferred catalysts are organic titanium compounds. The amount of these catalysts is 0.0 based on the total amount of polymer produced.
03-0. It is preferably within the range of % by weight of the sword. The polyester-polyether copolymer of the present invention can be melt-molded, has excellent curing properties, and has excellent moldability as a transparent and flexible material with elasticity.

The thin-film structure for medical use or for food and beverage use of the present invention is obtained by melt-molding the above-mentioned polyester-polyether copolymer and has a wall thickness of about 5 skins or less.

The obtained thin laminate structure may be subjected to a stretching operation and a heat treatment operation as necessary. As the molding method, methods such as extrusion molding, blow molding, and injection molding can be adopted. Examples of thin structures include tubes, films, sheets, bottles,
Various containers, instruments, nipples, bottle stoppers, syringes, parts for food and drink vending machines, surgical gloves, condoms, disposable blood transfusion set instruments, disposable ring fluid set instruments, disposable blood collection set instruments, artificial Examples include tubular bodies, hollow bodies, and other thin bodies such as devices for cardio-brachial disposable sets.

The thin leaf structure of the present invention, for example, has a wall thickness of 0.5 to 1. The tubular body, which is about the size of a proboscis, has high transparency, and its transparency is equivalent to that of medical plasticized polyvinyl chloride.

In addition, the tubular body is subjected to high temperature steam sterilization (steam, l
K9/G, 12RO, 40 minutes) or ethylene oxide sterilization [ethylene oxide gas (1 ol%,
Even when subjected to the following tests, the transparency retention is extremely high and is close to that of medical plasticized polyvinyl chloride tubes. Furthermore, the dimensional stability during sterilization is also significantly superior, far exceeding that of plasticized polyvinyl chloride tubes for medical use. The polyester-polyether copolymer of the present invention has very little coloring, and for example, a tubular body with a wall thickness of about 0.5 to 1.0 is colorless and transparent.
It is completely equivalent to medical plasticized PVC tube. In addition, polyester/polyether copolymers include
Antioxidants, light stabilizers, fillers, brighteners, colorants, etc. can be added within a range that does not impair the purpose of the present invention.

Since the thin film structure for medical use or for food and drink according to the present invention does not require the addition of any plasticizer, there is no need to worry about toxicity to the human body due to elution of the plasticizer.

Moreover, it has the characteristics of being sufficiently colorless and transparent, flexible, and elastic. EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited by these. In the examples, "part" means part by weight. Further, the reduced viscosity is a value determined from the solution viscosity measured at 35° C. by dissolving Polymer 1.2 in Orthochlorophyll/100. Moreover, the softening point is a value measured with a Vicat softening point measuring device. Examples 1 and 2 (Production of polyester/polyether copolymer) The raw material composition shown in Table 1 was charged into a reactor equipped with a flywheel, a distillation device, and a nitrogen introduction tube, and heated to 180 to 220°C. ,
After distilling off 90% of the theoretical amount of methanol produced,
The reaction temperature was raised to 245 qo, the reaction was carried out for 10 minutes at normal pressure, and then the temperature was increased to about 3 qo. The reaction was carried out for 30 minutes in a weak vacuum of 0.1 to 0.3 side Hga. 5. Under high vacuum.
The insect time was superimposed.

The obtained polymer was discharged from the reactor and made into chips. The physical properties of this polymer are shown in Table 1. Table 1 Boma 1 yen 7 ethylene glycol Sole included (Sele)
×loo Cherry Blossom Gourai Chinpo Sun Seedling (Saru Amount (Desk) Ku Tube Forming) After drying the polymer obtained above in a 100 qo hot air dryer for 2 hours, using an extruder with an annular die, The tubes shown in Table 2 were extruded at a cylinder temperature of 160 to 165 oo and a die temperature of 16,000, cooled in a water bath, and wound onto a roll.

The moldability of the tube is extremely good, and since the crystallization rate of the polymer is fast, even if the tube is extruded from an extruder through an annular die into a water tank and immediately rolled up, it will not be set in a rolled shape. In addition, almost no tackiness was observed. The obtained tube was stretched by applying tension in all axial directions.

Stretching was performed at room temperature. The stretched tube was further subjected to a free shrink heat treatment of 130 qo x 5 minutes in a hot air dryer. The transparency and longitudinal dimensional stability of the obtained tube were as shown in Table 2.

{1' Transparency was measured by cutting open the tube before and after sterilization and using a Poick integrating sphere ultramicroturbidity meter SEP-TU manufactured by Nippon Seimitsu Kogaku Co., Ltd.

The results are shown in Table 2. ‘2} Sterilization treatment Each tube was cut into 20 skin lengths and treated under the following conditions.

■ 40 minutes in steam under high temperature steam sterilization conditions ■ Ethylene oxide sterilization treatment conditions 6 hours in ethylene oxide gas Table 2 -Bo,.

Vinyl chew Vicat softening point 141℃, hardness (
Shore A) 81) Charge the raw materials shown in Table 3 into a reactor equipped with a distiller, a distillation device, and a nitrogen introduction tube.
90% of the theoretical amount of methanol produced by heating at 180 to 22 piciC was distilled off, the reaction temperature was raised to 260 qC, the reaction was carried out for 10 minutes at normal pressure, and then about 3 piHgabs
．． The reaction was carried out for 30 minutes in a weak vacuum of 0.1 to 0.3 Yanagi Hga 戊. Polymerization was carried out for 100 minutes under high vacuum.

Subsequently, the reaction temperature was lowered to 250°C and polymerization was continued for an additional 50 minutes. The obtained polymer was discharged from the reactor and made into chips. Table 3 After drying the chip in a hot air dryer at 100°C for 2 hours,
Using an extrusion with an annular die, the cylinder temperature 1
90~200oo, outside diameter indicated at die temperature 190℃,
The thick-walled tubular body was extruded, cooled in a water bath, and wound up onto a roll.

Since the tube had extremely poor crystallinity, the tube moldability was extremely poor, the tube after molding had great stickiness, and when it was wound up into a roll, it was set in a rolled shape.

Further, the transparency and longitudinal shrinkage (shrinkage rate) of the tube were measured in the same manner as in Example 1. The second result is
Shown in the table. In addition, medical vinyl chloride tubes (Vica
The softening point (t) of 141° C. and the hardness (Shore A) of 81) were measured in the same manner as above.

Claims (1)

[Claims] 1 Terephthalic acid as dicarboxylic acid component, tetramethylene glycol, ethylene glycol and molecular weight 500
~2000 carbon atoms to oxygen atoms ratio of 2 to 4.5
It is a copolymer containing polyoxyalkylene glycol as a glycol component, and the polyoxyalkylene glycol accounts for 50 to 85% by weight of the copolymer and the ethylene glycol accounts for 10 to 50% by weight based on the sum of ethylene glycol and tetramethylene glycol. A thin film structure for medical use or food/drinks that is melt-molded from a polyester/polyether copolymer copolymerized in a mol% ratio.