JPS6025449B2 - 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 food or drink use.

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 and polymerized by a specific manufacturing method. BACKGROUND ART Hitherto, as materials for medical or food/drink thin structures such as tubes, bottles, containers, etc., bonito-ized polyvinyl chloride, rubber, polyurethane, and the like have been widely used.

However, rubber or polyurethane is easily affected by light or oxygen, and tends to gradually lose its strength or elasticity during use, and when using its thin structure, heat sterilization or ethylene oxide disinfection is necessary. Degas sterilization is often performed, but there is a drawback that there is a large risk of deterioration under such conditions. In addition, plasticized polyvinyl chloride does not have sufficient elasticity and is not necessarily satisfactory as a material for thin leaf moldings, and it generally contains a large amount of plasticizer, so it may cause problems during use. There is a disadvantage that the plasticizer leaches out, and there is also a disadvantage that the vinyl chloride monomer remains. Recently, the toxicity of such plasticizers and vinyl chloride monomers to the human body has become a serious problem, and there is a demand for thin-film structures made of compounds that do not contain these plasticizers and vinyl chloride monomers. The present invention provides a thin sheet structure for medical or food use using a new material that is transparent, flexible, elastic, and melt-moldable without the drawbacks of conventional materials.

That is, the present invention provides: Terephthalic acid and/or its ester-forming derivative, (o) Tetramethylene glycol and/or its ester-forming derivative, Molecular weight: 500-5
The ratio of the number of carbon atoms to the number of oxygen atoms in 000 is 2.0 to 4.5
Among the low-molecular and/or high-molecular ester compounds containing a terephthalic acid residue and an ethylene glycol residue, the above-mentioned 'a', '
A polyester/polyether copolymer obtained by reacting one component of o' and one of 1 and reacting a superposition component at a stage when the reduced viscosity of the reaction product becomes 0.1 (d〆') or more. The present invention relates to a thin film structure for medical use or for food and drink.

The polyester/polyether copolymer used in the present invention is a polymer consisting essentially of linear ether ester units and ester units within the molecule. Such polymers are produced as follows.

The above-mentioned 'I', 'Rho' and '1' components are first reacted, and at the stage when the reduced viscosity of the reaction product becomes 0.1 (d and/or) or more, the above-mentioned 0 component is added and reacted. A particularly desirable timing for adding the eight components is when the reduced viscosity of the reaction products of the three components 'A', {Q, and SI1 is 0.15 to 2.0 (d〆').

Reduced viscosity is 0. If component 0 is added when the temperature is less than d/d, the resulting polymer becomes cloudy and loses its transparency, which is not preferable.

The reaction temperature is preferably in the range from the melting point of the reaction product to 270°C,
If it is too high than 270 oo, polymer deterioration will be significant, which is not preferable.

Examples of the terephthalic acid ester-forming derivative of the above component (I) include lower alkyl esters such as methyl ester, aryl esters such as phenyl ester, and the like.

Examples of the tetramethylene glycol ester-forming derivative of component (o) include monocarboxylic acid esters such as acetic acid mono or ester.
Furthermore, examples of the polyoxyalkylene glycol of the soybean component include poly(oxytetramethylene) glycol, poly(oxypropylene) glycol, poly(oxyethylene) glycol, poly(oxyhexamethylene) glycol, and the like. .

These polyoxyalkylene glycols include not only those consisting of a single component as exemplified above, but also those formed by copolymerization. A typical copolymer is an ethylene oxide/propylene oxide copolymer. These may be used alone or in combination of two or more, but poly(oxytetramethylene) glycol and poly(oxyethylene) glycol are preferred;
In particular, poly(oxytetramethylene) glycol is preferably used. Examples of the ester-forming conductor include monoesters and gesters with monocarboxylic acids.

As one component, a polyfunctional compound having trifunctionality or more, such as pentaerythritol, can be used as a crosslinking agent for various modification purposes. Low-molecular and/or high-molecular ester compounds containing 8 components of terephthalic acid residues and ethylene glycol residues have the general formula ○ ○ CH2-CH21○1, m is 1 to 200) can be exemplified.

Among these, particularly preferable ones are x=HO-CH2-
It is a compound of CH2-○-, m=1, that is, bis(B-hydroxyethyl) terephthalate (hereinafter sometimes abbreviated as BHET). When component 0 is a polymer, various additives such as antioxidants, light stabilizers, polymerization accelerators, fillers, brighteners, colorants, etc. may be added as necessary to the extent that the purpose of the present invention is not impaired. In addition, for the purpose of various modifications, trifunctional or higher functional compounds such as bentaerythritol can be copolymerized as a crosslinking agent to the extent that the purpose of the present invention is not impaired. .

Quite unexpectedly and quite surprisingly, the polyester-polyether copolymer of the present invention produced by the above production method contains the above-mentioned (i}, {o', and shii) as the ethylene glycol components in the polymer. It has extremely superior transparency compared to polyester/polyether copolymers produced by the usual polymerization method in which ethylene glycol is charged at the same time as ethylene glycol is reacted.A suitable catalyst for use in the above production method is tetrabutyl. Titanate, tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, di-butyl-tin-laurate, di-butyl-tin-oxide, dibutyl-tin-sebacinoate, lead acetate and antimony oxide, magnesium acetate and antimony oxide, zinc acetate and germanium oxide, Examples include magnesium acetate, germanium oxide, lead monoxide, lead dioxide, magnesium oxide, and zinc oxide.

Among them, preferred catalysts are organic titanium compounds. These catalysts are 0.003% based on the total weight of the polymer produced.
~0. The preferred range is % by weight. The polyester-polyether copolymer used in the present invention horizontally forms soft segments with the 'A' component and the thorn component,
The 'a' component, {o' and eight components constitute a hard segment.

The content of one component constituting the soft segment is 10 to 85% by weight, preferably 20 to 75% by weight in the copolymer.
Weight%. If the content of one component is less than 1% by weight, the flexibility will be insufficient, and if it exceeds 85% by weight, the polymer will become extremely soft or difficult to mold when forming thin structures such as tubular bodies. This is not preferable because it deteriorates the properties and develops tackiness. Or the content of the component is 5% of the ethylene glycol component to the sum of the ethylene glycol component in the {o} component barb component in the copolymer.
It is preferable that the proportion is 95 mol% to 95 mol%, and more preferably 10 to 90 mol%. The ratio of ethylene glycol component is 5
When the amount is less than mol%, the transparency of the copolymer decreases. Such a polyester/polyether copolymer may contain an antioxidant, a light stabilizer, a polymerization accelerator, a filler, a brightener, a coloring agent, etc., within a range that does not impair the purpose of the present invention.

The above-mentioned polyester/polyether copolymer can be melt-molded, has excellent curing properties, and has excellent moldability as a transparent and flexible material having elasticity.

The thin film structure for medical or food use of the present invention is obtained by melt-molding the English polymerized polyester/polyether copolymer having the above-mentioned specific composition as a material.

As the molding method, any method such as extrusion molding, blow molding, injection molding, etc. can be adopted. The thin-sheet structure of the present invention is a molded article with a wall thickness of about 5 m/m or less, such as tubes, bottles, films, sheets, various containers, instruments, nipples, stoppers for bottles, syringes, food and drink vending machines. parts, surgical gloves,
Examples include tubular bodies, hollow bodies, and thin lamellar bodies such as condoms, blood sampling instruments, blood transfusion instruments, and artificial organ instruments.

The thin-film structure of the present invention, for example, a tube having a wall thickness of about 0.5 to 1.0 feet, is colorless and has extremely high transparency, and its transparency is comparable to that of medical plastic polypinyl chloride.

Furthermore, this product is subjected to high temperature steam sterilization treatment (steam, lk
9/G, 121qo, 40 minutes) or ethylene oxide sterilization [ethylene oxide gas (1 mol%, C
〇29 biol%), 1E9/dislike G, 50-6 bi○ Tsumugi rs
] It has excellent transparency retention and dimensional stability during processing, and far exceeds the properties of medical plasticized polyvinyl chloride tubes. Further, the thin film structure in the present invention may be subjected to stretching operation and heat treatment operation as necessary. 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 extraction of the plasticizer.

Moreover, it has the characteristics of being sufficiently colorless and transparent, flexible, and elastic. EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited by these.

In the examples, "parts" mean parts by weight.

Further, the reduced viscosity is a value determined from the solution viscosity measured at 3yo by dissolving 1.2yo of polymer in 100o of orthochlorophenol. Moreover, the softening point is a value measured using a Vicat softening point measuring device. Examples and Comparative Examples The raw materials shown in Table 1 were charged into a reactor equipped with a rope frame machine, a distillation device, and a nitrogen inlet pipe, and heated to 180 to 220°C. After the crabs were released, the reaction temperature was raised to 245 oo, and the reaction was carried out at normal pressure for 10 minutes, and then the reaction was carried out under a weak vacuum of about 300 ooohg.
Let it react for an additional 0.1 to 0.3 minutes. Polymerization was carried out for 30 minutes under high vacuum.

Here, the inside of the system was returned to normal pressure with nitrogen, and bis(8-hydroxyethyl) terephthalate (BHET) was added in the amount shown in Table 1, and further 0.1 to 0.3 side Hgabs. After reacting for 7 hours under high vacuum, the mixture was discharged and made into chips. Table-1
A ribbed plate was quickly cooled in ice water to produce a sheet.

Transparency was measured using a Pock integrating sphere type cryothermometer model SEP-TU manufactured by Nippon Precision Optical Co., Ltd.

10 pieces of transparent soft polyester chips obtained above
After drying in a hot air dryer at 0qo for 2 hours, using an extruder with an annular die, the cylinder temperature was 160-165.
℃, and a die temperature of 160° C., a tubular body having the outer diameter and wall thickness shown in Table 2 was extruded and wound onto a roll that was cooled in a water bath.

The above polymer has extremely good tube formability,
Furthermore, because the crystallization speed of the polymer is slow, even if the tube extruded from the extruder into the water tank using an annular die is immediately rolled up, it will not be set in a rolled shape. The molded product exhibits almost no tackiness, and has excellent transparency, comparable to that of plasticized polyvinyl chloride tubes. Furthermore, the tube of this example had very little coloration (nearly colorless).The physical properties of the tube of the present invention and the medical plasticized polyvinyl chloride tube were as shown in Table 2.

Table - 2 x Orac style dragon ball cannon? Measured with a chest cough meter (previous life) × armpit liquid set river; sold product) Plasticized polyvinyl chloride tube (manufactured by Japan Medical Supply) Cut each of the above tubes into 20 skin lengths. , high temperature steam sterilization treatment and ethylene oxide gas sterilization treatment were performed.

However, tube A and the vinyl chloride tube were directly sterilized, and tube B was heat-treated at 130° C. for 5 minutes before being sterilized. still,
The sterilization treatment conditions are as follows.

1 High-temperature steam sterilization treatment conditions Land-produced... 4 powder in steam 2 Ethylene oxide sterilization conditions 6 hours in ethylene oxide gas 90 pseudo%} Land-produced total G} Molding Table 3 shows the results of transparency retention and longitudinal dimensional stability (shrinkage rate) after sterilization of the product.

Table-3

Claims (1)

[Scope of Claims] 1 (a) Terephthalic acid and/or its ester-forming derivative, (b) Tetramethylene glycol and/or its ester-forming derivative, (c) Number of carbon atoms to oxygen atoms with a molecular weight of 500 to 5,000. Number ratio is 2~
4.5 polyoxyalkylene glycol and/or its ester-forming derivative, and (d) low-molecular and/or high-molecular ester compounds containing terephthalic acid residues and ethylene glycol residues, first of all the above ( A), (b), and (c) components were reacted, and when the reduced viscosity of the reaction product became 0.1 (dl/g) or more, the above (d) component was added and reacted. A thin film structure for medical or food use made of polyester/polyether copolymer. The reduced viscosity here is a value determined from the solution viscosity measured at 35° C. by melting 1.2 g of polymer in 100 ml of orthochlorophenol.