JPS5932308B2 - Laminated molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminate formed from a polyester elastomer and polyvinyl chloride.

The purpose is to be flexible and transparent, and to have a hygienic aspect that prevents the monomer (MVC) contained in polyvinyl chloride and various plasticizers from leaching into the contents of the molded product. It is an object of the present invention to provide laminated structures in the form of tubes and bags (laminated tubes, laminated bags, laminated bottles) that are excellent in quality, and particularly preferably to provide laminated structures in various forms suitable for medical use. That's true. Soft polyvinyl chloride resin and silicone rubber are widely used as medical tube materials for blood transfusion sets, infusion sets, catheters, artificial heart-lung circuits, etc.

In particular, polyvinyl chloride is the most widely used because it is transparent and flexible, but recently several problems have been raised. The first is the elution of plasticizer from the product. The plasticizer content is generally very large, and many of the plasticizers useful as plasticizers for softening are concerned about their toxicity. The second problem is the elution of vinyl chloride monomer, and the third problem is the elution of metal ions such as lead, tin, cadmium, barium, etc. used as heat stabilizers. In other words, plasticized soft vinyl chloride materials have been developed as disposable medical materials because they are transparent, flexible, and inexpensive; however, they pose safety problems due to the elution of plasticizers, monomers, stabilizers, etc. There is. On the other hand, silicone rubber has no safety problems, but its uses are limited because it lacks transparency and has insufficient mechanical strength. Although it is known that medical materials have recently been developed from polyurethane elastomers and polyester elastomers, polyurethane elastomers have problems with flexibility and coloring, and are also inferior in terms of bioreactivity.

Furthermore, medical materials made only of polyester elastomer are the safest materials, but they have problems with flexibility and transparency, and if these are satisfied, they become too sticky and cannot be molded. One of the objects of the present invention is to provide a medical material that is excellent in flexibility, transparency, and safety and hygiene in view of the drawbacks of conventional materials.

The present inventors focused on the fact that polyetherester elastomer has a high affinity with polyvinyl chloride, and by forming a thin layer of polyetherester elastomer as an inner layer of polyvinyl chloride, the adhesive surface of both layers Strong and without compromising the flexibility and transparency of polyvinyl chloride,
The inventors have discovered that safety can be improved and have arrived at the present invention.
That is, the present invention provides a laminate molded product characterized by having a plasticized polyvinyl chloride resin compound as an outer layer and a thin layer of polyetherester elastomer as an inner layer.

The polyether ester elastomer in the present invention is defined as at least one dicarboxylic acid having a molecular weight of less than 300, (B) at least one diol having a molecular weight of less than 250, and (B) at least one diol having a molecular weight of less than 250.
A copolymer derived from at least one long chain glycol having a molecular weight of 0.00.

The dicarboxylic acid (4) and diol (B) constitute the hard segment of the polyetherester elastomer.

Dicarboxylic acids having a molecular weight smaller than 300 are terephthalic acid, isophthalic acid, phthalic acid, aromatic dicarboxylic acids such as 2,6- and 1,5-naphthalene dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, 1,3 −
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, oxalic acid, glutaric acid, adipic acid, azelaic acid,
These include aliphatic dicarboxylic acids such as sebacic acid and their ester-forming derivatives, and two or more of these may be copolymerized and used.

Diols (B
) means ethylene glycol, propylene glycol, 1
, 4-butanediol, neopentyl glycol, 1,
These include alkylene glycols such as 5-pentanediol and 1,6-hexanediol, and cycloalkylene glycols such as 1,4-cyclohexanedimethanol. Among them, the most suitable combination of dicarboxylic acid and diol is 50 to 100 moles of terephthalic acid as the dicarboxylic acid. The remaining 50 to 0 mol% dicarboxylic acid component is copolymerized with isophthalic acid, phthalic acid, adipic acid, etc., and the diol component is 1,4
-Butanediol or 1,6-hexanediol is used as the main component. The reason why such a combination is suitable for the present invention is that it not only has excellent moldability, chemical resistance, and heat resistance during sterilization, but also has particularly good affinity with polyvinyl chloride resin, which eliminates problems such as peeling at the laminated interface. There is no Long chain glycols (O refers to polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol, poly(tetra Examples include poly(alkylene oxide) glycols such as methylene oxide) glycol and copolymers of ethylene oxide and propylene oxide. Among these, poly(tetramethylene oxide) glycol has particularly good heat resistance, hydrolysis resistance, and chemical resistance. beginning,
It is suitable for the elastic properties it provides to polyether ester.

The number average molecular weight of poly(alkylene oxide) glycol is 600 to 6,000, preferably 600 to 4,500; if the molecular weight is too large, the poly(alkylene oxide) glycol unit itself becomes crystalline and loses its elastic function. In addition, the compatibility deteriorates.

On the other hand, if the molecular weight is less than 600, the length of the polyester hard block becomes too short, so that elasticity is lost in this case as well, and chemical resistance is also reduced. In the copolyether ester, the weight ratio of polyether ester soft segment/polyester hard segment is 85/1.
It is necessary to make the ratio between 5 and 10/90. 85/1
If it is 5 or more, the affinity of the polyether ester to the polyvinyl chloride resin decreases, and the effect of suppressing plasticizer elution in the polyvinyl chloride resin decreases.

If the ratio is less than 10/90, the polyether ester loses its flexibility, and the curing speed becomes extremely slow, resulting in poor moldability and transparency. The physical properties of the copolyetherester elastomer suitable for preparing the laminate of the present invention include a melting point of 130 to 1800 and an intrinsic viscosity measured in C1 orthochlorophenol at a concentration of 0.5% at 30°C. is 0.8 or more and 3.0 or less.

A copolymer with a melting point in this range is suitable because it can prevent thermal decomposition of vinyl chloride resin during extrusion lamination, and when a copolyester ether is dissolved in a solvent for solution coating, a copolymer with a melting point of 180°C or higher is suitable. You can also use things. Further, the solution viscosity is preferably within the above range from the viewpoint of molding stability and mechanical strength. The plasticized polyvinyl chloride resin compound, which is another component constituting the laminate molded product of the present invention, contains 10 to 60% plasticizer by weight. Other vinyl polymers such as polyvinylidene chloride and polyvinyl acetate may be copolymerized with the polyvinyl chloride in an amount of up to 20 moles or less.

As the plasticizer, phthalic acid esters such as diethylhexyl phthalate, dioctyl phthalate, and dibutyl phthalate, dioctyl adipate, dioctyl sebacate, epoxidized oil, and other plasticizers that plasticize general polyvinyl chloride can be used. Further, in order to soften the polyvinyl chloride resin and improve adhesion to the polyether ester layer, it is also possible to use the polyether ester itself blended with the polyvinyl chloride. The laminate molded product of the present invention is a laminate molded product in the form of a tube, a hose, a bottle, a bag, etc., which has a soft polyvinyl chloride resin layer as an outer layer and a polyetherester layer as an inner layer. In the case of the tube shown in Figure 1, the inner layer 2 of the tube in contact with the liquid or gas 3 passing through the tube is a thin layer of polyetherester elastomer, and the outer layer 1 is a plasticized polyvinyl chloride compound. .

Further, referring to a portion of the pin shown in Fig. 2, the inner layer 2 in contact with the liquid or gas 3 is formed of polyether polyester elastomer as described above, and the outer layer 1 is formed of a thick layer of polyvinyl monochloride compound. That's what I do.

In this case, the thickness composition ratio of the laminated body is inner layer/outer layer 1/1.
A range of approximately 0.01/1 to 0.01/1 is suitable.

In other words, a polyether ester layer alone cannot achieve desired flexibility, transparency, and moldability at the same time, but by laminating a thin polyether ester layer on an outer polyvinyl chloride layer, the flexibility and transparency of polyvinyl chloride can be improved. It is possible to obtain a laminate with excellent safety and hygiene properties without any elution of plasticizers or vinyl chloride monomers without any loss in properties. Therefore, the polyvinyl chloride resin outer layer is laminated to a thickness smaller than approximately the same thickness and approximately 1/100 times thicker. Generally, for medical vinyl chloride materials, a thickness of about 1 mm is suitable for use, so the polyetherester inner layer thickness is 10 microns to 0.
, about 5 mm. As a method for forming the laminate molded product of the present invention, a method in which a polyether ester elastomer and a plasticized polyvinyl chloride resin are laminated in one step to form a multilayer structure is preferred.

That is, polyether ester and plasticized PVC are simultaneously extruded into tubes, sheets, and bottles using a conventional direct composite extruder heated to 130 to 180°C.
(In the case of bottles, polyether ester is used as the inner layer), and a suitable solidifying device such as a cooling bath, mold, or drum is used to provide shape retention. The laminated sheet is formed into a bag shape by thermal bonding or applying adhesive, with the polyester elastomer layer facing inside. It is also possible to form a laminate by directly laminating polyether ester onto a pre-prepared vinyl chloride sheet or coating it with a solution. The laminated structure of the present invention can be used as medical materials such as various medical tubes, catheters, and bags such as infusion sets, blood transfusion sets, blood bags, infusion bags, artificial dialysis circuits, intravenous catheters, sheet-type oxygenators, and artificial heart-lung circuits. More transparency,
Due to its flexibility, chemical resistance, and hydrolysis resistance, it can be used as a variety of tubes, bottles, and bags, including chemical liquid transfer tubes and chemical storage bags.

EXAMPLES Specific examples of the present invention will be explained in detail below using Examples.

Example 1 13.9 parts of terephthalic acid, 5.98 parts of isophthalic acid
, 21.6 parts of 4-butanediol and 20.0 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of about 1000 were charged into a reactor equipped with a rectification column, and after esterification at 210°C for 2 hours at normal pressure, The temperature was raised to 245° C. for minutes, and polymerization was carried out under reduced pressure of 0.37×1 Hg to obtain a polybutylene terephthalate/polybutylene isophthalate/poly(tetramethylene oxide) glycol copolymer.

35 weight using this polyether ester and diethylhexyl phthalate (DEHP) as a plasticizer? The polyvinyl chloride resin contained therein was introduced into a direct composite extruder heated to 160°C, and extruded into water in a cylindrical shape through a die, with an outer diameter of 10 m and an inner diameter of 8 mm, an inner layer thickness of 0.1 mm, and a total inner and outer layer thickness of 1. It was made into a laminated tube of .0 mm.

This laminated tube has excellent transparency with a transmittance of 83%, and has a bending modulus of 180k9/d, making it highly flexible and kick (
bending of the tube) is less likely to occur. Furthermore, the adhesion at the interface between the polyetherester and polyvinyl chloride layers was strong, and remained strongly bonded even after treatment with hot water (9'C) for 3 hours. Example 2 81.5 parts of dimethyl terephthalate, 5 parts of dimethyl phthalate
A polyetherester elastomer was made according to Example 1 from 4.3 parts of 1,4-butanediol, 94.5 parts of 1,4-butanediol, and 70.0 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of about 800. .

Next, this polyether ester and a polyvinyl chloride resin containing 30% diethylhexyl phthalate (DEHP) as a plasticizer were directly introduced into a composite extruder heated to 170°C, and 0.4 to 1. 0 Dragon polyether ester was extruded as a laminate or single layer sheet having a thickness of 0.6 to 0 TIL, 1 L, and a total thickness of 1 u1. The laminated sheet was folded with the polyether ester layer inside and the three corners were heat-sealed, then 200 cc of blood was injected and stored in a refrigerator at 5° C. for one month. It is clear that the concentration of DEHP contained in the storage solution is significantly suppressed by the polyetherester inner layer5. Furthermore, if the polyetherester layer becomes too thick, the transparency and flexibility will decrease, which is undesirable. Example 3 The polyetherester obtained in Example 1 was made into a 50 μm thick film by hot pressing.

On the other hand, a sheet (0.8 m!) of plasticized PVC containing 35% dioctylephthalate was prepared, and both were sealed with a heat sealer heated to 180°C at a pressure of about 11<g/d.
When heat bonding was performed for seconds, the stress required for T-peel peeling at the interface was 1000 g/CTIl or more.

Even after hot water treatment (100 x 3 hr), the adhesive strength was approximately 1
00% retained. For comparison, polyethylene terephthalate (4), poly ε-caprolactam (B), 50/50 (molar ratio) of ε-caprolactam and laurolatatum.
Copolymer (C), polyester-type urethane (D: Japan Polyurethane “Paraprene” 26S), polyether-type urethane (E: Japan Elastolan゜“Elastraso゜E”)
385F) was adhered to a plasticized PVC sheet under the same conditions, but the adhesion strength was extremely low in both cases.

[Brief explanation of drawings]

FIGS. 1 and 2 show a cross-sectional view of a tube, which is an embodiment of the medical laminate molded article according to the present invention, and a partial cross-sectional view of a pin, respectively. Explanation of main symbols: 1: Inner layer portion of laminate molded product, 2. The outer layer of a laminated molded product.

Claims (1)

[Claims] 1. A laminate molded product having an outer layer 1 made of a plasticized polyvinyl chloride resin compound and an inner layer 2 made of a thin layer of polyetherester elastomer.