JPS5850964A - Resin composition for medical device - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Takaaki Moto is a medical specialist, especially bags for storing ring waves.

#I for the blood flow of the artificial kidney.
Regarding the tree #111 suitable for making.

Conventionally, as si*m5nt, for example, blood bags have been used to transport and store blood, and KIIL, which performs dialysis using an artificial kidney for patients with renal failure, and blood circuit chains have been used.

The properties required for them are to be flexible and not change in quality, and even if they come into contact with blood for a long time, they must not change the quality of the blood or transfer foreign substances into the tube. Na-.

In addition, the blood tract chape is transparent so that blood passing through the inside can be observed from the outside, and is flexible enough to be freely deformed, and is removed with a clamp from the outside of the chape.
The IIK Chape quickly returns to its original shape, and by repeating this process, the blood flow is stopped at any time. Since the tubes may adhere to each other, a non-adhesive surface is required.

By the way, the chape for the blood circuit in the blood bag has conventionally been made from a composition made by adding a large amount of dioctyl 7-talate to a vinyl chloride resin. Although this composition has excellent flexibility and transparency, the disadvantage is that a small amount of dioctyl 7-talate is eluted and is collected and accumulated in the body through the blood. Ninth, Tugu for one circuit of blood may come in contact with ethylene oxinide gas, but in such cases, the disadvantage is that it has the property of collecting ethylene oxidite. picture.

Therefore, there is a need to create a resin composition for blood bags and blood circuit tube structures that do not have these drawbacks.

The present inventors have added dioctyl tsthalate to vinyl chloride resin to overcome the 9 types of harmful substances. 1. There is no release of harmful substances to the human body, and it is transparent. 1. Softness. 1M elasticity. Non-adhesion.
It was discovered that a graft copolymer in which vinyl chloride is grafted onto an ethylene-vinyl acetate copolymer is effective as a material that can obtain 1F, and as a result of intensive study, an ethylene-vinyl acetate copolymer was found to be effective. 9. We have invented an m* product that can significantly reduce the resulting adhesiveness of the surface.

The gist of the present invention is to obtain a graft copolymer k obtained by brat polymerizing vinyl chloride to an ethylene-acetate bis Jl/copolymer,
, l' is a bis1. It is characterized by containing a mite-based compound.

II Therapy 111#M14ft Existing in the collection.

Next, the #fat composite material for m5m5 of the present invention will be explained in more detail.

Ethylene-vinyl acetate copolymer (hereinafter referred to as l) in the present invention
It is preferable that the copolymerized amount of vinyl acetate is in the range of 30 to 80% by weight.

When the amount of the co-16 component of vinyl acetate exceeds IImIK, a graft copolymer having particularly excellent flexibility and transparency can be obtained. In addition, vinyl acetate obtained by IVAFi high-pressure polymerization, suspended heavy metal polymerization, and emulsion polymerization according to the present invention may also be used, but it is particularly preferable to use vinyl acetate obtained by aqueous turbidity polymerization. The amount of copolymerization component is 50 to 80
Count in the weight range of ducks.

Graft polymerization of vinyl chloride in the presence of the above-mentioned Mvm is carried out by mixing EVA, vinyl chloride, water, a dispersant, etc., forming an aqueous turbidity, and reacting using a radical polymerization agent. Examples of the agent include 1, for example, a saponification degree of 70 to 90.
Partially saponified polyvinyl acetate, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl hexafluoride, polyacrylic sodium, polyvinyl vinyl 111 ton, etc. are used.

Radical polymerization agents include 9oyl74++okinai F, penzoylno-1-okinide, azobisbutyloethryl, t-butyl-oxycycaponate, etc., and these dispersants and electrolyte-fighting agents. Conventionally, vinyl chloride has been used as an aqueous polymer, and in the present invention, these have been combined. , 411 (used. &o, The temperature of the 1-layer pot for the above-mentioned Darafushi polymerization is #
KIllL1tL1kSn#, S@-70t#*t L
After graft polymerizing vinyl chloride onto the wing mum in the Kyoto suspension box in this manner, the grafted polymer was sedimented, dehydrated and dried to obtain a polymer obtained using the Guft copolymer produced by ZeroajjiK. The dispersing agent is eluted from the medical equipment used and becomes hemolytic and cytotoxic.

In addition to vinyl chloride, the graft copolymer of the present invention may contain other monomers that can be copolymerized with vinyl chloride, such as acrylic acid, methacrylic acid, and methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, and 2-ethyl. Acrylic esters and methacrylic esters such as kydylacrylate, 2-ethylhexyl methacrylate, stearyl acrylate, stearyl kS methacrylate; α- such as ethylene and propylene
Olefins; May contain vinyl esters such as vinyl acetate and vinyl stearate IIS/vinyl ethers such as tyl vinyl ether and cetyl vinyl ether, %#I of the above preferred ones are CHm=CI
-X (X is a hydrogen atom or a methyl group, 0OY Y is a water bulk atom or an alkyl group having 1 to 18 carbon atoms), so the monomers include (meth)ac9lic acid and (meth)acrylic acid. ) Acrylic acid esters, particularly ethylhexyl acrylate or butyl acrylate. It is possible to copolymerize these monomers with vinyl chloride and graft copolymerize them onto the above ethylene-vinyl acetate copolymer. The transparency and low temperature flexibility are significantly improved compared to the grafted hook polymer. These monomers are used for vinyl chloride IK (LOI In(
,,It was alarming that there was F @ at the opening of the 10 weight ratio.

These monomers and vinyl chloride 2 may be added all at once before starting the heavy metal, or they may be added continuously or in portions during the polymerization (as described above, by adding the heavy metal in an aqueous suspension in the presence of 9 Nv Heavy money is carried out.

The graft copolymer obtained by the above method is.

The graft copolymer composition itself has excellent transparency and flexibility, and is moderately cytotoxic. Do not leave medical equipment piled up for a long time.vh
The material has a so-called surface tackiness that easily adheres to other Kll materials. However, by incorporating a bisamide compound into the graft copolymer, the above-mentioned surface tackiness can be significantly suppressed.

The bisamide compound used in the present invention has the formula % (where n is an integer of 1 to 180, and R and R' are an alkyl group or alkenyl group having 8 to 29 carbon atoms).
Is). Examples of those in which R and II' are an alkyl group include methylene diamine distearate, ethylene diamine dipelargonate,
Hemethylenediamine dipelargonate, hemethylenediamine dibecurgonate, methylenediamine dirafuto.

Ethylene diamine dilaurate, tetramethylene diamine dilumitate, hexydemethylene diamine dicrate, methylene diamine dilumitate, ethylene diamine dilumitate, tetramethylene diamine dilumitate, hequinamethylene diamine dilumitate, methylene diamine distearate, Ethylene diamine distearate, tetraethylene diamine distearate, hexamethylene diamine distearate, hexamethylene di-1
Assuming that minster ν and belargonate and hequinate and ethylenediamineste 1 and 1′) consist of 1 luquer group.

For example, methylene diamine di9-desylate.

Ethylene diamine dicundesylate, tetramethylene diamine dicundacylate, hequinamethylene diamine dicundacylate, methylene diamine dioleate, ethylene diamine dioleate, tetramethylene diamine dioleate.

Hexidemethylene diamine dioleate, methylene diamine dilysylate, ethylene diamine dilysylate,
Examples include 7F totsumethylene diamine dilysylate, hexamethylene diamine dilysylate, hexamethylene diamine lysylate kundesylate, hexamethylene diamine lysylate oleate, and the like.

Among the above compounds, those used are stearinamides, such as methylene diamine distearate, ethylene diamine distearate, tetramethylene diamine distearate, and hequinamethylene diamine distearate. All of these have melting points of 13
It is obtained as a white powdery mass of 00 to 14013.

The bisamide compound is a graft copolymer Zo obtained by graft polymerizing vinyl chloride to the nine ethylene-vinyl acetate copolymer described above.

It is preferable to use it in a range of 0.1 to 5 parts by weight.

The bisamide-based compound is not only used alone, but also combined with low molecular weight polyethylene (average molecular weight 101
) (101) (1-) Can be used in combination with one or more lubricants containing polyhydric acids, and in such a case, the effect of preventing the surface tackiness of the former will appear.

In order to improve the thermal stability and aging resistance of the graft copolymer obtained by graft polymerizing the KVAK vinyl chloride and the bisamide compound obtained in the present invention, Stabilizers and emollients that are known in the art and have no deleterious effects can be incorporated into the tank. As the stabilizer, for example, stearin shunriki #Vt^, lead stearate, paricum stearate, etc. can be used, and as the stabilizer, Ebokireka 1m, dioctyl tstalate, etc. can be used. It's cloudy.

As described above, the resin composition for medical equipment of the present invention includes:
Because the bisamide-based compound is added to the nine-graft co-polymerized body obtained by graft polymerizing EVAK vinyl chloride, the molded body has excellent flexibility and transparency, and does not exhibit hemolytic or cytotoxic properties. In addition, the stone surface adhesion caused by the EVA component of the brat copolymer is significantly suppressed, and the KWh materials adhere to each other when medical devices obtained by the composition of the present invention are stacked and left for a long time. There will be nothing left to do.

The resin composition of the present invention can be suitably used for molding medical equipment such as medical catheters, tubes for blood transfusions and infusions, blood bags, infusion bags, and blood tanks for artificial dialysis.

Examples of the present invention will be described below. The hemolytic test is Glass Tik I for ring waves in the "General test method" of the Japanese Pharmacopoeia Law.
It was conducted in accordance with the vs test method.

Example 1 A graft copolymer obtained by graft polymerizing vinyl chloride to an EV film obtained by high-pressure polymerization (copolymerization amount of vinyl acetate 322 parts by weight)
Is weight storage, conjugate composition of vinyl acetate 14.4 parts by weight) 100 parts by weight, methylene diamine distearate a
7 W1 part, Cm-Za type tranquilizer, 1 layer 1L, 5 parts by weight of oxygenated soybean oil were kneaded in two rolls at 140°C to obtain a roll sheet.
C. and a pressure of 10011 F/- for 3 minutes to form a sheet with a smooth surface and a thickness of as■. A hemolytic test was conducted on this sheet, and it showed no hemolytic effect.

A surface tack test was then conducted. The surface adhesion theory is
The above sheet was cut into rectangular test pieces with a diameter of 813 mm and a length of 813 mm, and two of these sheets were stacked one on top of the other, and a load of 500 f712 mm was uniformly applied to sections from one end of the test piece to 61 mm. The sample was left at SO℃ for 24 hours and then subjected to profking at a tensile speed of 10 aw for 7 minutes. This was done by peeling off the sample and determining the maximum peeling force. As a result, the maximum peel force was 27 p/2 am, and the maximum peel force when methylene diamine distearate was not used was 1702 p/2 am.
It was observed that the maximum peeling force was smaller compared to the two countries, and the surface tackiness was significantly reduced.

Examples 2-S In Example 1, methylene diamine distearate o
, Example 1 except that ethylene di-1 (17 parts by weight (Example 2) and hexamethylene cyadiene distearate Q7 (Example 3) were used in place of 7-layered Hiroshi). A sheet was formed using the same machine, and then a bloodletting test and a surface adhesion test were conducted.The results showed no hemolytic properties.

Also, the maximum peel force is 24 f/2 as (Run #1
2), 11t/2 (to) (Example 3), and the maximum as force is 17Of when methylene diamine distearate or hexame diamine distearate is not used.
/ 2 as, and it was observed that the surface tackiness was significantly reduced.

Example 4 Graft copolymer obtained by graft polymerizing EYAK vinyl chloride obtained by high-pressure polymerization in Example I (copolymerization content of vinyl chloride 55% by weight, copolymerization content of vinyl acetate 1) (4% by weight) instead of 100% by weight,
Graft copolymer obtained by graft polymerization of vinyl chloride to Evmu (II vinyl acetate copolymerization amount of 600% by weight) obtained by suspension enrichment (copolymerization amount of vinyl chloride★ of 50% by weight, Copolymerization amount of vinyl acetate: 30% by weight) 1
A sheet was formed using the same machine as Example 1, except that 06 parts by weight was used, and then a bloodletting property test and a surface adhesion test were conducted. As a result, no hemolytic property was shown.
The maximum peeling force is 4 II y / Z-, methycinthiadendisteare) (maximum peeling force when 17 parts by weight is not used!! It is smaller than 9.t/2-, and the surface tackiness is noticeable. ζ has been reduced and ξ has been expanded.

Examples S to 6 In Example 4, methylene shift distearate a
Instead of 7 parts by weight, ethylene cyanodiasterate 7rate a
A sheet was formed in the same manner as in Example 4, except that 7 parts by weight of irises (II Example 5) and hexamethylene cyanodendistearate (17 parts by weight (Example 6) were used), and then a phlebotomy sheet was formed. Test, surface tack test was conducted.

As a result, none of them showed any hemolytic properties.

Also, the maximum *m force is 44 t/2 m <Example S)
, 18 f/2 g (Example 6) and 1 ethylene cyano distearate, maximum 111 I force without hexamethylene cyano distearate 29
It was observed that the surface tackiness was smaller than that of 0ri/2 as Iζ, and that the surface tackiness was significantly reduced.

Claims (1)

[Claims] 1. A graft copolymer obtained by graft polymerizing vinyl chloride to an ethylene-vinyl acetate copolymer, 1 (wherein l is an integer from 1 to M18, and R and R' are carbon atoms. Resin composition 2 for medical equipment, characterized in that it contains a bisamide-based compound having a number of 8Jjt to 29 or less and which is milled with a mulberry, an alkyl group or an alkenyl group. , which is obtained by graft polymerizing an ethylene-vinyl acetate copolymer with vinyl chloride and other monomers copolymerizable therewith. Resin assembly 3 for medical l materials as described in Claims column 111, wherein the bis-1-mite thickness compound is contained in an amount of 0.1 to IIjIll parts with respect to the weight of the Gutsu 7F copolymerized body Zoo llK. Claim 1m11 characterized by
111xFil12m Description O [Resin assembly for 111B material