JPH0246614B2 - - Google Patents

Info

Publication number
JPH0246614B2
JPH0246614B2 JP57146529A JP14652982A JPH0246614B2 JP H0246614 B2 JPH0246614 B2 JP H0246614B2 JP 57146529 A JP57146529 A JP 57146529A JP 14652982 A JP14652982 A JP 14652982A JP H0246614 B2 JPH0246614 B2 JP H0246614B2
Authority
JP
Japan
Prior art keywords
weight
ethylene
parts
copolymer
vinyl chloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP57146529A
Other languages
Japanese (ja)
Other versions
JPS5936153A (en
Inventor
Kazuhiko Kamyoshi
Seiichiro Pponda
Seiya Hosokawa
Hiroyoshi Hata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sekisui Chemical Co Ltd
Original Assignee
Sekisui Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Priority to JP57146529A priority Critical patent/JPS5936153A/en
Publication of JPS5936153A publication Critical patent/JPS5936153A/en
Publication of JPH0246614B2 publication Critical patent/JPH0246614B2/ja
Granted legal-status Critical Current

Links

Description

【発明の詳細な説明】[Detailed description of the invention]

本発明は医療用樹脂組成物に関し、詳しくは、
透明性、耐熱性、耐候性、低温柔軟性、成型加工
性、シール加工性、耐ブロツキング性に優れたオ
ートクレーブ滅菌可能な医療用樹脂組成物に関す
る。 従来塩化ビニル樹脂系に、ジオクチルフタレー
ト、ジオクチルアジペート等の可塑剤が多量に配
合された組成物が、柔軟でありながら優れた強度
物性を持つため、多くの分野で使用されてきた。 しかしながらこのような組成物は可塑剤が多量
に配合されているため長期間使用する間に、ある
いは、加熱状態で使用する間に可塑剤が移行し、
柔軟性が失われ脆化する欠点を有していた。又、
医療分野等で血液バツグ、輸液バツグ等に使用す
る際には、上記の可塑剤が血液や輸液中に溶出
し、このためそれらの材料を用いて治療を受ける
人達の健康がおびやかされる問題点が存してい
た。 従来軟質塩化ビニル樹脂の有する上記欠点を解
消するために、例えば塩素化ポリエチレンを塩化
ビニル樹脂に混合した組成物、エチレン・酢酸ビ
ニル共重合体に塩化ビニルをグラフト共重合させ
た樹脂等が採用されてきた。しかしこれらのいず
れにおいても透明性、耐熱性の諸性質が充分改善
されなかつた。 本発明者らは、上記問題点を解決するため、塩
化ビニル・エチレン共重合体からなる塩化ビニル
系樹脂にエチレン・酢酸ビニル・一酸化炭素共重
合体を配合し、更に特定のブロツク共重合体を加
えた系について種々検討を行なつた結果、可塑剤
を加えなくても、柔軟であつて、しかも透明性に
優れ、且つ、耐熱性、然候性、低温柔軟性に優れ
た特性を有し、しかもオートクレーブ滅菌可能な
組成物が得られることを見出し本発明を完成する
に至つた。 本発明の要旨は、 (イ) 重合度が600〜3000で、エチレン含有量2〜
15重量%の塩化ビニル・エチレン共重合体、 (ロ) エチレン・酢酸ビニル・一酸化炭素共重合
体、 (ハ) 式A−B−Aで表わされるブロツク共重合体
であつて、Aはスチレン重合体、Bはオレフイ
ン重合体である共重合体、 上記(イ)、(ロ)、(ハ)を成分とし、上記(イ)100重量

に対し上記(ロ)が5〜200重量部含有され、かつ、
上記(イ)及び(ロ)の合計量100重量部に対し上記(ハ)が
15〜150重量部含有されてなるオートクレーブ滅
菌可能な医療用樹脂組成物に存する。 次に本発明医療用樹脂組成物について更に詳細
に説明する。 本発明においては塩化ビニル系樹脂として、重
合度が600〜3000で、エチレン含有量2〜15重量
%の塩化ビニル・エチレン共重合体が用いられ
る。 又、本発明においては、エチレン・酢酸ビニ
ル・一酸化炭素共重合体が用いられるが、この共
重合体としてはエチレン含量が40乃至85重量%、
酢酸ビニル含量が15乃至50重量%、一酸化炭素含
量が5乃至20重量%の範囲のものが好適である。
又、該エチレン・酢酸ビニル・一酸化炭素共重合
体の分子量としては、重量平均分子量が2乃至
100万のものが好適である。 上記の塩化ビニル・エチレン共重合体及びエチ
レン・酢酸ビニル・一酸化炭素共重合体を混合す
ることにより、柔軟性に富む樹脂組成物が得られ
る。しかし、該組成物においては、高温における
強度低下、低温における柔軟性の低下が大きいと
いう欠点を有している。又、該樹脂組成物より得
られる成形物の表面は粘着性が大きく、自着性が
大きいという欠点を有していた。 本発明者らは、特定のブロツク共重合体が該組
成部に対して極めて優れた相溶性を有し、且つ上
記の問題点がいずれも解消されることを発見し
た。本発明において用いられるブロツク共重合体
としては式A−B−Aで示されるものである。こ
の式におけるB部分のオレフイン重合体として
は、ポリエチレン、ポリプロピレン、ポリイソブ
チレン、エチレン、プロピレン共重合体、エチレ
ン・ブチレン共重合体等のいずれであつてもよ
い。これらのオレフイン重合体部分の重量平均分
子量は1万乃至10万の範囲が好適である。スチレ
ン重合体がB部分の両側につながつて居り、A部
分を形成している。片側のスチレンポリマーの部
分は重量平均分子量2千乃至5万の範囲が好適で
ある。 該ブロツクポリマーにおけるスチレン重合体と
オレフイン重合体との組成比率は重量比率で5対
95乃至30対70の範囲にあることが好適である。 又、該ブロツクポリマー全体としての重合度は
1万乃至50万の範囲にあることが好適である。 上記の塩化ビニル・エチレン共重合体、及びエ
チレン・酢酸ビニル・一酸化炭素共重合体の重量
比率は100対5乃至100対200の範囲となされる。 該塩化ビニル・エチレン共重合体及びエチレ
ン・酢酸ビニル・一酸化炭素共重合体の混合物
100重量部に対する該ブロツク共重合体の使用量
は15重量部乃至150重量部の範囲となされる。 ブロツクポリマーの上記比率が15重量部より少
いと、ブロツキング性が強くあらわれ、且つ加熱
性における膜強度の低下、形崩れ等が起り易く、
耐熱性の乏しい成形物しか得られない。また該ブ
ロツクポリマーの上記比率が150重量部を越える
と、誘電率の低下にもとづき高周波加工が困難と
なり、又、耐磨耗性が著しく低下する。 上記の塩化ビニル・エチレン共重合体、エチレ
ン・酢酸ビニル・一酸化炭素共重合体及びブロツ
ク共重合体は通常の溶融混練の手段により混合さ
れる。例えばミキシングロール、押出型混練機等
により混練することができる。 本発明組成物の熱安定性を維持するために安定
剤を添加することが好ましい。例えば、ステアリ
ン酸カルシウム、ステアリン酸亜鉛、ステアリン
酸マグネシウム、エポキシ化大豆油、酸化マグネ
シウム等の熱安定剤を使用できる。 又、フエノール系、亜燐酸エステル系の抗酸化
剤を適宜使用することができる。 その他、少量ならば、例えばジオクチルフタレ
ート、ジオクチルアジペート等の可塑剤を添加す
ることができる。 本発明医療用樹脂組成物は透明であり、且つ柔
軟性に優れている。しかも耐熱性が極めて良好で
オートクレーブによる滅菌が可能であるため、従
来使用が困難であつた多くの分野に展開すること
ができる。 特に好適な応用途は、オートクレーブ内で蒸気
滅菌を必要とする医療器材、例えば、血液バツ
グ、輸液バツグ、カテーテル、血液回路、人工心
蔵用回路、手術手袋等である。 その他、レザー、食器包装用フイルム、テープ
基材、電線波覆材料、絶縁材料等に使用すること
ができる。 実施例 1 重合度1070、エチレン含量7重量%の塩化ビニ
ル・エチレン共重合体、エチレン・酢酸ビニル・
一酸化炭素三元共重合体(エチレン対酢酸ビニル
対一酸化炭素の組成比率が64対24対12)、及びブ
ロツクポリマーとして式A−B−AにおけるA部
分がスチレンポリマー、B部分がエチレン・ブチ
レン共重合体であり、スチレンの重量比率が28%
であるブロツク共重合体を用いた。 上記塩化ビニル・エチレン共重合体100重量部
に対して、上記三元共重合体及びブロツク共重合
体を夫々75重量部加え、安定剤として、カルシウ
ムステアレート粉末を0.1重量部、亜鉛ステアレ
ート粉末を0.2重量部、エポキシ化大豆油を10重
量部加えた。 上記混合物をミキシングロールにより、ロール
温度150℃で5分間混合し、シートを作成した。
このシートを160℃、100Kg/cm2の圧力条件でプレ
スしシートを作成した。 第1表の実施例1の蘭より明らかなように本発
明による組成物は従来材料と比較して、全く遜色
のない透明性及び柔軟性を持ち、耐油性や移行性
の測定値に見られるように優れた物性を有し、特
にオートクレーブ内での蒸気加熱による耐久性が
極めて優れていた。 実施例 2 実施例1において作成したロールシートを細か
く裁断して角状ペレツトを作成した。このペレツ
トを用いて、厚さ0.45m/mのシートを押出成形
により作成した。このシートを高周波シール加工
により長さ16cm、幅12cmの寸法のバツグを作成し
た。このようにして作成したバツグが輸液用容器
として適するか否かを調べるため以下の試験を実
施した。 該バツグ材料から溶出される成分の分析及び安
全性を知るため日本薬局「一般試験法」のなかの
輸液用プラスチツク容器試験法に準拠して、溶出
物試験及び溶血性試験を実施した。 また、該バツグがオートクレーブ蒸気加熱に耐
えるか否かを知るため、該バツグ内に生理食塩水
200mlを入れた状態で、オートクレーブに入れ、
121℃、20分間加熱蒸気内で放置した。 以上の結果を第表に示した。第表の結果か
ら明らかなように本発明組成物によつて作製した
バツグは輸液用バツグとして極めて適したもので
あることが明らかとなつた。 比較例 重合度1400のポリ塩化ビニル100重量部に、ジ
オクチルフタレート55重量部を加え、安定剤とし
てカルシウムステアレート粉末0.1重量部、亜鉛
ステアレート粉末0.2重量部、エポキシ化大豆油
10重量部を加えた。 実施例1と同様にしてシートを作成し、各種物
性を測定した結果を表の比較例の欄に示す。
The present invention relates to a medical resin composition, and more specifically,
The present invention relates to an autoclave-sterilizable medical resin composition that has excellent transparency, heat resistance, weather resistance, low-temperature flexibility, moldability, sealability, and blocking resistance. Conventionally, compositions containing a vinyl chloride resin and a large amount of plasticizers such as dioctyl phthalate and dioctyl adipate have been used in many fields because they are flexible but have excellent strength properties. However, since such compositions contain a large amount of plasticizer, the plasticizer migrates during long-term use or when used under heating.
It had the disadvantage of losing flexibility and becoming brittle. or,
When used in blood bags, infusion bags, etc. in the medical field, the above-mentioned plasticizers elute into the blood and infusions, which poses the problem of endangering the health of people receiving treatment using these materials. It existed. In order to eliminate the above-mentioned drawbacks of conventional soft vinyl chloride resins, for example, compositions in which chlorinated polyethylene is mixed with vinyl chloride resin, resins in which vinyl chloride is graft copolymerized to ethylene/vinyl acetate copolymer, etc. have been adopted. It's here. However, in none of these cases were the properties such as transparency and heat resistance sufficiently improved. In order to solve the above problems, the present inventors blended an ethylene/vinyl acetate/carbon monoxide copolymer into a vinyl chloride resin made of a vinyl chloride/ethylene copolymer, and further developed a block copolymer containing a specific block copolymer. As a result of various studies on systems with the addition of plasticizers, we found that they are flexible, have excellent transparency, and have excellent properties in heat resistance, weatherability, and low-temperature flexibility without the addition of plasticizers. However, the present inventors have discovered that a composition that can be sterilized in an autoclave can be obtained, leading to the completion of the present invention. The gist of the present invention is that (a) the degree of polymerization is 600-3000 and the ethylene content is 2-3000;
15% by weight vinyl chloride/ethylene copolymer, (b) ethylene/vinyl acetate/carbon monoxide copolymer, (c) a block copolymer represented by the formula A-B-A, where A is styrene. The polymer, B is a copolymer which is an olefin polymer, the above (a), (b), and (c) are the components, and the above (b) is contained in 5 to 200 parts by weight per 100 parts by weight of the above (a). and,
The above (c) is added to the total amount of 100 parts by weight of the above (a) and (b).
The present invention is an autoclave-sterilizable medical resin composition containing 15 to 150 parts by weight. Next, the medical resin composition of the present invention will be explained in more detail. In the present invention, a vinyl chloride/ethylene copolymer having a degree of polymerization of 600 to 3000 and an ethylene content of 2 to 15% by weight is used as the vinyl chloride resin. Further, in the present invention, an ethylene/vinyl acetate/carbon monoxide copolymer is used, and this copolymer has an ethylene content of 40 to 85% by weight,
Preferably, the vinyl acetate content is in the range of 15 to 50% by weight, and the carbon monoxide content is in the range of 5 to 20% by weight.
Furthermore, the molecular weight of the ethylene/vinyl acetate/carbon monoxide copolymer is such that the weight average molecular weight is 2 to 2.
1 million is preferred. By mixing the vinyl chloride/ethylene copolymer and the ethylene/vinyl acetate/carbon monoxide copolymer described above, a highly flexible resin composition can be obtained. However, this composition has the drawbacks of a large decrease in strength at high temperatures and a large decrease in flexibility at low temperatures. In addition, the surface of the molded product obtained from the resin composition had the disadvantage of being highly adhesive and highly self-adhesive. The present inventors have discovered that a particular block copolymer has extremely good compatibility with the composition, and that all of the above problems are solved. The block copolymer used in the present invention is represented by the formula ABA. The olefin polymer for the B portion in this formula may be any of polyethylene, polypropylene, polyisobutylene, ethylene, propylene copolymers, ethylene-butylene copolymers, and the like. The weight average molecular weight of these olefin polymer portions is preferably in the range of 10,000 to 100,000. Styrene polymers are attached to both sides of the B section to form the A section. The weight average molecular weight of the styrene polymer portion on one side is preferably in the range of 2,000 to 50,000. The composition ratio of styrene polymer and olefin polymer in the block polymer is 5:5 by weight.
A range of 95 to 30:70 is preferred. Further, the degree of polymerization of the block polymer as a whole is preferably in the range of 10,000 to 500,000. The weight ratio of the vinyl chloride/ethylene copolymer and the ethylene/vinyl acetate/carbon monoxide copolymer is in the range of 100:5 to 100:200. The vinyl chloride/ethylene copolymer and the mixture of ethylene/vinyl acetate/carbon monoxide copolymer
The amount of the block copolymer used per 100 parts by weight is in the range of 15 to 150 parts by weight. If the above ratio of the block polymer is less than 15 parts by weight, blocking properties will appear strongly, and the film will tend to lose its strength and lose its shape when heated.
Only molded products with poor heat resistance can be obtained. If the above ratio of the block polymer exceeds 150 parts by weight, high frequency processing becomes difficult due to a decrease in dielectric constant, and wear resistance is significantly reduced. The above-mentioned vinyl chloride/ethylene copolymer, ethylene/vinyl acetate/carbon monoxide copolymer and block copolymer are mixed by ordinary melt-kneading means. For example, kneading can be performed using a mixing roll, an extrusion type kneader, or the like. It is preferred to add a stabilizer to maintain the thermal stability of the composition of the invention. For example, heat stabilizers such as calcium stearate, zinc stearate, magnesium stearate, epoxidized soybean oil, magnesium oxide, and the like can be used. Furthermore, phenol-based and phosphorous acid ester-based antioxidants can be used as appropriate. In addition, a small amount of plasticizers such as dioctyl phthalate and dioctyl adipate can be added. The medical resin composition of the present invention is transparent and has excellent flexibility. Moreover, it has extremely good heat resistance and can be sterilized by autoclaving, so it can be used in many fields where it has been difficult to use in the past. Particularly suitable applications include medical equipment that requires steam sterilization in an autoclave, such as blood bags, infusion bags, catheters, blood circuits, artificial cardiac circuits, surgical gloves, and the like. In addition, it can be used for leather, tableware packaging films, tape base materials, electric wire covering materials, insulating materials, etc. Example 1 Vinyl chloride/ethylene copolymer with polymerization degree of 1070 and ethylene content of 7% by weight, ethylene/vinyl acetate/
Carbon monoxide terpolymer (composition ratio of ethylene to vinyl acetate to carbon monoxide is 64 to 24 to 12), and as a block polymer in the formula A-B-A, the A part is a styrene polymer and the B part is an ethylene polymer. It is a butylene copolymer, and the weight ratio of styrene is 28%.
A block copolymer was used. To 100 parts by weight of the above vinyl chloride/ethylene copolymer, 75 parts by weight of the above terpolymer and block copolymer were added, and as stabilizers, 0.1 part by weight of calcium stearate powder and zinc stearate powder were added. and 10 parts by weight of epoxidized soybean oil were added. The above mixture was mixed using a mixing roll at a roll temperature of 150° C. for 5 minutes to prepare a sheet.
This sheet was pressed at 160° C. and a pressure of 100 Kg/cm 2 to produce a sheet. As is clear from the orchid of Example 1 in Table 1, the composition according to the present invention has transparency and flexibility that are comparable to conventional materials, and is seen in the measured values of oil resistance and migration properties. It had excellent physical properties, and especially its durability when heated with steam in an autoclave was extremely excellent. Example 2 The rolled sheet prepared in Example 1 was cut into small pieces to form square pellets. Using this pellet, a sheet with a thickness of 0.45 m/m was produced by extrusion molding. This sheet was subjected to high-frequency sealing to create a bag with dimensions of 16 cm in length and 12 cm in width. The following test was conducted to determine whether the bag thus prepared was suitable as an infusion container. In order to analyze the components eluted from the bag material and find out its safety, an eluted substance test and a hemolytic test were conducted in accordance with the plastic container test method for infusions in the Japanese Pharmacy's "General Test Methods." In addition, in order to know whether the bag can withstand autoclave steam heating, saline solution is added to the bag.
Put 200ml into the autoclave,
It was left in heated steam at 121°C for 20 minutes. The above results are shown in Table 1. As is clear from the results shown in Table 1, the bags made from the compositions of the present invention are extremely suitable as bags for infusions. Comparative example 55 parts by weight of dioctyl phthalate was added to 100 parts by weight of polyvinyl chloride with a degree of polymerization of 1400, and 0.1 parts by weight of calcium stearate powder, 0.2 parts by weight of zinc stearate powder, and epoxidized soybean oil were added as stabilizers.
10 parts by weight were added. A sheet was prepared in the same manner as in Example 1, and various physical properties were measured. The results are shown in the Comparative Example column of the table.

【表】【table】

【表】【table】

【表】【table】

【表】【table】

Claims (1)

【特許請求の範囲】 1 (イ) 重合度が600〜3000で、エチレン含有量
2〜15重量%の塩化ビニル・エチレン共重合
体、 (ロ) エチレン、酢酸ビニル、一酸化炭素共重合
体、 (ハ) 式A−B−Aで表わされるブロツク共重合体
であつて、Aはスチレン重合体、Bはオレフイ
ン重合体である共重合体、 上記(イ)、(ロ)、(ハ)を成分とし、上記(イ)100重量

に対し上記(ロ)が5〜200重量部含有され、かつ、
上記(イ)及び(ロ)の合計量100重量部に対し上記(ハ)が
15〜150重量部含有されてなるオートクレーブ滅
菌可能な医療用樹脂組成物。
[Scope of Claims] 1 (a) A vinyl chloride/ethylene copolymer with a degree of polymerization of 600 to 3,000 and an ethylene content of 2 to 15% by weight, (b) An ethylene, vinyl acetate, carbon monoxide copolymer, (c) A block copolymer represented by the formula A-B-A, where A is a styrene polymer and B is an olefin polymer; As a component, 5 to 200 parts by weight of the above (B) is contained per 100 parts by weight of the above (A), and
The above (c) is added to the total amount of 100 parts by weight of the above (a) and (b).
An autoclave-sterilizable medical resin composition containing 15 to 150 parts by weight.
JP57146529A 1982-08-23 1982-08-23 Thermoplastic resin composition Granted JPS5936153A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP57146529A JPS5936153A (en) 1982-08-23 1982-08-23 Thermoplastic resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP57146529A JPS5936153A (en) 1982-08-23 1982-08-23 Thermoplastic resin composition

Publications (2)

Publication Number Publication Date
JPS5936153A JPS5936153A (en) 1984-02-28
JPH0246614B2 true JPH0246614B2 (en) 1990-10-16

Family

ID=15409700

Family Applications (1)

Application Number Title Priority Date Filing Date
JP57146529A Granted JPS5936153A (en) 1982-08-23 1982-08-23 Thermoplastic resin composition

Country Status (1)

Country Link
JP (1) JPS5936153A (en)

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ES2061938T3 (en) * 1988-06-08 1994-12-16 Shell Int Research COMPOSITION OF POLYMER.
JP2010090394A (en) * 2010-01-12 2010-04-22 Riken Technos Corp Dip-molding composition and dip-molding solvent paste for glove
CN110819039B (en) * 2019-11-27 2021-08-24 上海新泊地化工技术服务有限公司 TPE (thermoplastic elastomer) elastomer material special for anti-skid foot pad of bathroom and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5181845A (en) * 1975-01-14 1976-07-17 Chisso Corp NANNENSEIJUSHISOSEIBUTSU

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5181845A (en) * 1975-01-14 1976-07-17 Chisso Corp NANNENSEIJUSHISOSEIBUTSU

Also Published As

Publication number Publication date
JPS5936153A (en) 1984-02-28

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