JPS6096623A - Production of resin molding - Google Patents
Production of resin moldingInfo
- Publication number
- JPS6096623A JPS6096623A JP20562783A JP20562783A JPS6096623A JP S6096623 A JPS6096623 A JP S6096623A JP 20562783 A JP20562783 A JP 20562783A JP 20562783 A JP20562783 A JP 20562783A JP S6096623 A JPS6096623 A JP S6096623A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- ethylene
- acrylate
- meth
- vinyl acetate
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/085—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using gamma-ray
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
- B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/06—PVC, i.e. polyvinylchloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2031/00—Use of polyvinylesters or derivatives thereof as moulding material
- B29K2031/04—Polymers of vinyl acetate, e.g. PVAc, i.e. polyvinyl acetate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2096/00—Use of specified macromolecular materials not provided for in a single one of main groups B29K2001/00 - B29K2095/00, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0085—Copolymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0088—Blends of polymers
Abstract
Description
【発明の詳細な説明】
本発明は耐熱性及び弾性にすぐれる樹脂成形物、特に医
療用としての用途に適する樹脂成形物の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a resin molded article having excellent heat resistance and elasticity, particularly a resin molded article suitable for medical use.
医療用樹脂成形物として血液を運搬、保存するための血
液バッグ、人工腎臓による透析を行なうための血液回路
用チューブ等が広く用いられている。このような樹脂成
形物は、その使用目的から細胞毒性や溶血作用をイ１し
ないことは勿論、柔軟性、透明性、耐熱性、弾性等にす
ぐれていることが要求される。例えば、血液回路用チュ
ーブは、内部を流れる血液を外部から観察し得る透明性
、自在に変形し得る柔軟性、クランプで締め付けたり、
はずしたりする際に容易に変形すると共に容易に当初の
形状を回復し、或いは血液ポンプにて血液等の体液を循
環させるのに使用されるポンプ部チューブのように長時
間しごきを継続しても流量が変化せず、また、破裂しな
い弾性等が強く要求される。BACKGROUND ART Blood bags for transporting and storing blood, tubes for blood circuits for dialysis using artificial kidneys, and the like are widely used as medical resin moldings. Such resin moldings are required to have excellent flexibility, transparency, heat resistance, elasticity, etc. as well as being free from cytotoxicity and hemolytic effects due to their intended use. For example, tubes for blood circuits are transparent so that the blood flowing inside can be observed from the outside, flexible enough to be deformed freely, tightened with a clamp,
It easily deforms when removed and easily recovers its original shape, or even if it is squeezed for a long time, such as the pump tube used to circulate blood and other body fluids in a blood pump. It is strongly required that the flow rate does not change and the elasticity does not rupture.
しかし、従来、上記のような医療用樹脂成形物は、多く
の場合、フタル酸エステル系可塑剤、例えば、ジオクチ
ルフタレートを多量に含有する塩化ビニル樹脂から成形
されており、これらは柔軟性、透明性の点ではすぐれる
が、使用の際に可ｆ４１ｊ剤が僅かながら血液中に溶出
し、体内に吸収蓄積されるおそれがある。また、上記の
ような医療用樹脂成形物は滅菌のために加圧蒸気に曝し
た場合、成形物が相互に、又は器物壁との間で強くブロ
ッキングを生じ、透明性が失われて白化しやすく、また
、変形しやすい等の欠点を有している。However, in the past, medical resin moldings such as those mentioned above were often molded from vinyl chloride resin containing a large amount of phthalate ester plasticizers, such as dioctyl phthalate, and these were made of vinyl chloride resin that was flexible and transparent. Although it has excellent properties, there is a risk that a small amount of f41j agent may be eluted into the blood during use and absorbed and accumulated in the body. Furthermore, when medical resin moldings such as those mentioned above are exposed to pressurized steam for sterilization, the moldings strongly block with each other or with the walls of the instrument, causing loss of transparency and whitening. It has drawbacks such as being easy to deform and being easily deformed.
このために可塑剤を含む塩化ビニル樹脂に代わる医療用
樹脂成形物の製造方法として、特開昭５３−８５９８０
号公報には、エチレン−酢酸ビニル共重合樹脂からなる
医療用成形物に放射線又は電子線を照射して架橋させる
方法が開示されている。しかし、この方法によれば、成
形物に十分な耐熱性を付与するには、照射線量を大量に
する必要があり、この結果、樹脂の分解、脱酢酸等が起
こって、溶血作用を自するに至る問題があり、更に、従
来の塩化ビニル樹脂成形物に比べて柔軟性に乏しい。For this reason, as a method for manufacturing medical resin moldings to replace vinyl chloride resin containing plasticizers, JP-A-53-85980
The publication discloses a method of crosslinking a medical molded article made of an ethylene-vinyl acetate copolymer resin by irradiating it with radiation or an electron beam. However, according to this method, in order to impart sufficient heat resistance to the molded product, it is necessary to apply a large dose of irradiation, which results in decomposition of the resin, deacetic acid, etc., and hemolysis. In addition, it is less flexible than conventional vinyl chloride resin molded products.
本発明は上記した問題を解決するためになされたもので
あって、可塑剤を含まずして柔軟且つ透明であるのみな
らず、すぐれた耐熱性及び高弾性を有し、従って、局に
医療用途に好適な樹脂成形物の製造方法を提供すること
を目的とする。The present invention has been made to solve the above-mentioned problems, and is not only flexible and transparent without containing a plasticizer, but also has excellent heat resistance and high elasticity. It is an object of the present invention to provide a method for manufacturing a resin molded article suitable for various uses.
本発明の樹脂成形物の製造方法は、塩化ビニル７ｉＪＪ
１１１１００重量部についてエチレン−酢酸ビニル系樹
脂５０〜３００重量部及び多官能性（メタ）アクリレー
ト１〜３０重量部を含有する樹脂組成物を所定形状の成
形物に成形した後、この成形物にγ線又は電子線を照射
してゲル分率５０〜９０％とすることを特徴とする。The method for producing a resin molded product of the present invention includes vinyl chloride 7iJJ
After molding a resin composition containing 50 to 300 parts by weight of an ethylene-vinyl acetate resin and 1 to 30 parts by weight of a polyfunctional (meth)acrylate for 100 parts by weight of 111 into a molded product of a predetermined shape, this molded product is coated with γ. It is characterized in that the gel fraction is set to 50 to 90% by irradiation with a beam or an electron beam.
本発明において、塩化ビニル系樹脂としては、塩化ビニ
ルの単独重合体、又は塩化ビニルとこれに共重合性を有
するその他のｆｆｌｑ体との共重合体が使用される。こ
のような共重合性単量体としては、例えば、アクリル酸
、メタクリル酸、メチルメタクリレート、メチルアクリ
レート、ブチルアクリレート、プチルメククリレート、
２−エチルへキシルアクリレート、２−エチルへキシル
メタクリレート、ステアリルアクリレート、ステアリル
メタクリレート等の（メタ）アクリル酸及びそのアルキ
ルエステル頬、エチレン、プロピレン等のα−オレフィ
ン類、酢酸ビニル、ステアリン酸ビニル等のビニルエス
テル類、メチルビニルエーテル、セチルビニルエーテル
等のビニルエーテル類が用いられる。特に好ましくはエ
チレン、ブチルアクリレート及び２−エチルへキシルア
クリレートが用いられる。これらの共重合性単量体は塩
化ビニル１００重量部について２０重量部以下の範囲で
共重合されるのが好ましい。In the present invention, as the vinyl chloride resin, a homopolymer of vinyl chloride or a copolymer of vinyl chloride and another fflq body having copolymerizability with vinyl chloride is used. Examples of such copolymerizable monomers include acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate, butyl acrylate, butyl meccrylate,
(Meth)acrylic acid and its alkyl esters such as 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, stearyl acrylate, stearyl methacrylate, α-olefins such as ethylene and propylene, vinyl acetate, vinyl stearate, etc. Vinyl ethers such as vinyl esters, methyl vinyl ether, and cetyl vinyl ether are used. Particularly preferred are ethylene, butyl acrylate and 2-ethylhexyl acrylate. These copolymerizable monomers are preferably copolymerized in an amount of 20 parts by weight or less per 100 parts by weight of vinyl chloride.
エチレン−酢酸ビニル系樹脂としては、酢酸ビニル含ｍ
２０〜６０％のエチレン−酢酸ビニル共重合体や、エチ
レンと白酸ビニルとこれらに共重合性を有する他の単量
体との三元共重合体が使用されるが、特に、エチレン−
酢酸ビニルー−酸化炭素共重合体が好ましく用いられる
。特に、エチレン７２〜５０％、酢酸ビニル２０〜３５
％及び−酸化炭素８〜１３％からなるエチレン−酢酸ビ
ニルー−酸化炭素共１０合樹脂が好ましく用いられる。As the ethylene-vinyl acetate resin, vinyl acetate-containing m
20 to 60% ethylene-vinyl acetate copolymers and terpolymers of ethylene, vinyl sulfate, and other monomers copolymerizable with these are used, but in particular, ethylene-vinyl acetate copolymers are used.
Vinyl acetate-carbon oxide copolymer is preferably used. In particular, ethylene 72-50%, vinyl acetate 20-35%
An ethylene-vinyl acetate-carbon oxide co-polymer resin consisting of 8 to 13% of carbon oxide and carbon oxide is preferably used.
このような三元共１ｎ合体は市販品（例えば、デュポン
社製「エルハ１．１イ」等）として入手できる。エチレ
ン−酢酸ビニル系樹脂は前記塩化ビニル系樹脂１００重
口部について５０〜３００重量部の範囲で配合される。Such a ternary 1n combination is available as a commercial product (for example, "Elha 1.1" manufactured by DuPont). The ethylene-vinyl acetate resin is blended in an amount of 50 to 300 parts by weight per 100 parts by weight of the vinyl chloride resin.
５０重量部よりも少ないときは、得られる樹脂成形物が
柔軟性に乏しく、一方、３００重量部より多いときは成
形物の粘着性が増し、使用に際して種々支障が生じると
共に強度も低下するので好ましくない。If it is less than 50 parts by weight, the resulting resin molded product will have poor flexibility, while if it is more than 300 parts by weight, the molded product will have increased stickiness, causing various problems in use and decreasing strength, so it is preferable. do not have.
また、多官能性くメタ）アクリレートとしては、好まし
くは次式で表わされる二官能性又は三官能性（メタ）ア
クリレートが用いられる。Further, as the polyfunctional meth)acrylate, preferably a bifunctional or trifunctional (meth)acrylate represented by the following formula is used.
ＣＨ□−ＣＸ−Ｃｏ（ＯＣＨ２ＣＨ□）ｎＯＣＯ−ＣＨ
２ＣＨ２（１）ＣＨ２ＣＨ２
Ｚ−ＣＨ−Ｃ（ＣＨ０−Ｃｏ−ＣＸ＝ＣＨ２）３（ＩＩ
Ｉ ）２
（但し、Ｘ、Ｙ及びＺはそれぞれ独立に水素又はメチル
基、ｎは１〜１４の数を示す。）具体的には、例えば（
１）としてポリエチレングリコールジ（メタ）アクリレ
ート、（ＩＩ）としてアルキレンジオールジ（メタ）ア
クリレート、（Ｉ）としてトリメチロールプロパントリ
（メタ）アクリレート等が用いられる。CH□-CX-Co(OCH2CH□)nOCO-CH
2CH2(1)CH2CH2 Z-CH-C(CHO-Co-CX=CH2)3(II
I)2 (However, X, Y and Z each independently represent hydrogen or a methyl group, and n represents a number from 1 to 14.) Specifically, for example, (
As 1), polyethylene glycol di(meth)acrylate, as (II), alkylene diol di(meth)acrylate, and as (I), trimethylolpropane tri(meth)acrylate, etc. are used.
本発明においては、前記塩化ビニル系樹脂及びエチレン
−酢酸ビニル系樹脂と共に上記多官能性（メタ）アクリ
レ−１−とからなる樹脂組成物を例えばチューブやシー
トに成形した後、この成形物にγ線又は電子線を照射し
て、これら多官能性（メタ）アクリレートを架橋させる
が、その配合量は塩化ビニル系樹脂１００重量部につい
て１〜３０重量部である。配合量が少なずぎるときは十
分な架橋が得られず、１１１１・１熱性、弾性の改善効
果に乏しく、一方、余りに多量に配合するときは、架橋
度が高すぎる結果、成形物が硬くなり、柔軟性に欠ける
ようになるので好ましくない。In the present invention, after a resin composition comprising the polyfunctional (meth)acrylate 1- as well as the vinyl chloride resin and ethylene-vinyl acetate resin is molded into a tube or sheet, the molded product is These polyfunctional (meth)acrylates are crosslinked by irradiation with a beam or an electron beam, and the amount thereof is 1 to 30 parts by weight per 100 parts by weight of the vinyl chloride resin. If the amount is too small, sufficient crosslinking will not be obtained and the effect of improving 1111.1 thermal properties and elasticity will be poor. On the other hand, if the amount is too large, the degree of crosslinking will be too high and the molded product will become hard. , which is undesirable because it results in a lack of flexibility.
特に、本発明においては、成形物へのγ線又は電子線の
照射量を０．５〜７メガラツドの範囲として、樹脂成形
物のゲル分率が５０〜９０％となるように架橋するのが
好ましい。このようなゲル分率は通常、樹脂成形物をテ
トラヒドロフランに熔解させたときの不溶分としてめる
ことができる。In particular, in the present invention, crosslinking is carried out so that the gel fraction of the resin molded product is 50 to 90% by irradiating the molded product with gamma rays or electron beams in the range of 0.5 to 7 megarads. preferable. Such a gel fraction can usually be considered as the insoluble matter when the resin molded product is dissolved in tetrahydrofuran.
このゲル分率が５０％よりも小さいときは、架橋構造の
形成が不十分であって、耐熱性及び弾性の改善効果に乏
しく、一方、９０％よりも多いときは、架橋構造が過度
に形成される結果、前記したように成形物が柔軟性に欠
Ｌ）るほか、例えば、接着性にも劣るようになるので好
ましくない。When this gel fraction is less than 50%, the formation of a crosslinked structure is insufficient and the effect of improving heat resistance and elasticity is poor.On the other hand, when it is more than 90%, the formation of a crosslinked structure is excessive. As a result, the molded product lacks flexibility as described above, and also has poor adhesion, which is undesirable.
同様に、γ線又は電子線の照射量が０．５メガラツドよ
りも少ないときは、必要な量の架橋構造が形成されず、
反面、７メガラツドよりも多いときは架橋構造が過度に
形成されて、前記した問題が生じるのみならず、樹脂成
形物が着色する等の問題も生じる。Similarly, when the irradiation dose of gamma rays or electron beams is less than 0.5 megarads, the required amount of crosslinked structure is not formed,
On the other hand, when the amount is more than 7 megarads, a crosslinked structure is excessively formed, which not only causes the above-mentioned problems but also causes problems such as coloring of the resin molded product.
本発明においては、前記樹脂組成物は必要に応じて安定
剤その他の添加剤を合音することができる。例えば、安
定剤としてステアリン酸カルシウム、ステアリン酸亜鉛
、酸化カルシウム、１１マグネシウム、フェノール系抗
酸化剤、亜リン酸エステル系抗酸化剤、エポキシ系可塑
剤等を適宜量含有することができ、また、成形時におけ
る溶融流れ性の改善、金型付着防止等を目的としてポリ
エチレン系、酸アミド系、エステル系等の滑剤、ジエチ
ルへキシルツクレート、ジオクチルアジペート等の可塑
剤を適宜量含有させることもできる。In the present invention, the resin composition may contain stabilizers and other additives as required. For example, calcium stearate, zinc stearate, calcium oxide, 11 magnesium, phenolic antioxidants, phosphite antioxidants, epoxy plasticizers, etc. can be contained in appropriate amounts as stabilizers, and molding For the purpose of improving melt flowability during processing, preventing adhesion to molds, etc., suitable amounts of polyethylene-based, acid amide-based, ester-based lubricants, and plasticizers such as diethylhexyl slate and dioctyl adipate may be included.
本発明の方法において、成形物は通常、チューブやシー
トの形状であって、血液バッグ、輸液バッグ、血液回路
用チューブ等の医療用樹脂成形物に好適に使用されるが
、しかし、合成レザーや電線被覆等の一般の用途にも使
用し得ることはいうまでもない。In the method of the present invention, the molded product is usually in the shape of a tube or sheet, and is suitably used for medical resin molded products such as blood bags, infusion bags, and tubes for blood circuits. Needless to say, it can also be used for general purposes such as covering electric wires.
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。尚、以
下において、溶血性試験は、日本薬局方［一般試験法−
１輸ｌｆＫ用プラスチック容器試験法に準拠して行ない
、また、細胞毒性試験は、樹脂成形物を細１ｔｌｉ Ｌ
、、その１ｇをＭＥＭ培地中に加え、１２１°Ｃで２０
分間オートクレーブ中で抽出して抽出培地を対照培地で
希釈し、これを細胞に投与し、３７℃で５目間、炭酸ガ
ス濃度５％で培養した後、顕微鏡にて細胞数及び死細胞
数を数え、対照液と比較してＭ性を判定することにより
行なった。The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way. In the following, the hemolytic test is based on the Japanese Pharmacopoeia [General Test Methods]
The cytotoxicity test was carried out in accordance with the plastic container test method for 1000 mlfK.
,, add 1 g of it to MEM medium and incubate at 121°C for 20
After extraction in an autoclave for 1 minute, the extraction medium was diluted with a control medium, administered to cells, and incubated at 37°C for 5 days at a carbon dioxide concentration of 5%. The number of cells and dead cells were counted using a microscope. The M property was determined by counting and comparing with a control solution.
また、ポンプ部チコーーブの耐久性及び弾性については
、透析聖人］二腎臓承認基準に準拠して試験を行なった
。In addition, the durability and elasticity of the pump part Chicove were tested in accordance with the Dialysis Saint's Two Kidney Approval Standards.
実施例１〜３
第１表に示す組成の塩化ビニル−エチレン共重合樹脂、
エチレン−酢酸ビニルー−酸化炭素共重合樹脂、トリメ
チロールプロパントリメタクリレート、エポキシ化大豆
油及びＣａ−Ｚｎ安定剤からなる混合物を温度１４０′
ｃの８インチオープン２本ロールにて４分間混練した後
、ペレット化した。このペレットを４ｏφ単独押出機に
て外径１２關、内径８顛のチューブに成形し、これに所
定量の電子線を照射した。Examples 1 to 3 Vinyl chloride-ethylene copolymer resin having the composition shown in Table 1,
A mixture consisting of ethylene-vinyl acetate-carbon oxide copolymer resin, trimethylolpropane trimethacrylate, epoxidized soybean oil, and Ca-Zn stabilizer was heated at a temperature of 140'.
The mixture was kneaded for 4 minutes using two 8-inch open rolls, and then pelletized. This pellet was formed into a tube having an outer diameter of 12 mm and an inner diameter of 8 mm using a 4 oφ single extruder, and the tube was irradiated with a predetermined amount of electron beam.
このようにして得たチューブの特性を第１表に示す。併
せてトリメチロールプロパントリメタクリレートを含ま
ず、従って、電子線照射による架橋を行なわなかった樹
脂成形物についても、その特性を第１表に示す。本発明
の方法により得られた樹脂成形物は、耐熱性及び弾性に
すぐれ、また、溶血作用、細胞毒性共になく１．更にポ
ンプ部しごき試験においてもひび割れを生じないので、
ポンプ部チューブほか医療用途に好適に使用し得るが、
これに対して比較例の成形物によれば、耐熱性、弾性共
に劣ることが明らかである。The properties of the tube thus obtained are shown in Table 1. Table 1 also shows the properties of resin molded products that did not contain trimethylolpropane trimethacrylate and therefore were not crosslinked by electron beam irradiation. The resin molded product obtained by the method of the present invention has excellent heat resistance and elasticity, and has no hemolytic effect or cytotoxicity.1. Furthermore, no cracks occur in the pump part ironing test, so
It can be suitably used for pump tubes and other medical applications, but
On the other hand, it is clear that the molded products of Comparative Examples are inferior in both heat resistance and elasticity.
実施例４〜Ｇ
実施例１においてトリメチロールプロパントリメタクリ
レートに代えてポリエチレングリコールジメタクリレー
トを用いた以外は、実施例１と同様にして樹脂成形物を
得た。架橋剤を含まず、電子線照射を行なわなかった樹
脂成形物と共に、成形物の特性を第２表に示す。Examples 4 to G Resin molded articles were obtained in the same manner as in Example 1, except that polyethylene glycol dimethacrylate was used in place of trimethylolpropane trimethacrylate. Table 2 shows the properties of the molded products as well as the resin molded products that did not contain a crosslinking agent and were not irradiated with electron beams.
本発明による成形物は、耐熱性及び弾性にすぐれ、医療
用途に好適に用いることができるが、比較例による成形
物は耐熱性に劣るほか、耐久性試 □験において破裂し
、また、溶血性や細胞毒性を示すので、医療用途には使
用し得ない。The molded product according to the present invention has excellent heat resistance and elasticity, and can be suitably used for medical purposes.However, the molded product according to the comparative example has poor heat resistance, bursts in the durability test, and has hemolytic properties. It cannot be used for medical purposes because it exhibits cytotoxicity and cytotoxicity.
実施例３
実施例１において、トリメチロールプロパントリメクク
リレートに（ｔＬえて１，６−ヘキサンシオールジメタ
クリレートを用いた以外は、実施例１と同様にして樹脂
成形物を得た。この成形物の特性を第３表に示すように
、いずれも耐熱性及び弾性にすぐれることが明らかであ
る。Example 3 A resin molded product was obtained in the same manner as in Example 1, except that 1,6-hexanethiol dimethacrylate was used instead of trimethylolpropane trimecacrylate. As the properties are shown in Table 3, it is clear that all of them have excellent heat resistance and elasticity.
特許出願人 積水化学工業株式会社 代表者藤沼基利Patent applicant Sekisui Chemical Co., Ltd. Representative Mototoshi Fujinuma
Claims (1)
−酢酸ビニル系樹脂５０〜３００重量部及び多官能性（
メタ）アクリレート１〜３０重量部を含有する樹脂組成
物を所定形状の成形物に成形した後、この成形物にγ線
又は電子線を照射してゲル分率５０〜９０％とすること
を特徴とする樹脂成形物の製造方法。(1) 50 to 300 parts by weight of ethylene-vinyl acetate resin and polyfunctional (
A resin composition containing 1 to 30 parts by weight of meth)acrylate is molded into a molded article of a predetermined shape, and then the molded article is irradiated with gamma rays or electron beams to give a gel fraction of 50 to 90%. A method for manufacturing a resin molded article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20562783A JPS6096623A (en) | 1983-10-31 | 1983-10-31 | Production of resin molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20562783A JPS6096623A (en) | 1983-10-31 | 1983-10-31 | Production of resin molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6096623A true JPS6096623A (en) | 1985-05-30 |
| JPH0262137B2 JPH0262137B2 (en) | 1990-12-25 |
Family
ID=16510017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20562783A Granted JPS6096623A (en) | 1983-10-31 | 1983-10-31 | Production of resin molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6096623A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997021537A1 (en) * | 1995-12-11 | 1997-06-19 | Shell Internationale Research Maatschappij B.V. | Cross-linked polyketones |
| US5705539A (en) * | 1995-12-11 | 1998-01-06 | Shell Oil Company | Curing polyketones with high energy radiation |
| EP0976779A2 (en) * | 1998-07-31 | 2000-02-02 | Bayer Aktiengesellschaft | Rubber polymers with high gel content and elevated degree of swelling |
| EP0976778A2 (en) * | 1998-07-31 | 2000-02-02 | Bayer Corporation | Rubber polymerizates with a high gel content and a high swelling degree |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930438A (en) * | 1972-07-20 | 1974-03-18 |
-
1983
- 1983-10-31 JP JP20562783A patent/JPS6096623A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4930438A (en) * | 1972-07-20 | 1974-03-18 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997021537A1 (en) * | 1995-12-11 | 1997-06-19 | Shell Internationale Research Maatschappij B.V. | Cross-linked polyketones |
| US5705539A (en) * | 1995-12-11 | 1998-01-06 | Shell Oil Company | Curing polyketones with high energy radiation |
| EP0976779A2 (en) * | 1998-07-31 | 2000-02-02 | Bayer Aktiengesellschaft | Rubber polymers with high gel content and elevated degree of swelling |
| EP0976778A2 (en) * | 1998-07-31 | 2000-02-02 | Bayer Corporation | Rubber polymerizates with a high gel content and a high swelling degree |
| EP0976778A3 (en) * | 1998-07-31 | 2000-08-02 | Bayer Corporation | Rubber polymerizates with a high gel content and a high swelling degree |
| EP0976779A3 (en) * | 1998-07-31 | 2000-08-09 | Bayer Aktiengesellschaft | Rubber polymers with high gel content and elevated degree of swelling |
| US6399671B1 (en) | 1998-07-31 | 2002-06-04 | Bayer Aktiengesellschaft | Rubber polymers having an elevated gel content and an elevated degree of swelling |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0262137B2 (en) | 1990-12-25 |
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