JPH0133491B2 - - Google Patents
Info
- Publication number
- JPH0133491B2 JPH0133491B2 JP59032609A JP3260984A JPH0133491B2 JP H0133491 B2 JPH0133491 B2 JP H0133491B2 JP 59032609 A JP59032609 A JP 59032609A JP 3260984 A JP3260984 A JP 3260984A JP H0133491 B2 JPH0133491 B2 JP H0133491B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- molded article
- soft vinyl
- silicone rubber
- 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
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000004945 silicone rubber Substances 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 13
- 229920002379 silicone rubber Polymers 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 238000009832 plasma treatment Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 238000003851 corona treatment Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- -1 dimethylsiloxane Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000002785 anti-thrombosis Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- External Artificial Organs (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、塩化ビニル系樹脂―シリコーン複合
成形物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a vinyl chloride resin-silicone composite molded product.
〔従来技術〕
塩化ビニル樹脂は、可塑剤もしくは高分子エラ
ストマー等の添加により柔軟性が付与され、透明
性に優れ、接着性、高周波加工性等加工性が良い
ので、医療用具、食品包装等に広く使用されて来
た。しかしながら、医療用具の分野に於ては、塩
化ビニル系樹脂製品は抗血栓性、組織適合性に劣
る為に、血液と直接接触する用途とか、体内で長
期間使用する用途では種々の問題が生じる。[Prior art] Vinyl chloride resin is made flexible by adding plasticizers or polymeric elastomers, has excellent transparency, and has good processability such as adhesiveness and high-frequency processability, so it is used for medical devices, food packaging, etc. It has been widely used. However, in the field of medical devices, vinyl chloride resin products have poor antithrombotic properties and tissue compatibility, which causes various problems when used in direct contact with blood or used in the body for long periods of time. .
一方シリコーンは、優れた抗血栓性と組織適合
性の故に、医用材料として期待されながらも、高
価格及び強度が弱いなどの理由からまだその使用
量は少ない。 On the other hand, although silicone is expected to be used as a medical material due to its excellent antithrombotic properties and tissue compatibility, its usage is still small due to its high price and low strength.
両者の長所、欠点を補う目的で、塩化ビニル系
樹脂にシリコーンオイルを練込んだり、コーテイ
ング等の複合化する試みが多くなされている。し
かし、軟質塩化ビニル樹脂に於いては、一般に可
塑剤等の添加剤の影響で、シリコーンとの固着一
体化が困難と考えられていた。この問題を克服す
る為に、例えば軟質塩化ビニル系樹脂表面にプラ
イマー処理をし、しかる後にシリコーン層を形成
する方法が種々提案されているが、工程が煩雑で
あること、及び多くのプライマーは酢酸エチル、
トルエン等の溶剤を使用する為にそれらの残留が
懸念され、また一度接着しても経時的に剥離する
という問題があつた。 In order to compensate for the advantages and disadvantages of both, many attempts have been made to incorporate silicone oil into vinyl chloride resin or to combine it with coatings, etc. However, with soft vinyl chloride resins, it has generally been thought that it is difficult to firmly integrate them with silicone due to the influence of additives such as plasticizers. In order to overcome this problem, various methods have been proposed, for example, applying a primer treatment to the surface of a soft vinyl chloride resin and then forming a silicone layer, but the process is complicated, and many primers use acetic acid. ethyl,
Since solvents such as toluene are used, there is concern that they may remain, and even if they are once bonded, they will peel off over time.
一方、特開昭54−156083号公報などによれば、
塩化ビニル系樹脂表面を予じめ低温プラズマ処理
し、しかる後に縮合型の常温硬化型シリコーンの
硬化層を形成する方法、また特開昭58−34773号
公報によれば、塩化ビニル系樹脂材料の表面に予
じめプラズマ処理等により硬化層を形成したの
ち、ジメチルシロキサン、又はアルキル基による
変性ジメチルシロキサンからなるシリコーン層を
形成し、改質することが提案されている。この様
に低温プラズマ処理を行うことにより、縮合型の
RTVシリコーンゴムやシリコーン樹脂が、軟質
塩化ビニル樹脂表面に固着することは明らかであ
る。 On the other hand, according to Japanese Patent Application Laid-Open No. 54-156083, etc.
According to Japanese Patent Application Laid-Open No. 58-34773, the surface of a vinyl chloride resin material is subjected to low-temperature plasma treatment in advance, and then a cured layer of condensation type room temperature curing silicone is formed. It has been proposed that after a hardened layer is previously formed on the surface by plasma treatment or the like, a silicone layer made of dimethylsiloxane or dimethylsiloxane modified with an alkyl group is formed and modified. By performing low-temperature plasma treatment in this way, condensation type
It is clear that RTV silicone rubber and silicone resin adhere to the surface of soft vinyl chloride resin.
しかしながら、縮合型RTVシリコーンゴムは、
硬化反応時に副生する酢酸やオキシムの沸点がわ
りあいに高く、150℃以上の高温で数時間、また
は、軟質塩化ビニル系樹脂が変形しない温度範囲
では、減圧下で長時間、脱副生成物の操作を行な
わないと、シリコーンが本来持つている抗血栓等
の生体適合性を発揮出来ない。また、シリコーン
樹脂は一般的に接着力に欠け、その皮膜自体は硬
く、軟質塩化ビニル樹脂の様に柔軟性のあるもの
との組合せでは皮膜にクラツク等が発生する危険
性がある。 However, condensation type RTV silicone rubber
The boiling point of acetic acid and oxime, which are produced as by-products during the curing reaction, is relatively high, so by-products can be removed for several hours at a high temperature of 150°C or higher, or for a long time under reduced pressure in a temperature range where the soft vinyl chloride resin does not deform. If this operation is not performed, silicone will not be able to exhibit its inherent biocompatibility such as antithrombotic properties. Furthermore, silicone resins generally lack adhesive strength, and their coatings themselves are hard, and when used in combination with flexible materials such as soft vinyl chloride resins, there is a risk that cracks may occur in the coatings.
この様な問題のないものとして、白金触媒等を
用いた付加重合型シリコーンゴムがある。この付
加重合型シリコーンゴムには、いわゆるLTVと
呼ばれる低温硬化型のシリコーンゴムがあり、こ
れらは100℃前後という比較的低温で短時間に硬
化し、且つ副生成物がほとんどなく、抗血栓性等
の特性に優れたものである。発明者らは、この優
れた特性を有する付加重合型シリコーンゴムと軟
質塩化ビニル系樹脂との接着性について検討し、
驚くべきことに低温プラズマ処理等の物理的方法
により、軟質塩化ビニル系樹脂に前処理を施すこ
となしに接着できる、付加重合型シリコーンゴム
と軟質塩化ビニル系樹脂の組合せを見い出し、特
願昭58−95689号、特願昭58−203699号に特許出
願した。 Addition polymerization type silicone rubber using a platinum catalyst or the like is available as a material that does not have such problems. This addition polymerization type silicone rubber includes a low-temperature curing type silicone rubber called so-called LTV, which cures in a short time at a relatively low temperature of around 100°C, has almost no by-products, and has antithrombotic properties. It has excellent characteristics. The inventors investigated the adhesion between addition-polymerized silicone rubber, which has excellent properties, and soft vinyl chloride resin, and
Surprisingly, by using physical methods such as low-temperature plasma treatment, he discovered a combination of addition-polymerizable silicone rubber and soft vinyl chloride resin that could be bonded to soft vinyl chloride resin without pretreatment, and filed a patent application in 1982. -95689 and Japanese Patent Application No. 58-203699.
本発明は、これらに更に改良を加え、接着力を
向上させることを目的として鋭意検討した結果、
低温プラズマ処理、コロナ処理等の物理処理を、
軟質塩化ビニル樹脂系成形物表面に施した後に、
付加重合型シリコーンゴム組成物をコーテイン
グ、硬化させると、その接着力が大巾に向上する
ことを見い出し、本発明を完成するに至つたもの
である。
The present invention has been developed as a result of intensive studies aimed at further improving these and improving adhesive strength.
Physical treatments such as low-temperature plasma treatment and corona treatment,
After applying it to the surface of a soft vinyl chloride resin molded product,
The present inventors have discovered that coating and curing an addition polymerizable silicone rubber composition greatly improves its adhesive strength, leading to the completion of the present invention.
即ち本発明は、軟質塩化ビニル樹脂系成形品の
低温プラズマ、またはコロナ処理を施した表面
に、付加重合型シリコーンゴム組成物の硬化層を
設けてなる、塩化ビニル系樹脂―シリコーン複合
成形物に関するものである。
That is, the present invention relates to a vinyl chloride-based resin-silicone composite molded product, which is formed by providing a hardened layer of an addition polymerizable silicone rubber composition on the surface of a soft vinyl chloride resin-based molded product that has been subjected to low-temperature plasma or corona treatment. It is something.
本発明における付加重合型シリコーンゴムと
は、一般式(1)に示されるビニル基含有のポリシロ
キサンと、一般式(2)に示されるオルガノ水素ポリ
シロキサン、及び必要に応じて補強剤としてのシ
リカ等の無機物よりなる組成物を、白金系触媒等
によつて付加重合させることにより弾性体に固化
し得る組成物のことである。この中で、一般式(2)
に示されるオルガノ水素シロキサン単位が、一般
式(1)に示される全ビニル基に対し0.8以上、好ま
しくは１以上６倍の比率でケイ素原子に直結した
水素原子を与えるに充分な量のオルガノ水素ポリ
シロキサンが含有されていた方が良い。 The addition polymerizable silicone rubber in the present invention includes a vinyl group-containing polysiloxane represented by the general formula (1), an organohydrogen polysiloxane represented by the general formula (2), and silica as a reinforcing agent if necessary. A composition that can be solidified into an elastic body by addition-polymerizing a composition made of an inorganic substance such as a platinum-based catalyst or the like. Among these, general formula (2)
The organohydrogen siloxane units represented by formula (1) are present in an amount sufficient to provide hydrogen atoms directly bonded to silicon atoms at a ratio of 0.8 or more, preferably 1 or more and 6 times, to the total vinyl groups represented by general formula (1). It is better if it contains polysiloxane.
〔式中、
R1〜R4：炭素数６以下の同種又は異種の１価
の炭化水素基
ｍ：正の整数〕
〔式中、
R5，R7〜R10：炭素数６以下の同種または異種
の１価の炭化水素基
R6：水素基又は炭素数３以下の同種又は異種
の１価の炭化水素基
ｎ：２以上100以下の整数
ｌ：０又は100以下の正の整数〕
また、一般に自己接着性シリコーンゴムと言わ
れるものに示される成分としての、エポキシ化合
物、カルボン酸無水物、一般式(3)に示されるアク
リロキシアルキル基含有のシラン又はシロキサン
あるいは不飽和炭化水素基含有のオキシラン化合
物の添加や付加重合型シリコーンゴム組成物の固
化後に得られる硬化層の物性を向上させる為の成
分として、一般式(1)及び(2)に示される成分と相溶
するビニル基含有のレジン様の共重合体の添加も
可能である。例えば、一般式(4)，(5)及び(6)の共重
合体オルガノポリシロキサン等がある。 [In the formula, R 1 to R 4 : Same or different monovalent hydrocarbon groups having 6 or less carbon atoms m: Positive integer] [In the formula, R 5 , R 7 to R 10 : Same or different monovalent hydrocarbon groups having 6 or less carbon atoms R 6 : Hydrogen group or same or different monovalent hydrocarbon groups having 3 or less carbon atoms n : An integer of 2 or more and 100 or less l: 0 or a positive integer of 100 or less] In addition, epoxy compounds, carboxylic acid anhydrides, general formula (3) as components shown in what is generally called self-adhesive silicone rubber. As a component for improving the physical properties of a cured layer obtained after addition of an acryloxyalkyl group-containing silane or siloxane or an unsaturated hydrocarbon group-containing oxirane compound shown in It is also possible to add resin-like copolymers containing vinyl groups which are compatible with the components shown in formulas (1) and (2). For example, there are copolymer organopolysiloxanes of general formulas (4), (5) and (6).
〔式中、 R11：CH3又はＨ基 R12：（CH2）o基 ｎは１以上３以下の整数〕 （CH2＝CH）（R13）（R14）SiO0 [In the formula, R 11 : CH 3 or H group R 12 : (CH 2 ) o group n is an integer from 1 to 3] (CH 2 = CH) (R 13 ) (R 14 ) SiO 0
Claims (1)
重合型シリコーンゴム組成物の硬化層を有する複
合成形物であつて、該付加重合型シリコーンゴム
組成物はその組成物中のビニル基１ケあたり、ケ
イ素原子に直結した水素原子を0.8乃至６個与え
るに充分な量の、１分子中に該水素原子を２個以
上有するオルガノ水素ポリシロキサンを含有して
おり、また、前記軟質塩化ビニル系樹脂成形品
は、該樹脂中に含有されている安定剤中の金属
が、カルシウム、亜鉛、バリウム、マグネシウ
ム、アルミニウムの内の一つ又は二つ以上であ
り、且つ該成形品の表面が、予じめ低温プラズマ
処理、又はコロナ処理が施されていることを特長
とする軟質塩化ビニル系樹脂―シリコーン複合成
形物。 ２ 軟質塩化ビニル系樹脂の表面に付加重合型シ
リコーンゴム組成物の硬化層を設ける際に、少な
くとも40℃以上の温度で加熱硬化させることを特
長とする、軟質塩化ビニル系樹脂―シリコーン複
合成形物の製造方法。[Scope of Claims] 1. A composite molded article having a cured layer of an addition polymerizable silicone rubber composition on the surface of a soft vinyl chloride resin molded article, wherein the addition polymerizable silicone rubber composition is included in the composition. Contains an organohydrogenpolysiloxane having two or more hydrogen atoms in one molecule in an amount sufficient to provide 0.8 to 6 hydrogen atoms directly bonded to silicon atoms per vinyl group, and The soft vinyl chloride resin molded article is such that the metal in the stabilizer contained in the resin is one or more of calcium, zinc, barium, magnesium, and aluminum, and the molded article A soft vinyl chloride resin-silicone composite molded article, the surface of which has been previously subjected to low-temperature plasma treatment or corona treatment. 2. A soft vinyl chloride resin-silicone composite molded article, which is characterized in that when a cured layer of an addition polymerizable silicone rubber composition is provided on the surface of the soft vinyl chloride resin, it is heated and cured at a temperature of at least 40°C or higher. manufacturing method.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59032609A JPS60179426A (en) | 1984-02-24 | 1984-02-24 | Flexible vinyl chloride resin/silicone composite molding and its production |
| EP84113150A EP0143994B1 (en) | 1983-11-01 | 1984-10-31 | Thermoplastic resin-silicone composite shaped article |
| DE8484113150T DE3485414D1 (en) | 1983-11-01 | 1984-10-31 | MOLDED COMPOSITE MADE OF THERMOPLASTIC RESIN AND SILICONE. |
| US06/675,997 US4686124A (en) | 1983-12-12 | 1984-11-29 | Thermoplastic resin-silicone rubber composite shaped article |
| US06/917,194 US4814231A (en) | 1983-12-12 | 1986-10-09 | Thermoplastic resin-silicone composite shaped article |
| US07/151,312 US4834721A (en) | 1983-12-12 | 1988-02-01 | Thermoplastic resin silicone composite shaped article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59032609A JPS60179426A (en) | 1984-02-24 | 1984-02-24 | Flexible vinyl chloride resin/silicone composite molding and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60179426A JPS60179426A (en) | 1985-09-13 |
| JPH0133491B2 true JPH0133491B2 (en) | 1989-07-13 |
Family
ID=12363593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59032609A Granted JPS60179426A (en) | 1983-11-01 | 1984-02-24 | Flexible vinyl chloride resin/silicone composite molding and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60179426A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2596771B2 (en) * | 1987-12-28 | 1997-04-02 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing silicone rubber-coated cloth laminate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5474291A (en) * | 1977-11-25 | 1979-06-14 | Japan Atom Energy Res Inst | Production of anit-clouding transparent composite |
| JPS56116466A (en) * | 1980-02-18 | 1981-09-12 | Toray Industries | Vinyl chloride resin medical material with improved surface |
| JPS57133129A (en) * | 1981-02-12 | 1982-08-17 | Asahi Chem Ind Co Ltd | Coating composition |
-
1984
- 1984-02-24 JP JP59032609A patent/JPS60179426A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5474291A (en) * | 1977-11-25 | 1979-06-14 | Japan Atom Energy Res Inst | Production of anit-clouding transparent composite |
| JPS56116466A (en) * | 1980-02-18 | 1981-09-12 | Toray Industries | Vinyl chloride resin medical material with improved surface |
| JPS57133129A (en) * | 1981-02-12 | 1982-08-17 | Asahi Chem Ind Co Ltd | Coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60179426A (en) | 1985-09-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |