JPS6249862B2 - - Google Patents
Info
- Publication number
- JPS6249862B2 JPS6249862B2 JP5625484A JP5625484A JPS6249862B2 JP S6249862 B2 JPS6249862 B2 JP S6249862B2 JP 5625484 A JP5625484 A JP 5625484A JP 5625484 A JP5625484 A JP 5625484A JP S6249862 B2 JPS6249862 B2 JP S6249862B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- silicone rubber
- resin composition
- soft vinyl
- 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 47
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 229920002379 silicone rubber Polymers 0.000 claims description 30
- 239000004945 silicone rubber Substances 0.000 claims description 22
- 229920005992 thermoplastic resin Polymers 0.000 claims description 17
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 7
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 6
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- -1 polypentadiene Polymers 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000012644 addition polymerization Methods 0.000 description 9
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000002785 anti-thrombosis Effects 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- SQNNHEYXAJPPKH-UHFFFAOYSA-N chloroethene;prop-2-enoic acid Chemical compound ClC=C.OC(=O)C=C SQNNHEYXAJPPKH-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
〔産業上の利用分野〕
本発明は塩化ビニル系樹脂組成物と付加重合型
シリコーンゴムとの複合成形物に関するものであ
る。
〔従来技術〕
塩化ビニル系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いては、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。
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
及び機械的強度が弱いなどの点からまだその使用
量は少ない。
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系樹脂に於いては、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。
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ゴ
ムの硬化層を形成する方法、また特開昭58−
32773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、ジメチルポリシロキサン又はアルキル
基による変性ジメチルポリシロキサンからなるシ
リコーン樹脂層を形成し改質することが提案され
ている。これらの方法によりシリコーン樹脂が固
着されることは明らかであるが、プラズマ処理は
細い径を持つチユーブ又は長いチユーブ状のもの
の内部まで完全に処理し硬化層を形成することが
困難である。
本発明者らは、以前にこれらプラズマ処理等の
硬化層を形成又はプラズマー処理等の前処理を全
くすることなく、従来困難であるとされてきた軟
質塩化ビニル系樹脂成形品表面へ直接抗血栓性に
優れたシリコーン固着層を形成させることを目的
にシリコーン及び塩化ビニル系樹脂について鋭意
検討した結果、強力に接着する軟質塩化ビニル系
樹脂とシリコーンとの組合せがあることを見出
し、特願昭58−203699号及び特願昭58−203700号
に示される発明を完成した。
〔発明の目的〕
しかし、本発明者らは、軟質塩化ビニル系樹脂
とシリコーンゴムとの接着性を更に向上させるこ
とを目的として検討を進める中で、軟質塩化ビニ
ル系樹脂中に炭素間二重結合を有する熱可塑性樹
脂を添加することによつて、付加重合型シリコー
ンゴムとの接着一体化が可能になることを見出
し、鋭意検討を進めて本発明を完成させるに至つ
た。
〔発明の構成〕
即ち、本発明は、塩化ビニル系樹脂100重量部
に対し、炭素間二重結合を有する熱可塑性樹脂を
0.1乃至10重量部含有する軟質塩化ビニル系樹脂
組成物よりなる成形品の表面に、付加重合型シリ
コーンゴムの硬化層を設けることを特長とする、
軟質塩化ビニル系樹脂組成物―シリコーンゴム複
合成形物を提供するものである。
本発明に於ける軟質塩化ビニル系樹脂組成物と
は、塩化ビニルホモポリマー、塩化ビニル―エチ
レン共重合体、塩化ビニル―酢酸ビニル共重合
体、塩化ビニル―エチレン―酢酸ビニル三元共重
合体、塩化ビニル―アクリル酸共重合体、塩化ビ
ニル―ウレタン共重合体といつた塩化ビニルを主
体とする共重合体などを主成分とし、それらに炭
素間二重結合を有する熱可塑性樹脂、可塑剤、安
定剤などが配合されたものである。
炭素間二重結合を有する熱可塑性樹脂とは、基
本的にはビニル基やアリル基等を含有する熱可塑
性樹脂であれば特に限定されるものではなく、そ
の数平均重合度が５以上、好ましくは10以上であ
るか、又は、その数平均分子量が2000以上、好ま
しくは5000以上であればよい。例えば、ジアリル
オルソフタレートプレポリマー、ジアリルイソフ
タレートプレポリマーをはじめ、ポリブタジエ
ン、ポリペンタジエン、エチレン―酢酸ビニル共
重合体、エチレン―ビニルアルコール共重合体、
ポリ塩化ビニリデン、などである。
尚、ここでエチレン―酢酸ビニル共重合体、エ
チレン―ビニルアルコール共重合体、ポリ塩化ビ
ニリデン等は、本来直鎖状の分子構造を有してい
るが、重合条件等によつて不飽和二重結合が分子
鎖中あるいは分子鎖末端に生成あるいは残留して
いることは知られている。本来は好ましくないこ
のような不飽和二重結合が、本発明においては有
効に作用するわけである。これら炭素間二重結合
を含有する熱可塑性樹脂の塩化ビニル系樹脂に対
する添加量は、炭素間二重結合の含有量によつて
異なるが、一般に塩化ビニル系樹脂100重量部に
対し、0.1乃至10重量部、好ましくは1.0乃至5.0重
量部が最適である。
塩化ビニル系樹脂に添加される可塑性について
は特に限定されるものではないが、付加重合型シ
リコーン組成物との接着に悪影響を与えることの
少ないジオクチルフタレートをはじめとするフタ
ル酸エステル、エポキシ化大豆油、エポキシ化ア
マニ油等を使用することが好ましい。
又、耐熱性、熱安定性を付与する安定剤として
は、ステアリン酸カルシウム、ステアリン酸亜
鉛、ステアリン酸バリウム、ステアリン酸マグネ
シウム等の金属石鹸の他、上記金属の有機金属安
定剤が特に好ましく、有機スズ系安定剤、ブチル
ステアレート等のエステル系安定剤、及びリン酸
系安定剤は付加重合型シリコーンゴムの硬化を阻
害するとともに、塩化ビニル系樹脂に添加された
炭素間二重結合含有の熱可塑性樹脂の添加効果を
も阻害してしまう為、使用上その併用はできな
い。
本発明に於ける付加重合型シリコーンゴムと
は、公知の様に一般式(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、さらに場合によつて補強
剤としてのシリカ等の無機物を添加した組成物
を、白金系の触媒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り、特
に限定しないが、好ましくはその組成物中のビニ
ル基１個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
キサンを含有していることが好ましい。また、接
着性を向上させる為の第三成分として、エポキシ
化合物、カルボン酸無水物等の添加されたものも
この範疇である。
〔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
ａ ：正の整数〕
〔式中R5、R7〜R10：炭素数６以下の同種又は異
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
ｂ ：２以上100以下の整数
ｃ ：０又は100以下の正の整数〕
本発明に於ける軟質塩化ビニル系樹脂組成物と
付加重合型シリコーンゴムとの複合成形物の製造
方法は、例えば炭素間二重結合含有の熱可塑性樹
脂を添加した軟質塩化ビニル系樹脂組成物を加熱
ロールで混練後造粒し、得られた成形材料を用い
て押出し法、プレス法、インジエクシヨン法等に
よつて成形し、該成形品の表面に付加重合型液状
シリコーンゴムをデイツピング法、スプレー法等
によつてコーテイングし、その後加熱炉等によつ
て40℃乃至130℃、好ましくは80℃乃至110℃に加
熱し、付加重合型液状シリコーンゴムを硬化させ
ればよく、これによりほぼ同時に該成形品との接
着一体化が達成されるわけで、製造方法は特に限
定されるものではないが、少なくとも40℃以上の
温度で加熱することを要件とする。
本発明に於ける接着機構は、塩化ビニル系樹脂
中の残留ビニル基あるいは加熱によつて生じた不
飽和二重結合に対する付加重合型液状シリコーン
ゴム組成物中のオルガノ水素シロキシ基の付加反
応であると推定した、本発明者らの先願特許であ
る特願昭58−203699号に於けるものと基本的には
同一であると推定している。即ち本発明に於い
て、炭素間二重結合含有の熱可塑性樹脂の添加に
よつて接着性がさらに改良されるのは、該熱可塑
性樹脂中の炭素間二重結合への付加重合型液状シ
リコーンゴム組成物中のオルガノ水素シロキシ基
の付加反応が起こる為と推定している。
しかし、該炭素間二重結合含有の熱可塑性樹脂
が数平均重合度５未満、あるいは数平均分子量
2000未満の場合は、接着に対するその添加効果は
ほとんどなく、逆に接着力を低下さることもあ
る。
〔発明の効果〕
本発明に於ける軟質塩化ビニル系樹脂組成物と
付加重合型シリコーンゴムとの複合成形物は強固
に接着一体化されており、軟質塩化ビニル系樹脂
のもつ強じん性、剛性を有しながら、その表面は
付加重合型シリコーンゴムのもつ優れた抗血栓
性、組織適合性を持ち、合わせて、コーテイング
されたその表面が極めて平滑である為、種々の用
途、特に医療分野に於いて有用なものである。
以下、実施例によつて本発明の効果を説明す
る。
実施例 １
塩化ビニル樹脂（東洋曹達（株）製700D）100
重量部に対し、金属重量換算でステアリン酸亜鉛
0.03重量部、ステアリン酸カルシウム0.03重量
部、ジオクチルフタレート40重量部、エポキシ化
大豆油10重量部を加えたものを軟質塩化ビニル樹
脂基本配合（第１表）とした。
次に炭素間二重結合を含有する熱可塑性樹脂と
して、ジアリルフタレートプレポリマー（大阪曹
達（株）製ダイソーダツプＬ）及び１，２―ポリ
ブタジエン（日本合成ゴム（株）製RB―820）を
用意し、各々第１表に示した量を上記軟質塩化ビ
ニル樹脂基本配合に対して添加したもの、及び比
較例として添加しなかつたものを、各々加圧ニー
ダーにて200℃で約５分間混練したのち造粒し
た。これらの成形材料を各々180℃で３分間プレ
ス成形し、厚み0.8m/mのシートを得た。このシ
ートから20m/m×50m/mの大きさのシートを２
枚づつ作成し、第１表に示した市販の付加重合型
液状シリコーンゴムを厚み１m/m、接触面積上
下各々20m/m×約25m/mになるようにしてはさ
み、105℃の恒温槽にて60分間加熱し、付加重合
型液状シリコーンゴムの硬化を行なつた。
こうして得られた試験片を室温で180度の剥離
試験を行ない接着力を比較した。結果は第１表に
示した通りで、本発明に於ける軟質塩化ビニル系
樹脂組成物は、一般の付加重合型液状シリコーン
ゴムと強固に接着一体化できることが明らかであ
る。
[Industrial Application Field] The present invention relates to a composite molded product of a vinyl chloride resin composition and an addition polymerizable silicone rubber. [Prior art] Vinyl chloride resins are made flexible by adding plasticizers or polymeric elastomers, and have excellent transparency, adhesive properties, and high-frequency processability, making them suitable for medical devices, food packaging, etc. 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. 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 limited due to its high price and low mechanical strength. 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, such as 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 ethyl acetate. Since solvents such as , toluene, etc. are used, there is concern that they may remain, and even if they are once bonded, they may peel off over time. On the other hand, according to JP-A No. 54-156083, etc., there is a method in which the surface of a vinyl chloride resin is treated with low-temperature plasma in advance, and then a cured layer of a condensation type room-temperature curing silicone rubber is formed. 58−
According to Publication No. 32773, after a hardened layer is formed in advance on the surface of a vinyl chloride resin material by plasma treatment or the like, a silicone resin layer made of dimethylpolysiloxane or dimethylpolysiloxane modified with an alkyl group is formed and modified. It is proposed to do so. Although it is clear that silicone resin can be fixed by these methods, it is difficult for plasma treatment to completely treat the inside of a tube with a small diameter or a long tube-like object to form a hardened layer. The present inventors have developed an anti-thrombotic solution directly onto the surface of a soft vinyl chloride resin molded product, which has been considered difficult in the past, without forming a hardened layer such as plasma treatment or performing any pretreatment such as plasma treatment. As a result of extensive research into silicone and vinyl chloride resins with the aim of forming a silicone adhesive layer with excellent properties, it was discovered that there was a combination of a soft vinyl chloride resin and silicone that bonded strongly. -Completed the inventions shown in No. 203699 and Japanese Patent Application No. 58-203700. [Purpose of the Invention] However, while proceeding with studies with the aim of further improving the adhesion between soft vinyl chloride resin and silicone rubber, the present inventors discovered that carbon double bonds were added to soft vinyl chloride resin. The inventors discovered that by adding a thermoplastic resin having a bond, it becomes possible to integrate the adhesive with an addition-polymerizable silicone rubber, and after conducting extensive studies, the present invention was completed. [Structure of the Invention] That is, the present invention comprises adding a thermoplastic resin having a carbon-carbon double bond to 100 parts by weight of a vinyl chloride resin.
A cured layer of addition polymerization type silicone rubber is provided on the surface of a molded article made of a soft vinyl chloride resin composition containing 0.1 to 10 parts by weight,
A soft vinyl chloride resin composition-silicone rubber composite molded article is provided. The soft vinyl chloride resin composition in the present invention includes vinyl chloride homopolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene-vinyl acetate terpolymer, Thermoplastic resins, plasticizers, etc. whose main components are vinyl chloride-based copolymers such as vinyl chloride-acrylic acid copolymers, vinyl chloride-urethane copolymers, etc., and which have double bonds between carbons, Contains stabilizers, etc. The thermoplastic resin having a carbon-carbon double bond is basically not particularly limited as long as it is a thermoplastic resin containing a vinyl group, an allyl group, etc., and its number average degree of polymerization is preferably 5 or more. is 10 or more, or its number average molecular weight is 2000 or more, preferably 5000 or more. For example, diallyl orthophthalate prepolymer, diallyl isophthalate prepolymer, polybutadiene, polypentadiene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer,
polyvinylidene chloride, etc. Note that ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinylidene chloride, etc. originally have a linear molecular structure, but depending on the polymerization conditions etc. It is known that bonds are formed or remain in molecular chains or at the ends of molecular chains. Such unsaturated double bonds, which are originally undesirable, function effectively in the present invention. The amount of thermoplastic resin containing these carbon-carbon double bonds added to vinyl chloride resin varies depending on the content of carbon-carbon double bonds, but is generally 0.1 to 10 parts by weight per 100 parts by weight of vinyl chloride resin. Parts by weight, preferably 1.0 to 5.0 parts by weight, are optimum. There are no particular restrictions on the plasticity added to the vinyl chloride resin, but phthalate esters such as dioctyl phthalate, which have little negative effect on adhesion with addition-polymerizable silicone compositions, and epoxidized soybean oil , epoxidized linseed oil, etc. are preferably used. In addition, as stabilizers that impart heat resistance and thermal stability, in addition to metal soaps such as calcium stearate, zinc stearate, barium stearate, and magnesium stearate, organometallic stabilizers of the above-mentioned metals are particularly preferred. System stabilizers, ester stabilizers such as butyl stearate, and phosphoric acid stabilizers inhibit the curing of addition-polymerized silicone rubber, and also inhibit the curing of thermoplastic resins containing carbon double bonds added to vinyl chloride resins. Since it also inhibits the effect of adding resin, they cannot be used together. In the present invention, the addition polymerization type silicone rubber includes a vinyl group-containing polysiloxane represented by the general formula (1), an organohydrogen polysiloxane represented by the general formula (2), and optionally a polysiloxane containing a vinyl group represented by the general formula (1). A composition that can be solidified into an elastic body by addition polymerizing a composition to which an inorganic material such as silica as a reinforcing agent is added using a platinum-based catalyst. Although not particularly limited, the composition is preferably hydrogen atom directly bonded to silicon atom per vinyl group in a substance
It is preferable to contain an organohydrogenpolysiloxane having two or more hydrogen atoms in one molecule in an amount sufficient to provide 0.8 to 6 hydrogen atoms. Also included in this category are those to which an epoxy compound, carboxylic acid anhydride, or the like is added as a third component to improve adhesion. [In the formula, R 1 to R 4 : Same or different 1 having 6 or less carbon atoms
Valent hydrocarbon group a: 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 b : An integer of 2 or more and 100 or less; c: 0 or a positive integer of 100 or less A soft vinyl chloride resin composition to which a bond-containing thermoplastic resin has been added is kneaded with a heating roll and then granulated, and the resulting molding material is molded by an extrusion method, a press method, an injection method, etc. Addition polymerization type liquid silicone rubber is coated on the surface of the molded product by a dipping method, spraying method, etc., and then heated in a heating furnace or the like to 40°C to 130°C, preferably 80°C to 110°C, to conduct addition polymerization. It is only necessary to cure the mold liquid silicone rubber, which achieves adhesion and integration with the molded product almost simultaneously.The manufacturing method is not particularly limited, but it can be heated at a temperature of at least 40°C or higher. It is a requirement to do so. The adhesion mechanism in the present invention is an addition reaction of organohydrogensiloxy groups in the addition polymerizable liquid silicone rubber composition to residual vinyl groups in the vinyl chloride resin or unsaturated double bonds generated by heating. It is presumed that this is basically the same as that in Japanese Patent Application No. 58-203699, which is the prior patent of the present inventors. That is, in the present invention, the adhesion is further improved by adding a thermoplastic resin containing a carbon-carbon double bond, because the addition polymerization type liquid silicone to the carbon-carbon double bond in the thermoplastic resin It is presumed that this is due to an addition reaction of organohydrogensiloxy groups in the rubber composition. However, if the thermoplastic resin containing carbon-carbon double bonds has a number average degree of polymerization of less than 5 or a number average molecular weight of
If it is less than 2000, its addition has almost no effect on adhesion, and may even reduce adhesive strength. [Effects of the Invention] The composite molded product of the soft vinyl chloride resin composition and addition polymerized silicone rubber in the present invention is strongly adhesively integrated, and has the toughness and rigidity of the soft vinyl chloride resin. However, its surface has the excellent antithrombotic properties and tissue compatibility of addition-polymerized silicone rubber, and the coated surface is extremely smooth, making it suitable for a variety of applications, especially in the medical field. It is useful in Hereinafter, the effects of the present invention will be explained with reference to Examples. Example 1 Vinyl chloride resin (700D manufactured by Toyo Soda Co., Ltd.) 100
Zinc stearate in terms of metal weight per part by weight
0.03 parts by weight of calcium stearate, 40 parts by weight of dioctyl phthalate, and 10 parts by weight of epoxidized soybean oil were added to form a basic soft vinyl chloride resin formulation (Table 1). Next, diallyl phthalate prepolymer (Daiso Tap L, manufactured by Osaka Soda Co., Ltd.) and 1,2-polybutadiene (RB-820, manufactured by Japan Synthetic Rubber Co., Ltd.) were prepared as thermoplastic resins containing carbon-carbon double bonds. , to which the amounts shown in Table 1 were added to the basic soft vinyl chloride resin formulation, and to which it was not added as a comparative example, were kneaded at 200°C for about 5 minutes in a pressure kneader. Granulated. Each of these molding materials was press-molded at 180°C for 3 minutes to obtain a sheet with a thickness of 0.8 m/m. From this sheet, make two sheets of size 20m/m x 50m/m.
One by one, the commercially available addition-polymerizable liquid silicone rubber shown in Table 1 was sandwiched with a thickness of 1 m/m and a contact area of 20 m/m (top and bottom) x approximately 25 m/m (approximately 25 m/m), and placed in a thermostatic oven at 105°C. The addition polymerization type liquid silicone rubber was cured by heating for 60 minutes. The thus obtained test pieces were subjected to a 180 degree peel test at room temperature and their adhesive strengths were compared. The results are shown in Table 1, and it is clear that the soft vinyl chloride resin composition of the present invention can be firmly bonded and integrated with a general addition polymerization type liquid silicone rubber.
【表】【table】
【表】
実施例 ２
塩化ビニル樹脂（住友化学工業（株）製SX―
DH）100重量部に対し、金属重量換算でステアリ
ン酸亜鉛、及びステアリン酸バリウムを各々0.03
重量部、ジオクチルフタレート45重量部、エポキ
シ化大豆油７重量部を添加したものを軟質塩化ビ
ニル樹脂基本配合（第２表）とした。
次に炭素間二重結合を含有する熱可塑性樹脂と
して、ジアリルフタレートプレポリマー（住友化
学工業（株）製DAPON）を、又、比較例として
ジアリルフタレートモノマー（大阪曹達（株）製
ダイソーダツプモノマー）を各々用意し、第２表
に示した量だけ上記軟質塩化ビニル樹脂基本配合
に対して添加したもの、及び添加しなかつたもの
について、各々180℃で約４分間加圧ニーダーに
て混練したのち造粒した。これらの成形材料を
各々190℃で約５分間プレス成形し厚み0.5m/m
のシートを得た。このシートから20m/m×50m/
ｍの大きさのシートを２枚づつ作成し、第２表に
示した市販の付加重合型液状シリコーンゴムを厚
み１m/m、接触面積上下各々20m/m×約25m/
ｍになるようにしてはさみ、110℃の恒温槽にて
90分間加熱し付加重合型液状シリコーンゴムの硬
化を行なつた。
こうして得られた試験片、及び各々を120℃、
60分間オートクレーブ処理した試験片について、
180℃剥離試験を行なつた。結果は第２表に示し
た通りで、ジアリルフタレートプレポリマーを添
加した本発明に於ける軟質塩化ビニル系樹脂組成
物は、付加重合型シリコーンゴムと強固に接着一
体化されており、オートクレーブ処理に対しても
優れた耐久性のあることが判る。しかし、ジアリ
ルフタレートモノマーではその添加効果が全くな
く、その添加量が多い場合には逆に接着力を低下
させることが判る。[Table] Example 2 Vinyl chloride resin (SX manufactured by Sumitomo Chemical Co., Ltd.)
DH) 0.03 each of zinc stearate and barium stearate in terms of metal weight per 100 parts by weight
45 parts by weight of dioctyl phthalate and 7 parts by weight of epoxidized soybean oil were added to form a basic soft vinyl chloride resin formulation (Table 2). Next, diallyl phthalate prepolymer (DAPON, manufactured by Sumitomo Chemical Industries, Ltd.) was used as a thermoplastic resin containing carbon-carbon double bonds, and diallyl phthalate monomer (Daiso DUP monomer, manufactured by Osaka Soda Co., Ltd.) was used as a comparative example. ) were prepared and kneaded in a pressure kneader for about 4 minutes at 180°C with and without addition to the basic soft vinyl chloride resin formulation in the amounts shown in Table 2. It was later granulated. Each of these molding materials was press-molded at 190℃ for about 5 minutes to a thickness of 0.5m/m.
I got a sheet of 20m/m×50m/from this sheet
Two sheets of size m were prepared, and the commercially available addition-polymerization type liquid silicone rubber shown in Table 2 was prepared with a thickness of 1 m/m and a contact area of 20 m/m on the upper and lower sides x approximately 25 m/m.
Place the scissors in a 110°C thermostatic oven.
The addition polymerization type liquid silicone rubber was cured by heating for 90 minutes. The test pieces thus obtained and each were heated at 120°C.
For specimens autoclaved for 60 minutes,
A 180°C peel test was conducted. The results are shown in Table 2, and the soft vinyl chloride resin composition of the present invention containing the diallyl phthalate prepolymer is strongly bonded and integrated with the addition-polymerized silicone rubber, and is resistant to autoclave treatment. It can be seen that it has excellent durability. However, it can be seen that the addition of diallyl phthalate monomer has no effect at all, and that when it is added in a large amount, it actually reduces the adhesive strength.
【表】【table】
Claims (1)
二重結合を有する熱可塑性樹脂を0.1乃至10重量
部含有する軟質塩化ビニル系樹脂組成物よりなる
成形品の表面に、付加重合型シリコーンゴムの硬
化層を設けることを特長とする、軟質塩化ビニル
系樹脂組成物―シリコーンゴム複合成形物。 ２ 炭素間二重結合を有する熱可塑性樹脂が、数
平均重合度５以上又は数平均分子量2000以上であ
ることを特長とする、特許請求の範囲第１項記載
の軟質塩化ビニル系樹脂組成物―シリコーンゴム
複合成形物。 ３ 炭素間二重結合を有する基がビニル基又はア
リル基であることを特長とする、特許請求の範囲
第１項及び第２項記載の軟質塩化ビニル系樹脂―
シリコーンゴム複合成形物。 ４ 炭素間二重結合を有する熱可塑性樹脂がジア
リルフタレートプレポリマーである、特許請求の
範囲第１項記載の軟質塩化ビニル系樹脂組成物―
シリコーンゴム複合成形物。 ５ 炭素間二重結合を有する熱可塑性樹脂が、ポ
リブタジエン、ポリペンタジエン、エチレン―酢
酸ビニル共重合体、エチレン―ビニルアルコール
共重合体、又はポリ塩化ビニリデンであることを
特長とする、特許請求の範囲第１項記載の軟質塩
化ビニル系樹脂組成物―シリコーンゴム複合成形
物。 ６ 軟質塩化ビニル系樹脂組成物に於いて使用さ
れ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１種又は
２種以上であることを特長とする、特許請求の範
囲第１項記載の軟質塩化ビニル系樹脂組成物―シ
リコーンゴム複合成形物。 ７ 付加重合型シリコーンゴムが、その組成物中
のビニル基一個あたり、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することを特長とする、特
許請求の範囲第１項記載の軟質塩化ビニル系樹脂
組成物―シリコーンゴム複合成形物。 ８ 軟質塩化ビニル系樹脂組成物よりなる成形品
の表面に付加重合型シリコーンゴムの硬化層を設
ける際に、少くとも40℃以上の温度に加熱するこ
とを特長とする、軟質塩化ビニル系樹脂組成物―
シリコーンゴム複合成形物の製造方法。[Scope of Claims] 1. On the surface of a molded article made of a soft vinyl chloride resin composition containing 0.1 to 10 parts by weight of a thermoplastic resin having a carbon-carbon double bond per 100 parts by weight of the vinyl chloride resin, A soft vinyl chloride resin composition-silicone rubber composite molded product, which is characterized by being provided with a cured layer of addition-polymerizable silicone rubber. 2. The soft vinyl chloride resin composition according to claim 1, wherein the thermoplastic resin having a carbon-carbon double bond has a number average degree of polymerization of 5 or more or a number average molecular weight of 2000 or more. Silicone rubber composite molded product. 3. A soft vinyl chloride resin according to claims 1 and 2, characterized in that the group having a carbon-carbon double bond is a vinyl group or an allyl group.
Silicone rubber composite molded product. 4. The soft vinyl chloride resin composition according to claim 1, wherein the thermoplastic resin having a carbon-carbon double bond is a diallyl phthalate prepolymer.
Silicone rubber composite molded product. 5. Claims characterized in that the thermoplastic resin having carbon-carbon double bonds is polybutadiene, polypentadiene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, or polyvinylidene chloride 1. A soft vinyl chloride resin composition-silicone rubber composite molded article according to item 1. 6 Claims characterized in that the metal in the stabilizer used in the soft vinyl chloride resin composition is one or more of calcium, zinc, barium, magnesium, and aluminum. 1. A soft vinyl chloride resin composition-silicone rubber composite molded article according to item 1. 7 Addition-polymerizable silicone rubber containing 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 in the composition. The soft vinyl chloride resin composition-silicone rubber composite molded article according to claim 1, characterized by containing hydrogen polysiloxane. 8. A soft vinyl chloride resin composition characterized in that it is heated to a temperature of at least 40°C or higher when providing a cured layer of addition polymerizable silicone rubber on the surface of a molded article made of the soft vinyl chloride resin composition. thing-
A method for producing a silicone rubber composite molded product.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5625484A JPS60201947A (en) | 1984-03-26 | 1984-03-26 | Soft vinyl chloride group resin composition-silicone rubber compositie molded part and manufacture thereof |
| 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 |
|---|---|---|---|
| JP5625484A JPS60201947A (en) | 1984-03-26 | 1984-03-26 | Soft vinyl chloride group resin composition-silicone rubber compositie molded part and manufacture thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60201947A JPS60201947A (en) | 1985-10-12 |
| JPS6249862B2 true JPS6249862B2 (en) | 1987-10-21 |
Family
ID=13021943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5625484A Granted JPS60201947A (en) | 1983-11-01 | 1984-03-26 | Soft vinyl chloride group resin composition-silicone rubber compositie molded part and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60201947A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2736667B2 (en) * | 1988-10-21 | 1998-04-02 | セイコーエプソン株式会社 | Electronic wristwatch with generator |
-
1984
- 1984-03-26 JP JP5625484A patent/JPS60201947A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2736667B2 (en) * | 1988-10-21 | 1998-04-02 | セイコーエプソン株式会社 | Electronic wristwatch with generator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60201947A (en) | 1985-10-12 |
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