JPH04159337A - Polymer material with modified surface and its production - Google Patents
Polymer material with modified surface and its productionInfo
- Publication number
- JPH04159337A JPH04159337A JP2283533A JP28353390A JPH04159337A JP H04159337 A JPH04159337 A JP H04159337A JP 2283533 A JP2283533 A JP 2283533A JP 28353390 A JP28353390 A JP 28353390A JP H04159337 A JPH04159337 A JP H04159337A
- Authority
- JP
- Japan
- Prior art keywords
- plasma
- polymer
- initiated graft
- graft polymerization
- modified
- 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.)
- Pending
Links
- 239000002861 polymer material Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 238000010559 graft polymerization reaction Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 208000007536 Thrombosis Diseases 0.000 abstract description 2
- 208000031737 Tissue Adhesions Diseases 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 208000026062 Tissue disease Diseases 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000001627 detrimental effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 21
- -1 polyethylene Polymers 0.000 description 21
- 239000008280 blood Substances 0.000 description 7
- 210000004369 blood Anatomy 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000002783 friction material Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical compound C=CN1CCCCC1 LEWNYOKWUAYXPI-UHFFFAOYSA-N 0.000 description 1
- NWHSSMRWECHZEP-UHFFFAOYSA-N 1-ethenylpyrazole Chemical compound C=CN1C=CC=N1 NWHSSMRWECHZEP-UHFFFAOYSA-N 0.000 description 1
- CWWYEELVMRNKHZ-UHFFFAOYSA-N 2,3-dimethylbut-2-enamide Chemical compound CC(C)=C(C)C(N)=O CWWYEELVMRNKHZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IJSCYIZQNHIKIU-UHFFFAOYSA-N 2-ethenyl-1,3-dihydropyrazole Chemical compound C=CN1CC=CN1 IJSCYIZQNHIKIU-UHFFFAOYSA-N 0.000 description 1
- YRPYTFXEHXXYQW-UHFFFAOYSA-N 2-ethenyl-1h-benzimidazole Chemical compound C1=CC=C2NC(C=C)=NC2=C1 YRPYTFXEHXXYQW-UHFFFAOYSA-N 0.000 description 1
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical compound C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- SDNHWPVAYKOIGU-UHFFFAOYSA-N 3-ethyl-2-methylpent-2-enamide Chemical compound CCC(CC)=C(C)C(N)=O SDNHWPVAYKOIGU-UHFFFAOYSA-N 0.000 description 1
- UVRCNEIYXSRHNT-UHFFFAOYSA-N 3-ethylpent-2-enamide Chemical compound CCC(CC)=CC(N)=O UVRCNEIYXSRHNT-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- MCXLQFOCWZMFHV-UHFFFAOYSA-N 4-ethenyl-2h-triazole Chemical compound C=CC1=CNN=N1 MCXLQFOCWZMFHV-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 208000005422 Foreign-Body reaction Diseases 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000000451 tissue damage Effects 0.000 description 1
- 231100000827 tissue damage Toxicity 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、表面が改質された高分子材料およびその製造
方法に関するものである。詳しく述べると、プラズマ開
始グラフト重合が容易に可能な重−合体の存在により基
財高分子表面に新たな官能基が導入された高分子材料お
よびその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a surface-modified polymeric material and a method for producing the same. More specifically, the present invention relates to a polymer material in which a new functional group is introduced onto the surface of a base polymer due to the presence of a polymer that can be easily subjected to plasma-initiated graft polymerization, and a method for producing the same.
（従来の技術）
医療用具としては、例えば、血液バッグ、輸液バッグ、
血液チューブ、カテーテル、バルーンカテーテル等があ
り、これらは、通常熱可密性樹脂等の高分子材料で作製
されている。(Prior art) Examples of medical devices include blood bags, infusion bags,
There are blood tubes, catheters, balloon catheters, etc., which are usually made of polymeric materials such as thermosealable resins.
一般に、このような高分子材料としては、ポリエチレン
、ポリエチレンテレフタレート、ポリブチレンテレフタ
レート等があるが、これらの高分子材料は優れた機械的
性質を有しているにもかかわらず、生体適合性、特に血
液適合性が不充分であるために、満足すべき結果は得ら
れていない。In general, such polymeric materials include polyethylene, polyethylene terephthalate, polybutylene terephthalate, etc. Although these polymeric materials have excellent mechanical properties, they have poor biocompatibility, especially Satisfactory results have not been achieved due to insufficient blood compatibility.
このような不具合を解消するために高分子材料の表面を
改質することは知られている。例えば、疎水性高分子材
料の表面に三重項増感剤または光により遊離ラジカルを
生成させて表面を重合性単量体でグラフト重合する改質
法（特開昭５２−１５２．９７２号）や重合体の表面に
シリコン含有重合体の層をプラズマ蒸着させる方法（特
開平１−２７０．８７２号）等が提案されている。It is known to modify the surface of polymeric materials in order to eliminate such problems. For example, a modification method in which free radicals are generated on the surface of a hydrophobic polymer material using a triplet sensitizer or light, and the surface is graft-polymerized with a polymerizable monomer (Japanese Patent Application Laid-Open No. 152-152-972); A method has been proposed in which a layer of a silicon-containing polymer is plasma-deposited on the surface of the polymer (Japanese Patent Laid-Open No. 1-270.872).
しかしながら、このような高分子材料の表面を改質して
表面に生体適合性層を設けようとする場合、ポリプロピ
レンのように分子構造中に第三級炭素を有する高分子材
料と比較して、ポリエチレン、ポリエチレンテレフタレ
ートのような高分子材料は、その分子構造中に第三級炭
素原子を有していないためにプラズマに対して比較的安
定な高分子化合物であり、このため、プラズマ開始グラ
フト重合法により表面改質を行なおうとすれば、高出力
でプラズマを照射させるか、もしくはプラズマ照射によ
るラジカルの生成ではなく中性子線、電子線、ガンマ線
等のエネルギーの高い放射線によりラジカルを生成させ
ざるを得ない。However, when attempting to modify the surface of such polymeric materials to provide a biocompatible layer on the surface, compared to polymeric materials that have tertiary carbon in their molecular structure, such as polypropylene, Polymeric materials such as polyethylene and polyethylene terephthalate are polymeric compounds that are relatively stable to plasma because they do not have tertiary carbon atoms in their molecular structure, and therefore are highly susceptible to plasma-initiated grafting. If you want to legally modify the surface, you will have to irradiate it with high-power plasma, or use high-energy radiation such as neutron beams, electron beams, and gamma rays to generate radicals instead of generating radicals through plasma irradiation. I don't get it.
また、高分子材料の表面の生体適合性を高めるために、
米国特許第４，１００．３０９号、特開昭５９−８１，
３４１号、特公平１−５５，０２３号等にみられるよう
に、低摩擦材料を基材として用いたり親水性重合体を被
覆したりして潤滑性が付与されている。In addition, to increase the biocompatibility of the surface of polymeric materials,
U.S. Patent No. 4,100.309, JP 59-81,
As seen in Japanese Patent Publication No. 341 and Japanese Patent Publication No. 1-55,023, lubricity is imparted by using a low-friction material as a base material or coating it with a hydrophilic polymer.
（発明が解決しようとする課題）
しかしながら、放射線を用いる方法は、基材に与える損
傷が大きく、特に電子線、ガンマ線等の強い放射線で処
理を行なうと、基材内部にまでラジカルが生成され、基
材の有している物性を大きく変化させてしまう場合が多
い。また、高出力プラズマの照射もやはり基材の物性を
大きく変化させてしまう場合が多い。このように、プラ
ズマ開始重合においては基材の種類に制限がみられ、第
三級炭素を有しない高分子材料へのプラズマ開始重合法
による表面改質の効果はあまり期待できないものであっ
た。(Problems to be Solved by the Invention) However, methods using radiation cause significant damage to the base material, and in particular, when processing with strong radiation such as electron beams and gamma rays, radicals are generated even inside the base material. In many cases, the physical properties of the base material are significantly changed. Furthermore, irradiation with high-power plasma also often significantly changes the physical properties of the base material. As described above, plasma-initiated polymerization is limited in the types of substrates that can be used, and the surface modification effect of plasma-initiated polymerization on polymeric materials that do not contain tertiary carbon cannot be expected to be very effective.
一方、従来方法による低摩擦材料の使用や親水性重合体
の被覆は、永続的な潤滑性が期待できないばかりでなく
、潤滑性を付与する際に特別な官能基が必要であり、基
材の種類にも制限があった。On the other hand, conventional methods of using low-friction materials or coating with hydrophilic polymers not only cannot be expected to provide permanent lubricity, but also require special functional groups to provide lubricity, and There were also restrictions on types.
したがって、本発明の目的は、基材である高分子材料の
特性や物性を損うことなく、いかなる高−分子材料にお
いてもプラズマ開始グラフト重合法を可能にした表面が
改質された高分子材料およびその製造方法を提供するこ
とにある。Therefore, an object of the present invention is to create a surface-modified polymer material that enables plasma-initiated graft polymerization to be applied to any polymer material without impairing the properties or physical properties of the polymer material that is the base material. and its manufacturing method.
（課題を解決するための手段）
上記目的は、プラズマ開始グラフト重合が可能な重合体
を予め高分子材料の表面に存在させ、プラズマを照射後
または照射時に、重合性単量体を供給することにより得
られる表面が改質された高分子材料により達成される。(Means for solving the problem) The above purpose is to pre-exist a polymer capable of plasma-initiated graft polymerization on the surface of a polymeric material, and supply a polymerizable monomer after or during plasma irradiation. This is achieved by using a surface-modified polymeric material.
本発明はまた、プラズマ開始グラフト重合が可能な重合
体が第三級炭素原子を有するものである表面が改質され
た高分子材料である。The present invention is also a surface-modified polymeric material in which the plasma-initiated graft polymerizable polymer has tertiary carbon atoms.
上記目的は、プラズマ開始グラフト重合が可能な重合体
を予め高分子材料の表面に存在させ、該表面にプラズマ
を照射したのちまたは照射時に、ラジカル重合性単量体
を供給することを特徴とする表面が改質された高分子材
料の製造方法によっても達成される。The above object is characterized in that a polymer capable of plasma-initiated graft polymerization is preliminarily present on the surface of a polymeric material, and a radically polymerizable monomer is supplied after or during irradiation of the surface with plasma. This can also be achieved by a method for producing surface-modified polymeric materials.
本発明はまた、プラズマ開始グラフト重合が可能な重合
体が第三級炭素原子を有するものである表面が改質され
た高分子材料の製造方法である。The present invention is also a method for producing a surface-modified polymeric material in which the plasma-initiated graft polymerizable polymer has tertiary carbon atoms.
上記目的はさらに、プラズマ開始グラフト重合が可能な
重合体を予め高分子材料の表面に存在させ、プラズマを
照射後または照射時に、ラジカル重合性単量体を供給す
ることにより表面が改質された高分子材料の成形物より
なる医療用具によっても達成される。The above purpose is further achieved by pre-existing a polymer capable of plasma-initiated graft polymerization on the surface of a polymeric material, and supplying a radically polymerizable monomer after or during plasma irradiation to modify the surface. This can also be achieved by medical devices made of molded polymeric materials.
本発明はまた、カテールまたはバルーン力テーチルであ
る医療用具である。The present invention is also a medical device that is a catheter or balloon catheter.
（作用）
本発明において表面を改質される高分子材料は、いかな
るものであってもよく、それが１種類もしくはそれ以上
であってもさしつかえない。例えば、ポリエチレン、ポ
リエチレンテレフタレート、ポリブチレンテレフタレー
ト、塩化ビニル樹脂、ポリカーボネート、ポリアミド、
ポリアセタール、フッ素樹脂等のように、その分子構造
中に第三級炭素を有しないものかに対し本発明によるプ
ラズマ処理の効果が顕著である。また、該高分子材料の
形状に関しても前記したものであれば、単独形状または
複合形状のいずれであってもさしつかえない。(Function) In the present invention, the surface of the polymeric material to be modified may be of any kind, and there may be no problem even if the number of polymeric materials is one or more. For example, polyethylene, polyethylene terephthalate, polybutylene terephthalate, vinyl chloride resin, polycarbonate, polyamide,
The effect of the plasma treatment according to the present invention is remarkable for materials that do not have tertiary carbon in their molecular structure, such as polyacetal and fluororesin. Furthermore, the shape of the polymeric material may be either a single shape or a composite shape as long as it is as described above.
プラズマ開始重合が容易な重合体としては、プラズマ開
始重合が容易でない高分子材料、例えば第三級炭素原子
を有しない高分子材料に対する接着性が高く、かつ第三
級炭素原子を有するものが好ましい。このような重合体
としては、例えば、ポリプロピレン、エチレン−プロピ
レン共重合体ポリスチレン、スチレン−マレイン酸共重
合体、スチレン−アクリロニトリル共重合体、ポリアク
リロニトリル、ポリアクリル酸、ポリアクリル酸塩、ア
ルキルアクリレートの単独重合体および共重合体、ポリ
酢酸ビニル、エチレン−酢酸ビニル共重合体、ポリ（１
，２−ブタジェン）等がある。As a polymer that can be easily subjected to plasma-initiated polymerization, it is preferable to use a polymer that has high adhesion to a polymer material that is not easily subjected to plasma-initiated polymerization, such as a polymer material that does not have a tertiary carbon atom, and that also has a tertiary carbon atom. . Examples of such polymers include polypropylene, ethylene-propylene copolymer polystyrene, styrene-maleic acid copolymer, styrene-acrylonitrile copolymer, polyacrylonitrile, polyacrylic acid, polyacrylate, and alkyl acrylate. Homopolymers and copolymers, polyvinyl acetate, ethylene-vinyl acetate copolymers, poly(1
, 2-butadiene), etc.
また、分子構造中に第三級炭素原子を有するポリエステ
ルもある。このようなポリエステルとしては、テレフタ
ル酸、イソフタル酸、コハク酸、アジピン酸、セバシン
酸、アイコサンニ酸、ナフタレンジカルボン酸、トリメ
リット酸等の酸成分と第三級炭素を有するグリコール、
例えば、プロピレングリコール、ネオペンチルグリコー
ル、トリメチロールプロパン等を必須の成分とし、必要
によりエチレングリコール、ジエチレングリコール、グ
リセリン等を含むグリコール成分との縮合物がある。ま
た、用いられる共縮合体は、１種類以上であればよく、
それが混合体もしくはブロック重合体、ランダム重合体
であってもよい。There are also polyesters that have tertiary carbon atoms in their molecular structure. Such polyesters include acid components such as terephthalic acid, isophthalic acid, succinic acid, adipic acid, sebacic acid, icosanniic acid, naphthalene dicarboxylic acid, and trimellitic acid, and glycols having a tertiary carbon;
For example, there are condensates containing propylene glycol, neopentyl glycol, trimethylolpropane, etc. as essential components, and optionally with glycol components containing ethylene glycol, diethylene glycol, glycerin, etc. Moreover, the cocondensate used may be one or more types,
It may be a mixture, a block polymer, or a random polymer.
これらの重合体は、その単独またはそれらの混合物、あ
るいは多層構造を有していてもさしつかえない。また、
保持される重合体は、直接プラズマ開始重合が可能な高
分子材料である必要はなく、ある化学物質を基材表面に
保持後、物理的処理ないしは化学的処理によりプラズマ
開始グラフト重合が容易な高分子材料に変換させたのち
、プラズマ開始グラフト重合を行なってもよい。These polymers may be used singly or as a mixture thereof, or may have a multilayer structure. Also,
The polymer to be retained does not need to be a polymer material that can be directly subjected to plasma-initiated polymerization, but rather a polymer material that can be easily subjected to plasma-initiated graft polymerization through physical or chemical treatment after retaining a certain chemical substance on the substrate surface. After conversion into a molecular material, plasma-initiated graft polymerization may be performed.
本発明は、高分子材料表面を構成する少なくとも一部の
表面にプラズマ開始グラフト重合が可能な重合体を予め
存在させ、プラズマを照射後または照射時に、重合性単
量体を供給することにより該単量体をグラフト重合させ
て前記高分子材料の表面を改質し、該表面に生体適合性
を付与するものである。In the present invention, a polymer capable of plasma-initiated graft polymerization is pre-existing on at least a part of the surface constituting the surface of a polymer material, and a polymerizable monomer is supplied after or during plasma irradiation. The surface of the polymeric material is modified by graft polymerization of monomers, thereby imparting biocompatibility to the surface.
前記プラズマ開始グラフト重合が容易な重合体の高分子
材料表面への存在量は、０．０１〜５００ｇ／ｍ２、好
ましくは１〜１００ ｇ／ｍ２である。なお、該プラズ
マ開始グラフト重合が可能な重合体は、必ずしも高分子
材料表面に直接塗布する必要はなく、該材料の付加価値
を高めるために他の化学物質を基材表面に存在させてか
ら該脱水素能力発現物質を塗布し、プラズマ開始グラフ
ト重合を行なってもよい。The amount of the polymer that can be easily subjected to plasma-initiated graft polymerization on the surface of the polymer material is 0.01 to 500 g/m2, preferably 1 to 100 g/m2. It should be noted that the polymer capable of plasma-initiated graft polymerization does not necessarily have to be applied directly to the surface of the polymeric material; other chemicals may be present on the surface of the base material in order to increase the added value of the material. A substance exhibiting dehydrogenation ability may be applied and plasma-initiated graft polymerization may be performed.
本発明で用いられるラジカル重合性単量体としては、ア
クリル酸、メタクリル酸、メチル（メタ）アクリレート
、エチル（メタ）アクリレート、イソプロピル（メタ）
アクリレート、ブチル（メタ）アクリレート等のアルキ
ルアクリレートまたはアルキルメタクリレート、シクロ
ヘキシル（メタ）アクリレート等のシクロアルキル（メ
タ）アクリレート、２−ヒドロキシエチル（メタ）アク
リレート、２−ヒドロキシプロピル（メタ）アクリレー
ト、３−ヒドロキシプロピル（メタ）アクリレート等の
ヒドロキシアルキル（メタ）アクリレート、メトキシエ
チル（メタ）アクリレート、エトキシエチル（メタ）ア
クリレート等のアルコキシアルキル（メタ）アクリレー
ト、メチルアミノエチル（メタ）アクリレート、エチル
アミノエチル（メタ）アクリレート、ジメチルアミノエ
チル（メタ）アクリレート、ジェチルアミノエチル（メ
タ）アクリレート、ジメチルアミノプロピル（メタ）ア
クリレート等のアルキルアミノアルキル（メタ）アクリ
レート、アクリロニトリル、メタクリロニトリル、ジア
セトンアクリルアミド、ジアセトンメタクリルアミド、
アクリルアミド、メタクリルアミド、ジメチルアクリル
アミド、ジエチルアクリルアミド、ジメチルメタクリル
アミド、ジエチルメタクリルアミド等のジアルキル（メ
タ）クリルアミド、ビニルシラン、ビニルピロリドン、
１−ビニルピラゾール、ビニルピラゾリン、ビニルトリ
アゾール、ビニルベンズイミダゾール、ビニルピリジン
、ビニルピペリジン、ビニルキノリン等がある。The radically polymerizable monomers used in the present invention include acrylic acid, methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate.
acrylate, alkyl acrylate or alkyl methacrylate such as butyl (meth)acrylate, cycloalkyl (meth)acrylate such as cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxy Hydroxyalkyl (meth)acrylate such as propyl (meth)acrylate, alkoxyalkyl (meth)acrylate such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, methylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate Acrylate, alkylaminoalkyl (meth)acrylate such as dimethylaminoethyl (meth)acrylate, dietylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, acrylonitrile, methacrylonitrile, diacetone acrylamide, diacetone methacrylamide ,
Dialkyl(meth)acrylamides such as acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, dimethylmethacrylamide, diethylmethacrylamide, vinylsilane, vinylpyrrolidone,
Examples include 1-vinylpyrazole, vinylpyrazoline, vinyltriazole, vinylbenzimidazole, vinylpyridine, vinylpiperidine, and vinylquinoline.
これらの単量体のグラフト量は、高分子材料の単位面積
当り０． ５〜５００ｇ／ｍ２、好ましくは１〜１００
ｇ／ｍ２である。The amount of grafting of these monomers is 0.00% per unit area of the polymer material. 5-500g/m2, preferably 1-100
g/m2.
プラズマ開始グラフト重合は、アルゴン、窒素、空気、
水素等の雰囲気中で、１０−３〜１００ｔ。Plasma-initiated graft polymerization can be performed using argon, nitrogen, air,
10-3 to 100 t in an atmosphere of hydrogen or the like.
ｒｒ、好ましくは１０’ 〜１０ｔｏｒｒの圧力下にプ
ラズマを０．１秒〜１０分間、好ましくは１〜６０秒間
照射し、その時同時にあるいはその後、前記ラジカル重
合性単量体をガス状または液状で供給し、２〜４０’Ｃ
１好ましくは１０〜３０℃の温度で０．５〜６０分間、
好ましくは１〜３０分間反応に供することにより行なわ
れる。rr, preferably 10' to 10 torr, for 0.1 seconds to 10 minutes, preferably 1 to 60 seconds, and at the same time or thereafter, the radically polymerizable monomer is supplied in gas or liquid form. 2~40'C
1 Preferably at a temperature of 10 to 30°C for 0.5 to 60 minutes,
The reaction is preferably carried out for 1 to 30 minutes.
このようにして、使用するラジカル重合性単量体の種類
を選ぶこと−により高分子材料の表面が改−質され、特
に単量体として親水性単量体を選ぶことにより生体適合
性、特に血液適合性の優れた表面を得ることかできる。In this way, by selecting the type of radically polymerizable monomer used, the surface of the polymeric material can be modified, and by selecting a hydrophilic monomer as the monomer, biocompatibility can be improved, especially by selecting a hydrophilic monomer. A surface with excellent blood compatibility can be obtained.
したがって、このようにして改質された高分子材料は、
血液バッグ、輸液バッグ、血液チューブ、カテーテル、
バルーンカテーテル、ガイデイングカテーテル等の医療
用具、特に単量体として親水性単量を使用したものは、
摩擦抵抗が小さいので、カテーテル、バルーンカテール
、ガイデイングカテーテル用の材料としても極めて優れ
ている。なお、本発明で使用される高分子基材の材質に
関しては、いかなる物であってもよく、それが１種類も
しくはそれ以−［であってもさしつかえない。さらに基
材の形状に関しても、いかなる単独形状および複合形状
であってもさしつかえない。Therefore, the polymer material modified in this way is
Blood bags, infusion bags, blood tubes, catheters,
Medical devices such as balloon catheters and guiding catheters, especially those using hydrophilic monomers,
Because of its low frictional resistance, it is also an excellent material for catheters, balloon catheters, and guiding catheters. Note that the polymer base material used in the present invention may be of any material, and may be one or more types. Furthermore, the shape of the base material may be any single shape or composite shape.
（実施例） 説明する。(Example) explain.
実施例１〜４
ポリエチレンテレフタレートフィルム（１２μｍ厚’）
（Ｈ１００ダイアホイル株式会社製）：こ、熱可塑性飽
和共重合ポリエステル（商品名エリ−チル、ユニチカ株
式会社製）の２重量％トルエン／メチルエチルケトン（
重量比８／２）溶液（こ５分間浸漬し、乾燥後、低温プ
ラズマ（アルゴン雰囲気、Ｑ、１ｔｏｒｒ）を１０秒間
照射し、２８８にの温度で、第１表に示す単量体を用０
て１０分間表面グラフト重合を行なった。該フィルムを
グラフト鎖に対する良溶媒で１日間洗浄を行な０、試料
を得た。さらに生体適合性の指標ととして血小板の粘着
試験を行なった。入断鮮血と該フィルム（１ｃｍＸ１ｃ
ｍ）を５分間接触させたのち、グルタルアルデヒドを用
いて固定化し、脱水後走査型電子顕微鏡にて３００倍の
倍率で血小板の粘着類を測定した。その結果を第１表に
示す。Examples 1-4 Polyethylene terephthalate film (12 μm thick)
(manufactured by H100 Diafoil Co., Ltd.): 2% by weight toluene/methyl ethyl ketone (produced by Unitika Co., Ltd.) of thermoplastic saturated copolyester polyester (trade name: Erythil, manufactured by Unitika Co., Ltd.)
Weight ratio 8/2) solution (immersed in this for 5 minutes, dried, then irradiated with low temperature plasma (argon atmosphere, Q, 1 torr) for 10 seconds at a temperature of 288°C, using the monomers shown in Table 1.
Surface graft polymerization was carried out for 10 minutes. The film was washed for one day with a good solvent for graft chains to obtain a sample. Furthermore, a platelet adhesion test was conducted as an indicator of biocompatibility. Cut fresh blood and the film (1cm x 1c
After contacting with m) for 5 minutes, the platelets were fixed using glutaraldehyde, and after dehydration, platelet adhesion was measured using a scanning electron microscope at 300x magnification. The results are shown in Table 1.
比較例１〜４
実施例１〜４と同様なフィルムに対して、エリ−チルを
保持さなかった以外は同様な方法でプラズマ開始重合を
行なった。その結果を第１表に示す。Comparative Examples 1 to 4 Plasma-initiated polymerization was performed on the same films as in Examples 1 to 4 in the same manner except that elythyl was not retained. The results are shown in Table 1.
（発明の効果）
以上述べたように、本発明は、プラズマ開始グラフト重
合が可能な重合体を予め高分子材料の表面に存在させ、
プラズマを照射後または照射時に、ラジカル重合性単量
体を供給することにより得られる表面が改質された高分
子材料およびその製造方法であるから、高分子材料の材
質に制限がなくあらゆる高分子材料に対してプラズマ開
始重合が可能となるだけでなく、特に第三級炭素原子を
有しない材料に対してはその効果が著しい。(Effects of the Invention) As described above, the present invention allows a polymer capable of plasma-initiated graft polymerization to be present on the surface of a polymeric material in advance,
Since this is a surface-modified polymer material obtained by supplying a radically polymerizable monomer after or during plasma irradiation, and its manufacturing method, there are no restrictions on the material of the polymer material, and it can be used with any polymer. Not only does plasma-initiated polymerization of materials become possible, but the effect is particularly remarkable for materials that do not have tertiary carbon atoms.
また、ラジカル重合性単量体を適宜選択することにより
生体適合性を有する表面を形成することができるので、
高分子材料において異物反応組織接着、組織障害、血栓
性等のごとき生体に対して悪影響を及ぼさず、しかも物
理的強度に関して申分のない材料が得られる。したがっ
て、医療用具、特にカテーテル、バルーンカテーテル等
に対して好適な材料が得られる。In addition, by appropriately selecting radically polymerizable monomers, a biocompatible surface can be formed.
A polymeric material can be obtained that does not have any adverse effects on living organisms such as foreign body reaction, tissue adhesion, tissue damage, thrombosis, etc., and has perfect physical strength. Therefore, a material suitable for medical devices, particularly catheters, balloon catheters, etc. is obtained.
Claims (6)
高分子材料の表面に存在させ、プラズマを照射後または
照射時に、ラジカル重合性単量体を供給することにより
得られる表面が改質された高分子材料。(1) A polymer capable of plasma-initiated graft polymerization is pre-existing on the surface of a polymeric material, and the surface obtained by supplying a radically polymerizable monomer after or during plasma irradiation is modified. Polymer materials.
級炭素原子を有するものである請求項１に記載の表面が
改質された高分子材料。(2) The surface-modified polymeric material according to claim 1, wherein the polymer capable of plasma-initiated graft polymerization has a tertiary carbon atom.
分子材料の表面に存在させ、該表面にプラズマを照射し
たのちまたは照射時に、ラジカル重合性単量体を供給す
ることを特徴とする表面が改質された高分子材料の製造
方法。(3) A surface characterized in that a polymer capable of plasma-initiated graft polymerization is preliminarily present on the surface of a polymeric material, and a radically polymerizable monomer is supplied after or during irradiation with plasma to the surface. A method for producing a modified polymeric material.
級炭素原子を有するものである請求項３項に記載の表面
が改質された高分子材料の製造方法。(4) The method for producing a surface-modified polymer material according to claim 3, wherein the polymer capable of plasma-initiated graft polymerization has a tertiary carbon atom.
高分子材料の表面に存在させ、プラズマを照射後または
照射時に、ラジカル重合性単量体を供給することにより
表面が改質された高分子材料の成形物よりなる医療用具
。(5) A polymer whose surface has been modified by pre-existing a polymer capable of plasma-initiated graft polymerization on the surface of a polymer material and supplying a radically polymerizable monomer after or during plasma irradiation. Medical devices made of molded materials.
５に記載の医療用具。(6) The medical device according to claim 5, which is a catheter or a balloon catheter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2283533A JPH04159337A (en) | 1990-10-23 | 1990-10-23 | Polymer material with modified surface and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2283533A JPH04159337A (en) | 1990-10-23 | 1990-10-23 | Polymer material with modified surface and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04159337A true JPH04159337A (en) | 1992-06-02 |
Family
ID=17666765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2283533A Pending JPH04159337A (en) | 1990-10-23 | 1990-10-23 | Polymer material with modified surface and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04159337A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0857038A (en) * | 1993-06-07 | 1996-03-05 | Agency Of Ind Science & Technol | Plastic tube, anti-thrombogenic medical material, medical tool, manufacture and manufacturing device thereof, and plasma processor |
| JPH08225673A (en) * | 1995-02-20 | 1996-09-03 | Agency Of Ind Science & Technol | Graft polymerization of vinyl monomer to the surface of ogranic polymer substrate |
| JPH08257112A (en) * | 1995-03-20 | 1996-10-08 | Clinical Supply:Kk | Medical apparatus having lubricated surface and manufacture thereof |
| US6126776A (en) * | 1996-06-28 | 2000-10-03 | Nkt Research Center A/S | Method of modifying the surface of a solid polymer substrate and the product obtained |
| GB2477410A (en) * | 2010-01-27 | 2011-08-03 | Universito De Mons | Grafted polymer coatings |
-
1990
- 1990-10-23 JP JP2283533A patent/JPH04159337A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0857038A (en) * | 1993-06-07 | 1996-03-05 | Agency Of Ind Science & Technol | Plastic tube, anti-thrombogenic medical material, medical tool, manufacture and manufacturing device thereof, and plasma processor |
| JPH08225673A (en) * | 1995-02-20 | 1996-09-03 | Agency Of Ind Science & Technol | Graft polymerization of vinyl monomer to the surface of ogranic polymer substrate |
| JPH08257112A (en) * | 1995-03-20 | 1996-10-08 | Clinical Supply:Kk | Medical apparatus having lubricated surface and manufacture thereof |
| US6126776A (en) * | 1996-06-28 | 2000-10-03 | Nkt Research Center A/S | Method of modifying the surface of a solid polymer substrate and the product obtained |
| USRE39000E1 (en) * | 1996-06-28 | 2006-03-07 | Nkt Research A/S | Method of modifying the surface of a solid polymer substrate and the product obtained |
| GB2477410A (en) * | 2010-01-27 | 2011-08-03 | Universito De Mons | Grafted polymer coatings |
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