JP2009292911A - Surface-hydrophilic polyolefin molded article and method for producing it - Google Patents
Surface-hydrophilic polyolefin molded article and method for producing it Download PDFInfo
- Publication number
- JP2009292911A JP2009292911A JP2008146951A JP2008146951A JP2009292911A JP 2009292911 A JP2009292911 A JP 2009292911A JP 2008146951 A JP2008146951 A JP 2008146951A JP 2008146951 A JP2008146951 A JP 2008146951A JP 2009292911 A JP2009292911 A JP 2009292911A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin molded
- molded article
- containing monomer
- polyolefin
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 104
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 75
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 46
- 229920000570 polyether Polymers 0.000 claims abstract description 46
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- 230000000977 initiatory effect Effects 0.000 claims description 21
- 238000010526 radical polymerization reaction Methods 0.000 claims description 17
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 39
- 229920000642 polymer Polymers 0.000 description 27
- -1 polypropylene Polymers 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 12
- 229910052794 bromium Inorganic materials 0.000 description 12
- 229920005672 polyolefin resin Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 8
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 229920001223 polyethylene glycol Polymers 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000031709 bromination Effects 0.000 description 5
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- 125000000524 functional group Chemical group 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
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- 230000002140 halogenating effect Effects 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
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- 239000004566 building material Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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- 238000004381 surface treatment Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
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- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-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
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Abstract
Description
本発明は、高度の親水性および導電性を有する表面親水性ポリオレフィン成形体およびその製造方法に関する。 The present invention relates to a surface hydrophilic polyolefin molded article having a high degree of hydrophilicity and conductivity and a method for producing the same.
ポリオレフィンは、加工性、耐薬品性、機械的強度および透明性などの物性が優れているために、フィルム、シートおよび容器などをはじめとする各種成形品として広く使用されている。しかしながら、ポリオレフィンは疎水性であるために、成形品の表面を塗装する必要があるなど、用途によっては、そのままでは対処できないという問題があった。 Polyolefins are widely used as various molded articles such as films, sheets and containers because of their excellent physical properties such as processability, chemical resistance, mechanical strength and transparency. However, since polyolefin is hydrophobic, there is a problem that it cannot be dealt with as it is depending on the application, for example, it is necessary to paint the surface of a molded product.
ポリオレフィン成形品の表面の親水性を高くするために、熱処理、波動エネルギーまたは粒子線による処理、プラズマ重合あるいはコロナ処理など、さまざまな表面処理が試みられており、それぞれに一応の成果を上げている。しかしながら、例えば、ポリプロピレンなどの熱分解型のポリオレフィン成形品にコロナ処理を行った場合、処理後、経時的に親水性が低下する傾向がみられ、親水性が不足しているという問題を充分に解決しているとはいえない。経時的に親水性が低下する原因としては、熱分解型ポリオレフィン成形品の成形時に生成した低分子量重合体が経時的に表面にブリードアウトし、これがコロナ処理面を覆うためと考えられている。また、プラズマ重合による表面処理では、モノマー連鎖重合体の単位で重合するのではなく、モノマーを形成する原子が重合し、該原子の再配列が重合過程で盛んに起きる。その結果、生じたポリマーの分子構造と出発物質のモノマーの分子構造とは構造上の類似性が極めて低いことが知られている（非特許文献１参照）。したがって、モノマーの官能基に基づいて発現する物性をポリオレフィン成形体表面に反映させることが難しい場合があった。 Various surface treatments such as heat treatment, wave energy or particle beam treatment, plasma polymerization, or corona treatment have been tried to increase the hydrophilicity of the surface of polyolefin molded products, and each has achieved some results. . However, for example, when a pyrolytic polyolefin molded product such as polypropylene is subjected to corona treatment, the hydrophilicity tends to decrease over time after the treatment, and there is a sufficient problem that the hydrophilicity is insufficient. It cannot be said that it has solved. It is considered that the reason why the hydrophilicity decreases with time is that the low molecular weight polymer produced during the molding of the thermally decomposable polyolefin molded product bleeds out to the surface over time, which covers the corona-treated surface. Also, in the surface treatment by plasma polymerization, the polymerization is not performed in units of monomer chain polymer, but the atoms forming the monomer are polymerized, and rearrangement of the atoms occurs actively in the polymerization process. As a result, it is known that the molecular structure of the resulting polymer and the molecular structure of the starting monomer are very similar in structure (see Non-Patent Document 1). Therefore, it may be difficult to reflect the physical properties expressed based on the functional group of the monomer on the surface of the polyolefin molded body.
また、高分子物質に紫外線照射により高親水性モノマーをグラフト化させる方法が開示されている（特許文献１参照）。しかしながら、一般に紫外線照射では、ポリオレフィンのような炭素−炭素結合または炭素−水素結合のみからなる高分子の結合を解離しラジカルを発生させることは難しい（非特許文献２参照）。そのため、ベンゾフェノンのような光増感剤等の添加が必要となるが、この場合、ポリオレフィン表面のみならず、よりラジカルを発生しやすいモノマー分子のラジカル発生を促進させ、非グラフト化ポリマーが生成するという問題がある。また、ポリオレフィン表面に発生したラジカルの重合反応もフリーラジカル機構で進行するため、分子量や分子量分布をコントロールすることが難しいという問題があった。 Also disclosed is a method of grafting a highly hydrophilic monomer onto a polymer substance by ultraviolet irradiation (see Patent Document 1). However, in general, with ultraviolet irradiation, it is difficult to generate a radical by dissociating a polymer bond composed of only a carbon-carbon bond or a carbon-hydrogen bond such as polyolefin (see Non-Patent Document 2). Therefore, it is necessary to add a photosensitizer such as benzophenone. In this case, not only the polyolefin surface but also the radical generation of monomer molecules that are more likely to generate radicals is promoted, and an ungrafted polymer is generated. There is a problem. Further, since the polymerization reaction of radicals generated on the polyolefin surface also proceeds by a free radical mechanism, there is a problem that it is difficult to control the molecular weight and molecular weight distribution.
一方、ポリオレフィンフィルム表面に導入した重合開始基から極性モノマーを制御ラジカル重合（controlled radical polymerization）することで（メタ）アクリルエステル
やアクリルアミドを表面にグラフト化したポリオレフィンフィルムを調製する方法が報告されている。非特許文献３、非特許文献４、非特許文献５参照）。これらの方法は、ポリオレフィンフィルム表面のみを極性モノマー重合体に導入することを可能にし、先に述べたブリードアウトの問題が改善されるか、あるいは、単独重合体生成等の副反応が抑えられる温和な表面改質方法だといえる。しかしながら、いずれの技術も、ポリオレフィン成形体表面の高親水性化という観点からは、必ずしも充分であるとはいえなかった。
本発明は、親水性、導電性が付与されたポリオレフィン成形体および該ポリオレフィン成形体の製造方法を提供することを課題とする。 An object of the present invention is to provide a polyolefin molded body to which hydrophilicity and conductivity are imparted and a method for producing the polyolefin molded body.
本発明者らは、上記課題を解決するために鋭意検討した結果、ポリオレフィン成形体の表面にポリエーテル基含有モノマーの（共）重合体層を形成させて得られた成形体が優れた表面親水性および導電性を示すことを見出し、本発明を完成させた。 As a result of diligent studies to solve the above problems, the present inventors have found that a molded body obtained by forming a (co) polymer layer of a polyether group-containing monomer on the surface of a polyolefin molded body has excellent surface hydrophilicity. As a result, the present invention was completed.
すなわち、本発明は以下の事項を含む。
〔１〕ポリオレフィン成形体の表面の少なくとも一部に、ポリエーテル基含有モノマーの（共）重合体層が形成されていることを特徴とする表面親水性ポリオレフィン成形体。
〔２〕前記ポリエーテル基含有モノマーの（共）重合体層が共有結合を介して形成されていることを特徴とする〔１〕に記載の表面親水性ポリオレフィン成形体。
〔３〕表面に重合開始基を有するポリオレフィン成形体と、ポリエーテル基含有モノマーとをラジカル重合して得られた表面親水性ポリオレフィン成形体。
〔４〕気温２３℃、湿度５０％の条件下で測定される、ポリオレフィン成形体の水接触角（θPO）と、表面親水性ポリオレフィン成形体の水接触角（θCPI）との関係がθCPI＜θPOであることを特徴とする〔１〕〜〔３〕のいずれかに記載の表面親水性ポリオレフィン成形体。
θCPI＜θPO
〔５〕ポリエーテル基含有モノマーを、ポリオレフィン成形体の表面の少なくとも一部で重合させてポリエーテル基含有モノマーの（共）重合体層を形成させることを特徴とする表面親水性ポリオレフィン成形体の製造方法。
〔６〕前記ポリオレフィン成形体の表面の少なくとも一部に、重合開始基を導入する工程と、表面に重合開始基を導入された該ポリオレフィン成形体と、ポリエーテル基含有モノマーとを重合して、該ポリオレフィン成形体の表面にポリエーテル基含有モノマーの（共）重合体層を形成させる工程とからなることを特徴とする〔５〕に記載の表面親水性ポリオレフィン成形体の製造方法。
〔７〕前記重合が制御ラジカル重合であることを特徴とする〔５〕または〔６〕に記載の表面親水性ポリオレフィン成形体の製造方法。
〔８〕前記重合が原子移動ラジカル重合であることを特徴とする〔５〕〜〔７〕のいずれかに記載の表面親水性ポリオレフィン成形体の製造方法。
That is, the present invention includes the following matters.
[1] A surface hydrophilic polyolefin molded product, wherein a (co) polymer layer of a polyether group-containing monomer is formed on at least a part of the surface of the polyolefin molded product.
[2] The surface hydrophilic polyolefin molded article according to [1], wherein the (co) polymer layer of the polyether group-containing monomer is formed through a covalent bond.
[3] A surface hydrophilic polyolefin molded article obtained by radical polymerization of a polyolefin molded article having a polymerization initiating group on the surface and a polyether group-containing monomer.
[4] The relationship between the water contact angle (θPO) of the polyolefin molded body and the water contact angle (θCPI) of the surface hydrophilic polyolefin molded body measured under the conditions of an air temperature of 23 ° C. and a humidity of 50% is θCPI <θPO The surface hydrophilic polyolefin molded article according to any one of [1] to [3], wherein
θCPI <θPO
[5] A surface hydrophilic polyolefin molded article characterized in that a polyether group-containing monomer is polymerized on at least a part of the surface of a polyolefin molded article to form a (co) polymer layer of the polyether group-containing monomer. Production method.
[6] The step of introducing a polymerization initiating group into at least a part of the surface of the polyolefin molded body, the polyolefin molded body having a polymerization initiating group introduced on the surface, and a polyether group-containing monomer are polymerized, The method for producing a surface hydrophilic polyolefin molded article according to [5], comprising a step of forming a (co) polymer layer of a polyether group-containing monomer on the surface of the polyolefin molded article.
[7] The method for producing a surface hydrophilic polyolefin molded article according to [5] or [6], wherein the polymerization is controlled radical polymerization.
[8] The method for producing a surface hydrophilic polyolefin molded article according to any one of [5] to [7], wherein the polymerization is atom transfer radical polymerization.
本発明によれば、高度な親水性および導電性を有する表面親水性ポリオレフィン成形体を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the surface hydrophilic polyolefin molded object which has high hydrophilicity and electroconductivity can be provided.
以下、本発明について具体的に説明する。
本発明の表面親水性ポリオレフィン成形体は、ポリオレフィン成形体の表面の少なくとも一部に、ポリエーテル基含有モノマーの（共）重合体層が形成されていることを特徴としている。
Hereinafter, the present invention will be specifically described.
The surface hydrophilic polyolefin molded article of the present invention is characterized in that a (co) polymer layer of a polyether group-containing monomer is formed on at least a part of the surface of the polyolefin molded article.
本発明に係るポリオレフィン成形体は、ポリオレフィン樹脂またはポリオレフィン樹脂を含む樹脂組成物を圧縮成形、射出成形、押出成形、押出しラミネート成形、インフレーション加工、熱成形、プレス成形または中空成形するか、あるいはこれらの方法を用いて成形した後さらに二次加工して得られるものであり、形状を保持できるものである。 The polyolefin molded body according to the present invention is formed by compression molding, injection molding, extrusion molding, extrusion laminating, inflation processing, thermoforming, press molding or hollow molding of a polyolefin resin or a resin composition containing a polyolefin resin. It is obtained by further secondary processing after being molded using the method, and can retain its shape.
本発明に係るポリオレフィン成形体は、その表面の一部または全部にポリオレフィン樹脂が露出している成形体であって、この要件を満たすのであれば、ポリオレフィン以外の材料と組み合わせた複合加工品であってもよい。 The polyolefin molded product according to the present invention is a molded product in which a polyolefin resin is exposed on a part or all of its surface, and is a composite processed product combined with a material other than polyolefin as long as this requirement is satisfied. May be.
本発明に係るポリオレフィン成形体を構成するポリオレフィン樹脂は、エチレンおよび／またはα−オレフィンの単独重合体または共重合体であり、具体的には、高密度ポリエチレン、中密度ポリエチレン、エチレン系エラストマー、プロピレン系エラストマー、イソタクチックポリプロピレン、シンジオタクチックポリプロピレンおよび高圧法低密度ポリエチレンならびに上記重合体とアクリル酸、アクリル酸エステルまたは酢酸ビニルとの共重合体；ポリオレフィン系アイオノマー；４−メチル−１−ペンテン（共）重合体；エチレン・環状オレフィン共重合体；エチレンおよび／またはα−オレフィンと極性基含有モノマーとの共重合体などが挙げられる。 The polyolefin resin constituting the polyolefin molded body according to the present invention is a homopolymer or copolymer of ethylene and / or α-olefin, specifically, high density polyethylene, medium density polyethylene, ethylene elastomer, propylene. Elastomers, isotactic polypropylene, syndiotactic polypropylene and high-pressure low-density polyethylene and copolymers of the above polymers with acrylic acid, acrylate ester or vinyl acetate; polyolefin ionomers; 4-methyl-1-pentene ( (Co) polymer; ethylene / cyclic olefin copolymer; copolymer of ethylene and / or α-olefin and a polar group-containing monomer.
また、ポリオレフィン樹脂はその一部または全部が架橋して３次元ネットワーク構造を形成していてもよいし、上記重合体の２種類以上がブロック的に結合したものであってもよいし、グラフト状に結合したものであってもよいし、モノマーの組成を傾斜的に変化させた重合させたものであってもよいし、過酸化物の存在下でアクリル酸エステルや無水マレイン酸などでグラフト変性したものであってもよい。また、本発明の目的を損なわない範囲で、ポリオレフィン樹脂以外の樹脂成分を含有させたものであってもよい。これらのポリオレフィン樹脂は単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 In addition, the polyolefin resin may be partially or wholly crosslinked to form a three-dimensional network structure, or two or more types of the above polymers may be combined in a block form, or may be grafted. The polymer may be bonded to the polymer, polymerized by changing the composition of the monomer in a gradient, or graft-modified with an acrylate ester or maleic anhydride in the presence of a peroxide. It may be what you did. Further, a resin component other than the polyolefin resin may be contained within a range not impairing the object of the present invention. These polyolefin resins may be used alone or in combination of two or more.
本発明に係るポリオレフィン成形体を構成するポリオレフィン樹脂またはポリオレフィン樹脂組成物には、本発明の目的を損なわない範囲で、必要に応じて添加剤を添加してもよい。添加剤としては、例えば、軟化剤、安定剤、充填剤、酸化防止剤、結晶核剤、ワックス、増粘剤、機械的安定性付与剤、レベリング剤、濡れ剤、造膜助剤、架橋剤、防腐剤、防錆剤、顔料、充填剤、分散剤、凍結防止剤および消泡剤等が挙げられる。これらは１種単独で、または２種類以上添加することができる。 If necessary, an additive may be added to the polyolefin resin or polyolefin resin composition constituting the polyolefin molded body according to the present invention as long as the object of the present invention is not impaired. Examples of additives include softeners, stabilizers, fillers, antioxidants, crystal nucleating agents, waxes, thickeners, mechanical stability imparting agents, leveling agents, wetting agents, film-forming aids, and crosslinking agents. , Antiseptics, rust inhibitors, pigments, fillers, dispersants, antifreeze agents and antifoaming agents. These can be used alone or in combination of two or more.
本発明に係るポリオレフィン成形体は市販されているものを用いてもよく、例えば、Ｆ１１３Ｇ（（株）プライムポリマー製、ポリプロピレン二軸延伸フィルム）、オピュラン（三井化学（株）製メチルペンテンコポリマー）およびアペルＡＰＬ６０１１Ｔ（三井化学（株）製環状オレフィンコポリマー）などを用いることができる。 Commercially available polyolefin moldings according to the present invention may be used, for example, F113G (manufactured by Prime Polymer Co., Ltd., polypropylene biaxially stretched film), Opyran (Mitsui Chemicals Co., Ltd. methylpentene copolymer) and Apel APL6011T (cyclic olefin copolymer manufactured by Mitsui Chemicals, Inc.) can be used.
本発明に係るポリエーテル基含有モノマーの（共）重合体層は、ポリエーテル基含有モノマーを単独重合あるいは共重合して得られる層である。
上記ポリエーテル基含有モノマーの基本構造となるビニル系モノマーは、１分子中に１以上の炭素−炭素二重結合を有する化合物であり、アニオン重合またはラジカル重合が可能なモノマーである。ビニル系モノマーとしては、例えば、アクリル酸エステル系モノマー、メタクリル酸エステル系モノマー、スチリル系モノマーおよび（メタ）アクリルアミド系モノマー等が挙げられる。
The (co) polymer layer of the polyether group-containing monomer according to the present invention is a layer obtained by homopolymerizing or copolymerizing a polyether group-containing monomer.
The vinyl-based monomer serving as the basic structure of the polyether group-containing monomer is a compound having one or more carbon-carbon double bonds in one molecule, and is a monomer capable of anionic polymerization or radical polymerization. Examples of vinyl monomers include acrylic acid ester monomers, methacrylic acid ester monomers, styryl monomers, and (meth) acrylamide monomers.
ポリエーテル基含有モノマーとしては、例えば、アクリル酸２−エトキシエチル、アクリル酸２−メトキシエチル、アクリル酸ジエチレングリコール、アクリル酸メトキシエトキシエチル、アクリル酸エトキシエトキシエチル、アクリル酸メトキシトリエチレングリコール、アクリル酸エトキシトリエチレングリコール、エチレングリコールユニット数が
４以上のアクリル酸ポリエチレングリコール、アクリル酸末端アルコキシポリエチレングリコール、メタクリル酸２−エトキシエチル、メタクリル酸２−メトキシエチル、メタクリル酸ジエチレングリコール、メタクリル酸メトキシエトキシエチル、メタクリル酸エトキシエトキシエチル、メタクリル酸メトキシトリエチレングリコール、メタクリル酸エトキシトリエチレングリコール、エチレングリコールユニット数が４以上のメタクリル酸ポリエチレングリコールおよびメタクリル酸末端アルコキシポリエチレングリコール等が挙げられる。
Examples of the polyether group-containing monomer include 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, diethylene glycol acrylate, methoxyethoxyethyl acrylate, ethoxyethoxyethyl acrylate, methoxytriethylene glycol acrylate, and ethoxy acrylate. Triethylene glycol, polyethylene glycol acrylate with 4 or more ethylene glycol units, acrylic acid-terminated alkoxy polyethylene glycol, 2-ethoxyethyl methacrylate, 2-methoxyethyl methacrylate, diethylene glycol methacrylate, methoxyethoxyethyl methacrylate, methacrylic acid Ethoxyethoxyethyl, methoxytriethylene glycol methacrylate, ethoxytriethylene glycol methacrylate, Chi glycol unit number and the like 4 or more polyethylene glycol and methacrylic acid terminated alkoxy polyethylene glycol methacrylate.
本発明では、上記のポリエーテル基含有モノマーの（共）重合体からなる層が、ポリオレフィン成形体の表面上に形成される。本発明では、ポリエーテル基含有モノマーの単独重合体をポリオレフィン成形体の表面にグラフト化してもよいし、２種類以上のポリエーテル基含有モノマーを共重合させて得られた重合体をグラフト化してもよい。また、ポリエーテル基含有モノマーの特徴である親水性が発現する限り、その他のビニル系モノマーとの共重合体をグラフト化してもよい。ポリエーテル基含有モノマーを他のビニル系モノマーと共重合させる場合、ポリエーテル基含有モノマーはランダムに共重合させても、ブロック的に共重合させても、傾斜的に共重合させてもよい。 In the present invention, a layer made of a (co) polymer of the above polyether group-containing monomer is formed on the surface of the polyolefin molded body. In the present invention, a homopolymer of a polyether group-containing monomer may be grafted on the surface of a polyolefin molded body, or a polymer obtained by copolymerizing two or more kinds of polyether group-containing monomers may be grafted. Also good. In addition, a copolymer with another vinyl monomer may be grafted as long as the hydrophilicity characteristic of the polyether group-containing monomer is expressed. When the polyether group-containing monomer is copolymerized with another vinyl monomer, the polyether group-containing monomer may be copolymerized randomly, copolymerized in a block manner, or copolymerized in a gradient manner.
ゲルパーミエーションクロマトグラフィーによるポリエーテル基含有モノマーの（共）重合体セグメントの分子量は、通常２００〜１，０００，０００ｇ/ｍｏｌ、好ましくは
２，０００〜１，０００，０００ｇ/ｍｏｌである。分子量が上記範囲にあると成型体の
機会物性を損なうことなく、良好に導電性を発現するので好ましい。
The molecular weight of the (co) polymer segment of the polyether group-containing monomer by gel permeation chromatography is usually 200 to 1,000,000 g / mol, preferably 2,000 to 1,000,000 g / mol. It is preferable that the molecular weight is in the above-mentioned range since the conductivity can be expressed well without impairing the opportunity physical properties of the molded body.
本発明の表面親水性ポリオレフィン成形体では、ポリエーテル基含有モノマーの（共）重合体層が、ポリオレフィン成形体の表面上に膜状に形成されているのが望ましい。ポリエーテル基含有モノマーの（共）重合体層の膜厚は、特に制限されないが、好ましくは１０〜２００ｎｍの膜厚である。膜厚が上記の範囲にあると、ポリオレフィン成形体にポリエーテル基含有モノマーの有する親水性を充分に付与することができるので好ましい。 In the surface hydrophilic polyolefin molded article of the present invention, it is desirable that the (co) polymer layer of the polyether group-containing monomer is formed in a film shape on the surface of the polyolefin molded article. The thickness of the (co) polymer layer of the polyether group-containing monomer is not particularly limited, but is preferably 10 to 200 nm. It is preferable for the film thickness to be in the above range since the hydrophilicity of the polyether group-containing monomer can be sufficiently imparted to the polyolefin molded article.
ポリエーテル基含有モノマーの（共）重合体層は、ポリオレフィン成形体の表面上に形成されていればよいが、より好ましくは、少なくともポリエーテル基含有モノマーの（共）重合体の末端が、ポリオレフィン成形体の表面に露出しているポリオレフィン樹脂鎖と共有結合によって形成されていることが望ましい。この共有結合は、ポリエーテル基含有モノマーの（共）重合体とポリオレフィン成形体の表面に露出しているポリオレフィン鎖との直接結合であることが望ましいが、ポリオレフィン成形体の表面を導電性を損なわない程度に被覆した短いスペーサーを介して結合したものであってもよい。なお、ポリオレフィン成形体の表面をスペーサーで被覆する場合、スペーサーの重量はポリエーテル基含有モノマーの（共）重合体の重量の５％未満であることが望ましい。 The (co) polymer layer of the polyether group-containing monomer may be formed on the surface of the polyolefin molded body, but more preferably, at least the terminal of the (co) polymer of the polyether group-containing monomer is a polyolefin. It is desirable that it is formed by a covalent bond with a polyolefin resin chain exposed on the surface of the molded body. This covalent bond is preferably a direct bond between the (co) polymer of the polyether group-containing monomer and the polyolefin chain exposed on the surface of the polyolefin molded product, but the surface of the polyolefin molded product is impaired in conductivity. It may be bonded through a short spacer coated to a certain extent. When the surface of the polyolefin molded body is covered with a spacer, the weight of the spacer is preferably less than 5% of the weight of the (co) polymer of the polyether group-containing monomer.
上述のようにして得られた本発明の表面親水性ポリオレフィン成形体は高度な親水性および表面濡れ性を有し、また、導電性を示す。
本発明では、純水による接触角試験におけるポリオレフィン成形体の接触角（θPO）と、表面親水性ポリオレフィン成形体の接触角（θCPＩ）との関係がθCPI＜θPOであ
り、好ましくはθCPI＜θPO＊０．９であり、より好ましくはθCPI＜θPO＊０．８で
ある。θCPI≧θPOである場合は、表面親水性ポリオレフィン成形体はポリオレフィン
成形体と比べ親水性が向上していないので、金属をはじめ種々の極性物質との親和性に乏しく、そのため用途も制限される。
The surface hydrophilic polyolefin molded article of the present invention obtained as described above has a high degree of hydrophilicity and surface wettability, and also exhibits electrical conductivity.
In the present invention, the relationship between the contact angle (θPO) of the polyolefin molded body in the contact angle test with pure water and the contact angle (θCPI) of the surface hydrophilic polyolefin molded body is θCPI <θPO, preferably θCPI <θPO * 0.9, more preferably θCPI <θPO * 0.8. In the case of θCPI ≧ θPO, the hydrophilic surface of the polyolefin molded body does not have improved hydrophilicity as compared with the polyolefin molded body, so that it has poor affinity with various polar substances including metals, and therefore its use is limited.
本発明の表面親水性ポリオレフィン成形体の表面固有抵抗率は、ポリオレフィン成形体の表面固有抵抗率より小さい。表面固有抵抗率の測定方法は、例えば、日本工業規格（ＪＩＳ）のＫ６９１１に準じて測定することができる。成形体表面の抵抗率が小さいと導電
性を発現するのに有利である。本発明の表面親水性ポリオレフィン成形体の表面固有抵抗率は１×１０14Ω・ｃｍ以下であり、好ましくは１×１０2〜１×１０13Ωであり、より
好ましくは１×１０3〜１×１０12Ωである。固有表面抵抗率が１×１０14Ω以上である
場合、導電性を発現することが困難となる場合がある。なお、本発明の表面親水性ポリオレフィン成形体の固有抵抗率の下限は、所望の物性を損なわない限り特にない。
The surface specific resistivity of the surface hydrophilic polyolefin molded product of the present invention is smaller than the surface specific resistivity of the polyolefin molded product. The surface resistivity can be measured according to, for example, Japanese Industrial Standard (JIS) K6911. A low resistivity on the surface of the molded body is advantageous for developing conductivity. The surface specific resistivity of the surface hydrophilic polyolefin molded article of the present invention is 1 × 10 14 Ω · cm or less, preferably 1 × 10 2 to 1 × 10 13 Ω, more preferably 1 × 10 3 to 1. × 10 12 Ω. When the intrinsic surface resistivity is 1 × 10 14 Ω or more, it may be difficult to develop conductivity. The lower limit of the specific resistivity of the surface hydrophilic polyolefin molded article of the present invention is not particularly limited as long as desired physical properties are not impaired.
本発明の表面親水性ポリオレフィン成形体は、ポリオレフィン成形体の表面上に存在する重合開始基を開始反応点として、上記のポリエーテル基含有モノマーを重合させて、ポリオレフィン成形体の表面上にポリエーテル基含有モノマーの（共）重合体層を形成させることにより製造することができる。 The surface hydrophilic polyolefin molded article of the present invention is obtained by polymerizing the above-mentioned polyether group-containing monomer using a polymerization initiating group present on the surface of the polyolefin molded article as an initiating reaction point, to form a polyether on the surface of the polyolefin molded article. It can be produced by forming a (co) polymer layer of group-containing monomers.
本発明の製造方法では、ポリエーテル基含有モノマーの（共）重合体層の形成するに際して、表面に重合開始基を有するポリオレフィン成形体を用いてもよいし、ポリオレフィン成形体の表面の少なくとも一部に重合開始基を導入して用いてもよい。ポリオレフィン成形体の表面に重合開始基を導入する方法は、あらかじめ重合開始基を導入したポリオレフィン樹脂を成形してもよいし、ポリオレフィン成形体に低分子または高分子の重合開始基を表面修飾させてもよい。また、重合開始基が導入され、かつ、フィルムやシートの形態に成形されたポリオレフィン樹脂を他の樹脂フィルム成形体、金属、紙および木材などに積層したものに双極イオン性ビニル系モノマーを重合させてもよい。 In the production method of the present invention, when forming the (co) polymer layer of the polyether group-containing monomer, a polyolefin molded body having a polymerization initiating group on the surface may be used, or at least a part of the surface of the polyolefin molded body Alternatively, a polymerization initiating group may be introduced into and used. The method of introducing a polymerization initiating group on the surface of a polyolefin molded body may be molding a polyolefin resin in which a polymerization initiating group has been previously introduced, or by modifying the surface of a polyolefin molded body with a low molecular or high molecular weight polymerization initiating group. Also good. In addition, a bipolar ionic vinyl-based monomer is polymerized on a polyolefin resin that has been introduced into a polymerization initiating group and is laminated in the form of a film or sheet on another resin film molding, metal, paper, wood, etc. May be.
表面に重合開始基を有するポリオレフィン成形体と、ポリエーテル基含有モノマーとを重合させる方法としては、イオン重合法やラジカル重合法などが挙げられるが、イオン重合法はポリエーテル基含有モノマーの重合活性点が被毒化を受ける場合があるので、ラジカル重合法が用いるのが好ましい。 Examples of a method for polymerizing a polyolefin molded body having a polymerization initiating group on the surface and a polyether group-containing monomer include an ionic polymerization method and a radical polymerization method. The ion polymerization method is a polymerization activity of a polyether group-containing monomer. Since the point may be poisoned, the radical polymerization method is preferably used.
ポリオレフィン成形体にポリエーテル基含有モノマーをグラフト化するグラフト重合の方法としては、有機過酸化物等のラジカル発生剤を作用させる方法あるいはＸ線照射、ガンマ線照射、電子線照射、マイクロ波または紫外線照射等を用いてグラフト化させる方法が知られており、これらの方法によって本発明に係るポリエーテル基含有モノマーを導入することができる。しかしながら、これらの方法では、（１）グラフト化していないビニルモノマーホモ重合体が生成してしまう（２）基材フィルムの表面上にポリエーテル基含有モノマーが高密度にグラフト化されたり、高分子量化し難い等の問題点を有する場合がある。 The graft polymerization method for grafting a polyether group-containing monomer to a polyolefin molded body may be a method in which a radical generator such as an organic peroxide is allowed to act, or X-ray irradiation, gamma ray irradiation, electron beam irradiation, microwave or ultraviolet ray irradiation. Etc. are known, and the polyether group-containing monomer according to the present invention can be introduced by these methods. However, in these methods, (1) an ungrafted vinyl monomer homopolymer is formed. (2) A polyether group-containing monomer is grafted at a high density on the surface of the base film, or a high molecular weight. In some cases, it may be difficult to convert.
このような問題点を解決する製造方法として、制御ラジカル重合の適用が挙げられる。制御ラジカル重合とは、従来の過酸化物添加系によるフリーラジカル重合技術と異なり、重合系中のラジカル濃度を低く抑えることで、停止反応や連鎖移動反応などの副反応を抑えたラジカル重合技術である。本方法によれば、しばしば重合がリビング重合様に進行することから、高分子量でかつ分子量分布の狭いセグメントを得ることができる。 As a production method for solving such problems, application of controlled radical polymerization can be mentioned. Controlled radical polymerization is a radical polymerization technique that suppresses side reactions such as termination reactions and chain transfer reactions by controlling the radical concentration in the polymerization system to a low level, unlike conventional free radical polymerization techniques using peroxide addition systems. is there. According to this method, since the polymerization often proceeds like a living polymerization, a segment having a high molecular weight and a narrow molecular weight distribution can be obtained.
本発明に適用される制御ラジカル重合法としては、Trend Polym. Sci.,（1996）, 4, 456 に開示された方法であってニトロキシドを有する基と結合し、熱的な開裂によりラジ
カルを発生させてモノマーを重合させる方法(NMRP: Nitroxide-Mediated Radical Polymerization)や原子移動ラジカル重合（ATRP：Atom Transfer Radical Polymerization）方
法が挙げられる。このうち原子移動ラジカル重合方法とは、Science,(1996),272,866、Chem. Rev., 101, 2921 (2001)、WO96/30421号公報、WO97/18247号公報、WO98/01480号公報、WO98/40415号公報、WO00/156795号公報、あるいは澤本ら、Chem. Rev., 101, 3689 (2001)、特開平8-41117号公報、特開平9-208616号公報、特開2000-264914号公報、特開2001-316410号公報、特開2002-80523号公報および特開2004-307872号公報に開示された方法で
あって、有機ハロゲン化物またはハロゲン化スルホニル化合物を開始剤とし、遷移金属を
中心金属とする金属錯体を触媒として、ラジカル重合性単量体をラジカル重合する方法または可逆的付加−開裂連鎖移動重合（RAFT ：Reversible Addition Fragmentation Chain
Transfer）する方法をいう。
The controlled radical polymerization method applied to the present invention is a method disclosed in Trend Polym. Sci., (1996), 4, 456, which is combined with a group having a nitroxide to generate a radical by thermal cleavage. And a monomer polymerization method (NMRP: Nitroxide-Mediated Radial Polymerization) and an atom transfer radical polymerization (ATRP) method. Among these, the atom transfer radical polymerization method includes Science, (1996), 272, 866, Chem. Rev., 101, 2921 (2001), WO96 / 30421, WO97 / 18247, WO98 / 01480, WO98 / No. 40415, WO00 / 156795, or Sawamoto et al., Chem. Rev., 101, 3689 (2001), JP-A-8-41117, JP-A-9-208616, JP-A-2000-264914, A method disclosed in JP-A-2001-316410, JP-A-2002-80523, and JP-A-2004-307872, wherein an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal is a central metal A radical polymerization of a radically polymerizable monomer using a metal complex as a catalyst, or reversible addition-fragmentation chain transfer polymerization (RAFT)
Transfer).
上記の制御ラジカル重合法のうち、原子移動ラジカル重合方法は、ラジカル重合開始基の導入が容易であること、および選択できるモノマー種が豊富であることから、本発明に係る重合体セグメントを導入するのに有効な重合方法である。 Among the above-mentioned controlled radical polymerization methods, the atom transfer radical polymerization method introduces the polymer segment according to the present invention because it is easy to introduce radical polymerization initiating groups and there are abundant monomer types that can be selected. This is an effective polymerization method.
原子移動ラジカル重合法を用いた製造方法についてさらに具体的に説明する。
Science,(1996),272,866等に開示されるように、原子移動ラジカル重合を開始するには、基材フィルムの表面にハロゲン原子が結合した部位を有していることが必要であり、しかも、該ハロゲン原子の結合解離エネルギーは小さい方がよい。例えば、３級炭素原子に結合したハロゲン原子、ビニル基、ビニリデン基およびフェニル基などの炭素−炭素不飽和結合に隣接する炭素原子に結合したハロゲン原子あるいはカルボニル基、シアノ基およびスルホニル基等の共役性の基に直接またはこれらの共役性の基に隣接する原子に結合したハロゲン原子が存在していることが好ましい。
The production method using the atom transfer radical polymerization method will be described more specifically.
As disclosed in Science, (1996), 272,866, etc., in order to initiate atom transfer radical polymerization, it is necessary that the surface of the substrate film has a site to which a halogen atom is bonded, The bond dissociation energy of the halogen atom is preferably small. For example, a halogen atom bonded to a carbon atom adjacent to a carbon-carbon unsaturated bond such as a halogen atom, vinyl group, vinylidene group, and phenyl group bonded to a tertiary carbon atom, or a conjugated group such as a carbonyl group, a cyano group, and a sulfonyl group. It is preferable that a halogen atom bonded to an atomic group directly or to an atom adjacent to these conjugated groups is present.
このような原子移動ラジカル重合開始能を有するハロゲン原子を基材フィルムの表面に導入する方法としては、官能基変換法や直接ハロゲン化法などが挙げられる。
官能基変換法は、水酸基、カルボキシル基、酸無水物基、ビニル基およびシリル基等の官能基が基材フィルムの表面に存在する場合に好ましく適用される。これらの官能基を原子移動ラジカル重合開始剤の構造に変換する方法は、例えば、特開2004-131620号公報に
開示され、水酸基含有ポリオレフィンを２−ブロモイソ酪酸ブロミドのような低分子化合物で修飾することにより原子移動ラジカル重合開始能を有する表面ハロゲン化フィルムを得る方法が開示されている。
Examples of a method for introducing a halogen atom having such an atom transfer radical polymerization initiating ability onto the surface of the substrate film include a functional group conversion method and a direct halogenation method.
The functional group conversion method is preferably applied when functional groups such as a hydroxyl group, a carboxyl group, an acid anhydride group, a vinyl group, and a silyl group are present on the surface of the base film. A method for converting these functional groups into the structure of an atom transfer radical polymerization initiator is disclosed in, for example, Japanese Patent Application Laid-Open No. 2004-131620, and a hydroxyl group-containing polyolefin is modified with a low molecular weight compound such as 2-bromoisobutyric acid bromide. A method for obtaining a surface halogenated film having the ability to initiate atom transfer radical polymerization is disclosed.
直接ハロゲン化法は、ハロゲン化剤を基材フィルムの表面に直接作用させ、炭素−ハロゲン結合を有するハロゲン化ポリオレフィンを得る方法である。使用するハロゲン化剤や導入するハロゲン原子の種類は特に限定されるものではないが、原子移動ラジカル重合開始骨格の安定性と開始効率とのバランスを考えると、臭素原子を導入した臭素化ポリオレフィンを得る方法が好ましい。ハロゲン化ポリオレフィンの製造に用いるハロゲン化剤としては、臭素やN-ブロモスクシンイミド（NBS）などが挙げられる。臭素化については、
例えば、G. A. RusselらによりJ. Am. Chem. Soc., 77, 4025 (1955) に開示された、臭
素を光照射下で反応させてアルケンを臭素化させる光臭素化反応、P. R. Schneinerらに
よりAngew. Chem. Int. Ed. Engl., 37, 1895 (1998) に開示された、５０％ＮａＯＨ水
溶液および四臭化炭素の存在下に溶液中で環状アルキルを加熱還流して臭素化する方法あるいはM. C. FordらによりJ. Chem. Soc., 2240 (1952) に開示された、Ｎ−ブロモスク
シンイミドをアゾビスイソブチロニトリル等のラジカル開始剤を用いてラジカル反応させてアルキル末端を臭素化する方法等が挙げられる。
The direct halogenation method is a method of obtaining a halogenated polyolefin having a carbon-halogen bond by allowing a halogenating agent to act directly on the surface of a base film. The type of halogenating agent to be used and the type of halogen atom to be introduced are not particularly limited, but considering the balance between the stability of the atom transfer radical polymerization initiation skeleton and the initiation efficiency, a brominated polyolefin having a bromine atom introduced can be used. The obtaining method is preferred. Examples of the halogenating agent used in the production of the halogenated polyolefin include bromine and N-bromosuccinimide (NBS). For bromination
For example, as disclosed in J. Am. Chem. Soc., 77, 4025 (1955) by GA Russel et al., Photobromination reaction in which bromine is reacted under light irradiation to bromine alkenes, Ang Schew by PR Schneiner et al. Chem. Int. Ed. Engl., 37, 1895 (1998) disclosed in the method of bromination by heating and refluxing cyclic alkyl in solution in the presence of 50% aqueous NaOH and carbon tetrabromide, or MC For example, disclosed in J. Chem. Soc., 2240 (1952) by Ford et al., A method in which N-bromosuccinimide is subjected to radical reaction using a radical initiator such as azobisisobutyronitrile to brominate an alkyl terminal, etc. Is mentioned.
上述のようにして得られた表面ハロゲン化フィルムのフィルム表面に導入されたハロゲン原子の存在はＸ線光電子分光測定等の分光学的方法により確認される。
原子移動ラジカル重合は表面ハロゲン化フィルムの存在下でビニルモノマーおよび触媒成分と接触させることにより行われる。このとき溶媒を用いてもよい。使用できる溶媒としては、重合反応を阻害せず、かつ、表面ハロゲン化フィルムを変質させない重合温度にできるものであれば特に制限されない。例えば、ベンゼン、トルエンおよびキシレン等の芳香族炭化水素系溶媒；ペンタン、ヘキサン、ヘプタン、オクタン、ノナンおよびデカン等の脂肪族炭化水素系溶媒；シクロヘキサン、メチルシクロヘキサンおよびデカヒドロナフタレンのような脂環族炭化水素系溶媒；クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、塩化メチレン、クロロホルム、四塩化炭素およびテトラクロロエチレン等の
塩素化炭化水素系溶媒；メタノール、エタノール、n-プロパノール、イソプロパノール、n-ブタノール、sec-ブタノールおよびtert-ブタノール等のアルコール系溶媒；アセトン
、メチルエチルケトンおよびメチルイソブチルケトン等のケトン系溶媒；酢酸エチルおよびジメチルフタレート等のエステル系溶媒；ジメチルエーテル、ジエチルエーテル、ジ-n-アミルエーテル、テトラヒドロフランおよびジオキシアニソールのようなエーテル系溶
媒等を挙げることができる。また、水を溶媒に使用してもよい。これらの溶媒は単独でも使用してもよいし、２種以上を混合して使用してもよい。重合温度は原子移動ラジカル重合開始基が導入された表面ハロゲン化フィルムが変質しない温度で、かつ、ラジカル重合反応が進行する温度であれば任意に設定することができる。重合温度は所望する重合体の重合度、使用するラジカル重合開始剤および溶媒の種類や量によって決定され、通常-50
〜150℃であり、好ましくは0〜80℃であり、より好ましくは0〜50℃である。重合反応は
減圧、常圧または加圧下のいずれの条件下で行ってもよい。反応終了後は従来公知の精製・乾燥方法を用いて、触媒残査、未反応モノマーおよび溶媒を除去する。
The presence of halogen atoms introduced on the surface of the surface halogenated film obtained as described above is confirmed by a spectroscopic method such as X-ray photoelectron spectroscopy.
Atom transfer radical polymerization is performed by contacting with a vinyl monomer and a catalyst component in the presence of a surface halogenated film. At this time, a solvent may be used. The solvent that can be used is not particularly limited as long as it does not inhibit the polymerization reaction and can be a polymerization temperature that does not alter the surface halogenated film. For example, aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane; alicyclics such as cyclohexane, methylcyclohexane and decahydronaphthalene Hydrocarbon solvents; chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and alcohol solvents such as tert-butanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; dimethyl ether, diethyl ether And ether solvents such as ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole. Further, water may be used as a solvent. These solvents may be used alone or in combination of two or more. The polymerization temperature can be arbitrarily set as long as it is a temperature at which the surface halogenated film into which the atom transfer radical polymerization initiating group is introduced does not change and the temperature at which the radical polymerization reaction proceeds. The polymerization temperature is determined by the degree of polymerization of the desired polymer, the type and amount of the radical polymerization initiator and solvent used, and is usually -50
It is -150 degreeC, Preferably it is 0-80 degreeC, More preferably, it is 0-50 degreeC. The polymerization reaction may be performed under any conditions of reduced pressure, normal pressure or increased pressure. After completion of the reaction, the catalyst residue, unreacted monomer and solvent are removed using a conventionally known purification / drying method.
成形体の表面にポリエーテル基含有モノマーの（共）重合体層（Ｂ）が形成されたことは、Ｘ線光電子分光法、電子線マイクロアナリシスまたは赤外分光法などの分光学的手法により確認される。 The formation of the (co) polymer layer (B) of the polyether group-containing monomer on the surface of the molded body was confirmed by a spectroscopic method such as X-ray photoelectron spectroscopy, electron microanalysis, or infrared spectroscopy. Is done.
本発明の表面親水性ポリオレフィン系成形体は特に制限なく種々の用途に使用される。以下に具体例を挙げる。
（１）フィルムまたはシート：本発明の表面親水性ポリオレフィン成形体は、ポリオレフィン特有の強度、耐衝撃性および耐溶剤安定性を保持しつつ、極めて高い親水性および生体適合性を有するため、フィルムまたはシートとして用いられる。
また、本発明の表面親水性ポリオレフィン成形体からなる層を少なくとも１層含む積層体、例えば、農業用フィルム、ラップ用フィルム、シュリンク用フィルム、プロテクト用フィルム、血漿成分分離膜および水選択透過気化膜等の分離膜例、イオン交換膜ならびにバッテリーセパレータおよび光学分割膜等の選択分離膜にも好適に用いられる。
The surface hydrophilic polyolefin-based molded article of the present invention is used for various applications without particular limitation. Specific examples are given below.
(1) Film or sheet: The surface hydrophilic polyolefin molded article of the present invention has extremely high hydrophilicity and biocompatibility while maintaining the strength, impact resistance and solvent resistance stability unique to polyolefin. Used as a sheet.
Also, a laminate comprising at least one layer comprising the surface hydrophilic polyolefin molded article of the present invention, such as an agricultural film, a wrapping film, a shrink film, a protective film, a plasma component separation membrane, and a water selective pervaporation membrane It is also suitably used for examples of separation membranes such as ion exchange membranes, and selective separation membranes such as battery separators and optical separation membranes.
（２）マイクロカプセル、ＰＴＰ包装、ケミカルバルブおよびドラッグデリバリーシステム。
（３）建材・土木用材料、例えば、床材、床タイル、床シート、遮音シート、断熱パネル、防振材、化粧シート、巾木、アスファルト改質材、ガスケット・シーリング材、ルーフィングシ-トおよび止水シート等の建材・土木用樹脂およびそれからなる成形体等。
(2) Microcapsules, PTP packaging, chemical valves and drug delivery systems.
(3) Building materials and civil engineering materials, such as floor materials, floor tiles, floor sheets, sound insulation sheets, heat insulation panels, anti-vibration materials, decorative sheets, baseboards, asphalt modifiers, gaskets / sealing materials, roofing sheets Building materials such as water-stop sheets, civil engineering resins, and molded articles made of them.
（４）自動車内外装材およびガソリンタンク：本発明の表面親水性ポリオレフィン成形体からなる自動車内外装材およびガソリンタンクは、剛性、耐衝撃性、耐油性および耐熱性に優れる。 (4) Automotive interior / exterior material and gasoline tank: The automotive interior / exterior material and gasoline tank comprising the surface hydrophilic polyolefin molded product of the present invention are excellent in rigidity, impact resistance, oil resistance and heat resistance.
（５）電気・電子部品等の電気絶縁材料、電子部品処理用器材、磁気記録媒体、磁気記録媒体のバインダー、導電性フィルム、電気回路の封止材、家電用素材、電子レンジ用容器等の容器用器材、電子レンジ用フィルム、高分子電解質基材および導電性アロイ基材等；コネクター、ソケット、抵抗器、リレーケーススイッチコイルボビン、コンデンサー、バリコンケース、光ピックアップ、光コネクター、発振子、各種端子板、変成器、プラグ、プリント配線板、チューナー、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、パワーモジュール、ハウジング、半導体、液晶ディスプレー部品、ＦＤＤキャリッジ、ＦＤＤシャーシ、ＨＤＤ部品、モーターブラッシュホルダー、パラボラアンテナおよびコンピューター関連部品等に代表される電気・電子部品；ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーディオレーザーディスク（登録商標）およびコンパクトディスク等の音声機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品およびワードプロセッサー部
品等に代表される家庭および事務電気製品部品、オフィスコンピューター関連部品、電話機関連部品、ファクシミリ関連部品、複写機関連部品、電磁シールド材ならびにスピーカーコーン材およびスピーカー用振動素子等。
(5) Electrical insulation materials such as electrical / electronic components, electronic component processing equipment, magnetic recording media, binders for magnetic recording media, conductive films, sealing materials for electrical circuits, materials for household appliances, containers for microwave ovens, etc. Container equipment, microwave oven film, polymer electrolyte substrate, conductive alloy substrate, etc .; connector, socket, resistor, relay case switch coil bobbin, capacitor, variable capacitor case, optical pickup, optical connector, oscillator, various terminals Board, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display component, FDD carriage, FDD chassis, HDD component, motor brush holder, Parabolic antenna and computer Electric / electronic parts typified by electronic parts, etc .; audio equipment parts such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio laser discs (registered trademark) and compact discs , Lighting parts, refrigerator parts, air conditioner parts, home and office electrical product parts such as typewriter parts and word processor parts, office computer related parts, telephone related parts, facsimile related parts, copier related parts, electromagnetic shielding materials and Speaker cone material and speaker vibration elements.
（６）塗料ベース表面硬化材料：本発明の表面親水性ポリオレフィン成形体からなる成形品は、各種の塗料および極性モノマーとの親和性に富むことから、アクリル系モノマー、多官能性アクリル系モノマーまたは塗料等をコートすることにより光硬化材料または熱硬化材料として用いられる。 (6) Paint-based surface-curing material: Since the molded article comprising the surface hydrophilic polyolefin molded article of the present invention has high affinity with various paints and polar monomers, acrylic monomers, polyfunctional acrylic monomers or It is used as a photo-curing material or a thermosetting material by coating a paint or the like.
（７）医療・衛生用材料不織布、不織布積層体、エレクトレット、医療用チューブ、医療用容器、輸液バッグ、プレフィルシリンジおよび注射器等の医療用品および医療用材料、細胞培養基板および再生医療に用いる細胞皿および組織培養皿、人工臓器、人工筋肉、濾過膜、食品衛生・健康用品、レトルトバッグならびに鮮度保持フィルム等。 (7) Medical / hygiene material non-woven fabric, non-woven fabric laminate, electret, medical tube, medical container, infusion bag, prefilled syringe, syringe and other medical supplies and medical materials, cell culture substrate and cells used for regenerative medicine Dishes and tissue culture dishes, artificial organs, artificial muscles, filtration membranes, food hygiene / health goods, retort bags and freshness-preserving films.
（８）雑貨類デスクマット、カッティングマット、定規、ペンの胴軸・グリップ・キャップ、ハサミおよびカッター等のグリップ、マグネットシート、ペンケース、ペーパーフォルダー、バインダー、ラベルシール、テープおよびホワイトボード等の文房具；衣類、カーテン、シーツ、絨毯、玄関マット、バスマット、バケツ、ホース、バック、プランター、エアコンおよび排気ファンのフィルター、食器、トレー、カップ、弁当箱、コーヒーサイフォン用ロート、メガネフレーム、コンテナ、収納ケース、ハンガー、ロープおよび洗濯ネット等の生活日用雑貨類：シューズ、ゴーグル、スキー板、ラケット、ボール、テント、水中メガネ、足ヒレ、釣り竿、クーラーボックス、レジャーシートおよびスポーツ用ネット等のスポーツ用品；ブロックおよびカード等の玩具；灯油缶、ドラム缶、洗剤およびシャンプー等の容器；看板、パイロンおよびプラスチックチェーン等の表示用具類。 (8) Accessories desk mats, cutting mats, rulers, pen barrels, grips, caps, grips such as scissors and cutters, magnetic sheets, pen cases, paper folders, binders, label seals, stationery such as tapes and whiteboards Clothing, curtains, sheets, carpets, doormats, bath mats, buckets, hoses, bags, planters, air conditioner and exhaust fan filters, dishes, trays, cups, lunch boxes, coffee siphon funnels, glasses frames, containers, storage cases Daily goods such as shoes, hangers, ropes and laundry nets: Sporting goods such as shoes, goggles, skis, rackets, balls, tents, underwater glasses, fins, fishing rods, cooler boxes, leisure seats and sports nets; The Signboard, pylon and display equipment such as plastic chain; container of kerosene cans, drums, such as detergents and shampoos; click and toys such as a card.
〔実施例〕
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
［調製例１］OPPフィルムの臭素化
ポリプロピレン製二軸延伸（OPP）フィルム（F113G （(株)プライムポリマー製）をＧ
Ｍ社製小型シート成形機(TS-300-200)を使用して樹脂温度:230℃、チルロール温度:50℃
、引取速度:1.0m/分にて厚さ500μmのシートを作製した後、ブルックナー社製延伸機(KARO IV)を使用して、予熱温度:153℃、予熱時間:60秒、延伸倍率:5(MD)×7(TD)、延伸速度:6m/分にて延伸（逐次二軸延伸）して、厚さ40μmの二軸延伸フィルムを得た。この二軸延伸フィルムを窒素置換された内容積1000ｍＬのガラス製容器に入れ、臭素0.2mLを容器の
底に封入した。約5分間後、臭素が完全に蒸気化した後、３００Ｗ白熱電球をフィルムよ
り１５ｃｍの距離から垂直に光照射した。１０分後、系内に存在する未反応の臭素蒸気を窒素ガスにより置換した後、フィルムを取り出した。
Ｘ線光電子分光法による表面解析の結果、フィルムの表面に12.8atom％の臭素原子がグラフト化した臭素化OPPフィルムが得られていることを確認した。
[Preparation Example 1] Bromination of OPP film Polypropylene biaxially stretched (OPP) film (F113G (manufactured by Prime Polymer Co., Ltd.))
Resin temperature: 230 ℃, chill roll temperature: 50 ℃ using a small sheet molding machine (TS-300-200) manufactured by M company
After taking a sheet having a thickness of 500 μm at a take-off speed of 1.0 m / min, using a Bruckner stretching machine (KARO IV), preheating temperature: 153 ° C., preheating time: 60 seconds, draw ratio: 5 The film was stretched (sequential biaxial stretching) at (MD) × 7 (TD) and stretching speed: 6 m / min to obtain a biaxially stretched film having a thickness of 40 μm. This biaxially stretched film was put into a glass container with an internal volume of 1000 mL purged with nitrogen, and 0.2 mL of bromine was sealed at the bottom of the container. About 5 minutes later, after bromine was completely vaporized, a 300 W incandescent bulb was irradiated with light vertically from a distance of 15 cm from the film. After 10 minutes, unreacted bromine vapor present in the system was replaced with nitrogen gas, and then the film was taken out.
As a result of surface analysis by X-ray photoelectron spectroscopy, it was confirmed that a brominated OPP film in which 12.8 atom% bromine atoms were grafted on the surface of the film was obtained.
［調製例２］ＴＰＸフィルムの臭素化
メチルペンテンコポリマー（ＴＰＸ）フィルム（オピュラン：三井化学（株）製）を窒素置換された内容積1000mLのガラス製容器に入れ、臭素0.2mLを容器に封入した。約5分間後、臭素が完全に蒸気化した後、光照射した。１０分後、系内に存在する未反応の臭素蒸気を窒素ガスにより置換し、フィルムを取り出した。
Ｘ線光電子分光法による表面解析の結果、10.5atom％の臭素原子がフィルムの表面にグラフト化した臭素化ＴＰＸフィルムが得られていることを確認した。
[Preparation Example 2] Bromination of TPX film A methylpentene copolymer (TPX) film (Opylan: manufactured by Mitsui Chemicals, Inc.) was placed in a glass container with an internal volume of 1000 mL purged with nitrogen, and 0.2 mL of bromine was sealed in the container. . After about 5 minutes, the bromine was completely vaporized and then irradiated with light. After 10 minutes, unreacted bromine vapor present in the system was replaced with nitrogen gas, and the film was taken out.
As a result of surface analysis by X-ray photoelectron spectroscopy, it was confirmed that a brominated TPX film in which 10.5 atom% of bromine atoms were grafted on the surface of the film was obtained.
［調製例３］ＣＯＣフィルムの臭素化
環状オレフィンコポリマー（ＣＯＣ）（アペルAPL6011T：三井化学（株）製）のプレスフィルム（フィルム厚：120μm）を窒素置換された内容積1000mLのガラス製容器に入れ、臭素0.1mLを容器に封入した。約5分間後、臭素が完全に蒸気化した後、光照射した。１０分後、系内に存在する未反応の臭素蒸気を窒素ガスにより置換し、フィルムを取り出した。
Ｘ線光電子分光法による表面解析の結果、8.0atom％の臭素原子がフィルム表面にグラ
フト化した臭素化ＣＯＣフィルムが得られていることを確認した。
[Preparation Example 3] Bromination of COC film A cyclic olefin copolymer (COC) (Appel APL6011T: Mitsui Chemicals, Inc.) press film (film thickness: 120 μm) is placed in a glass container with an internal volume of 1000 mL purged with nitrogen. Then, 0.1 mL of bromine was sealed in a container. After about 5 minutes, the bromine was completely vaporized and then irradiated with light. After 10 minutes, unreacted bromine vapor present in the system was replaced with nitrogen gas, and the film was taken out.
As a result of surface analysis by X-ray photoelectron spectroscopy, it was confirmed that a brominated COC film in which 8.0 atom% bromine atoms were grafted on the film surface was obtained.
[製造例１]
脱酸素処理されたトルエンおよびポリエチレングリコールメタクリレート（Ａｌｄｒｉｃｈ社製；Ｍｎ＝３００）を６７／３３の体積比で入れたガラス容器に製造例１で得られた臭素化OPPフィルムを完全に浸漬させた。そこに、臭化銅（Ｉ）とN,N,N' ,N",N"-ペン
タメチルジエチレントリアミンの１：２（モル比）のエタノール調製液（臭化銅（Ｉ）の濃度0.8M）を、臭化銅（Ｉ）濃度が2.5ｍMとなるように添加し、６０℃で１時間保持した。フィルムを取り出し、メタノールで２回浸漬洗浄し、８０℃で１０時間減圧乾燥させることにより、表面にポリエチレングリコールメタクリレート重合体が導入されたポリプロピレンフィルム（Ｆ−１）が得られた。
[Production Example 1]
The brominated OPP film obtained in Production Example 1 was completely immersed in a glass container containing deoxygenated toluene and polyethylene glycol methacrylate (manufactured by Aldrich; Mn = 300) at a volume ratio of 67/33. There, a 1: 2 (molar ratio) ethanol preparation of copper (I) bromide and N, N, N ', N ", N" -pentamethyldiethylenetriamine (concentration of copper (I) bromide 0.8M) Was added so that the copper (I) bromide concentration was 2.5 mM, and kept at 60 ° C. for 1 hour. The film was taken out, washed by immersion twice with methanol, and dried under reduced pressure at 80 ° C. for 10 hours to obtain a polypropylene film (F-1) having a polyethylene glycol methacrylate polymer introduced on the surface.
得られたポリプロピレンフィルム（Ｆ−１）の表面付近の断面をTEM観察したところ、
表面にメタクロイルコリンクロリド重合体の層と推定される約６０〜８０nmの厚みの染色領域が観察された。
When TEM observation of the cross section near the surface of the obtained polypropylene film (F-1),
A dyed region having a thickness of about 60 to 80 nm estimated to be a layer of methacryloylcholine chloride polymer was observed on the surface.
[製造例２]
製造例１において、臭素化フィルムとして、調製例２で得られた臭素化ＴＰＸフィルムを用いたこと以外は製造例１と同様にして表面の重合を行い、表面にポリエチレングリコールメタクリレート重合体が導入されたTPXフィルムを得た。
[Production Example 2]
In Production Example 1, the surface was polymerized in the same manner as in Production Example 1 except that the brominated TPX film obtained in Preparation Example 2 was used as the brominated film, and a polyethylene glycol methacrylate polymer was introduced on the surface. Obtained TPX film.
[製造例３]
製造例１において、臭素化フィルムとして、調製例３で得られた臭素化ＣＯＣフィルムを用いたこと以外は製造例１と同様にして表面の重合を行い、表面にポリエチレングリコールメタクリレート重合体が導入されたCOCフィルム（Ｆ−３）を得た。
[Production Example 3]
In Production Example 1, the surface was polymerized in the same manner as in Production Example 1 except that the brominated COC film obtained in Preparation Example 3 was used as the brominated film, and a polyethylene glycol methacrylate polymer was introduced on the surface. COC film (F-3) was obtained.
[フィルムの親水性評価]
製造例１〜３で得られたフィルム（F-1〜F-3）と、比較試料として調整例１で用いたポリプロピレン製二軸延伸フィルム（基材フィルム）とをそれぞれ5cm×5cmの大きさに切断し、試料とした。試料の水接触角試験は以下の試験条件で行った。
試験条件：温度23±２℃、湿度50±5%、フィルム膜厚約40μm
製造例１で得られたフィルム（F-1）は、上記試験に加えて、室温で水中に８時間浸して
水洗した後、20日間室温減圧下で乾燥したものを試料として、水接触角測定試験を行った。結果を表１に示す。
[Evaluation of hydrophilicity of film]
Each of the films (F-1 to F-3) obtained in Production Examples 1 to 3 and the polypropylene biaxially stretched film (base film) used in Preparation Example 1 as a comparative sample each have a size of 5 cm × 5 cm. And cut into samples. The water contact angle test of the sample was performed under the following test conditions.
Test conditions: Temperature 23 ± 2 ℃, humidity 50 ± 5%, film thickness about 40μm
In addition to the above test, the film (F-1) obtained in Production Example 1 was immersed in water at room temperature for 8 hours, washed with water, and then dried for 20 days at room temperature under reduced pressure. A test was conducted. The results are shown in Table 1.
[フィルムの導電性評価]
製造例１〜３で得られたフィルム（F-1〜F-3）と、比較試料として調整例１で用いた基材フィルムをそれぞれ5cm×5cmの大きさに切断し、試料とした。試料の導電性試験をJIS K 6911に準じて行った。
試験条件：温度23±２℃、湿度50±5%、フィルム膜厚約40μm
[Evaluation of film conductivity]
The films (F-1 to F-3) obtained in Production Examples 1 to 3 and the base film used in Preparation Example 1 as a comparative sample were each cut to a size of 5 cm × 5 cm to obtain samples. The conductivity test of the sample was performed according to JIS K 6911.
Test conditions: Temperature 23 ± 2 ℃, humidity 50 ± 5%, film thickness about 40μm
製造例１で得られたフィルム（F-1）は、上記試験に加えて、室温で水中に８時間浸し
て水洗した後、20日間室温減圧下で乾燥したものを試料として、導電性試験を行った。結果を表２に示す。
In addition to the above test, the film (F-1) obtained in Production Example 1 was immersed in water at room temperature for 8 hours, washed with water, and then dried for 20 days at room temperature under reduced pressure. went. The results are shown in Table 2.
Claims (8)
θPOであることを特徴とする請求項１〜３のいずれかに記載の表面親水性ポリオレフィン成形体。 The relationship between the water contact angle (θPO) of a polyolefin molded body and the water contact angle (θCPI) of a surface hydrophilic polyolefin molded body measured under the conditions of an air temperature of 23 ° C. and a humidity of 50% is θCPI <
It is (theta) PO, The surface hydrophilic polyolefin molded object in any one of Claims 1-3 characterized by the above-mentioned.
表面に重合開始基を導入された該ポリオレフィン成形体と、ポリエーテル基含有モノマーとを重合して、該ポリオレフィン成形体の表面にポリエーテル基含有モノマーの（共）重合体層を形成させる工程と
からなることを特徴とする請求項５に記載の表面親水性ポリオレフィン成形体の製造方法。 Introducing a polymerization initiating group into at least a part of the surface of the polyolefin molded body;
A step of polymerizing the polyolefin molded body having a polymerization initiation group introduced on the surface thereof and a polyether group-containing monomer to form a (co) polymer layer of the polyether group-containing monomer on the surface of the polyolefin molded body; It consists of these, The manufacturing method of the surface hydrophilic polyolefin molded object of Claim 5 characterized by the above-mentioned.
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