JP2008063534A - Molding for building material/civil engineering - Google Patents
Molding for building material/civil engineering Download PDFInfo
- Publication number
- JP2008063534A JP2008063534A JP2006245891A JP2006245891A JP2008063534A JP 2008063534 A JP2008063534 A JP 2008063534A JP 2006245891 A JP2006245891 A JP 2006245891A JP 2006245891 A JP2006245891 A JP 2006245891A JP 2008063534 A JP2008063534 A JP 2008063534A
- Authority
- JP
- Japan
- Prior art keywords
- molded body
- polyolefin
- group
- meth
- civil engineering
- 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
- 239000004566 building material Substances 0.000 title claims abstract description 28
- 238000000465 moulding Methods 0.000 title abstract description 15
- 229920000098 polyolefin Polymers 0.000 claims abstract description 53
- 229920006112 polar polymer Polymers 0.000 claims abstract description 42
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 24
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 9
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 7
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 239000000057 synthetic resin Substances 0.000 abstract description 2
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- 150000001875 compounds Chemical class 0.000 description 28
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- 238000000034 method Methods 0.000 description 27
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- 239000002904 solvent Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000000977 initiatory effect Effects 0.000 description 23
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
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- 238000005259 measurement Methods 0.000 description 10
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- 239000011347 resin Substances 0.000 description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 6
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- 150000001336 alkenes Chemical class 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
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- 239000005977 Ethylene Substances 0.000 description 4
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
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- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
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- 230000002140 halogenating effect Effects 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
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- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
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- 238000005211 surface analysis Methods 0.000 description 4
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- 229920001567 vinyl ester resin Polymers 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 3
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Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
本発明は、極性重合体がコーティングされたポリオレフィン系成形体からなる建材・土木用成形体に関する。 The present invention relates to a building material / civil engineering molded body comprising a polyolefin-based molded body coated with a polar polymer.
従来、床材、シート類、ガスケット・シーリング材、アスファルト改質材などの建材・土木用成形体の素材として、種々の合成樹脂、例えばポリオレフィンが用いられている。これらのうち、床材には耐衝撃性、耐傷付き性などが求められ、シート類には、柔軟性、耐ピンホール性、耐突き刺し性などが求められ、ガスケット・シーリング材には、柔軟性などが求められ、アスファルト改質材には、耐熱性、アスファルトとの相容性などが求められる。 Conventionally, various synthetic resins such as polyolefins have been used as materials for building materials such as floor materials, sheets, gaskets / sealing materials, asphalt modifiers, and the like. Of these, floor materials are required to have impact resistance and scratch resistance, sheets are required to have flexibility, pinhole resistance, puncture resistance, etc., and gaskets and sealing materials are flexible. Asphalt modifiers are required to have heat resistance and compatibility with asphalt.
本発明者らは、上記のような要求を満たす建材・土木用成形体について検討した結果、極性重合体が共有結合を介しコーティングされたポリオレフィン系成形体は上記のような要求を満たすことを見出して本発明を完成するに至った。 As a result of studying a molded article for building materials and civil engineering that satisfies the above-mentioned requirements, the present inventors have found that a polyolefin-based molded article coated with a polar polymer via a covalent bond satisfies the above-described requirements. The present invention has been completed.
かかる実状において本発明者らが解決しようとする課題は、建材・土木用途に求められる種々の要求を満たすような建材・土木用成形体を提供することである。 The problem to be solved by the present inventors in such a situation is to provide a building material / civil engineering molded body that satisfies various requirements for building materials / civil engineering applications.
本発明に係る建材・土木用成形体は、ポリオレフィン成形体（Ａ）表面に極性重合体（Ｂ）がコーティングされた成形体であり、当該極性重合体（Ｂ）がポリオレフィン成形体（Ａ）表面に共有結合を介し結合した構造を有することを特徴しており、この成形体の建材・土木用としての用途を提供する。 The building material / civil engineering molded body according to the present invention is a molded body in which the surface of the polyolefin molded body (A) is coated with the polar polymer (B), and the polar polymer (B) is the surface of the polyolefin molded body (A). It is characterized in that it has a structure bonded to the structure via a covalent bond, and the use of this molded body as a building material or civil engineering is provided.
本発明の建材・土木用成形体は、ポリオレフィン成形体表面に極性重合体セグメントが有機結合を介してコーティングされた構造を有し、ポリオレフィン基材の性質を損なうことなく、実質的にポリオレフィン成形体表面と極性重合体セグメント界面の剥離を伴わない。 The molded article for building materials and civil engineering according to the present invention has a structure in which a polar polymer segment is coated on the surface of a polyolefin molded body through an organic bond, and is substantially a polyolefin molded body without impairing the properties of the polyolefin base material. There is no separation between the surface and the polar polymer segment interface.
以下、本発明に係る建材・土木用成形体について具体的に説明する。なお本発明においては、「コーティング」とはポリオレフィン系成形体表面に、極性重合体の層が共有結合を介して被覆されることとして定義され、単なる物理的接着やイオン結合に基づく被覆は本発明に係わる「コーティング」の対象外である。 Hereinafter, the building material / civil engineering molded body according to the present invention will be described in detail. In the present invention, the term “coating” is defined as the surface of a polyolefin-based molded article being coated with a polar polymer layer via a covalent bond, and a coating based on mere physical adhesion or ionic bond is defined in the present invention. It is outside the scope of “coating”.
本発明に係る建材・土木用成形体は、ポリオレフィン成形体（Ａ）表面に極性重合体（Ｂ）がコーティングされた成形体であり、該極性重合体（Ｂ）がポリオレフィン成形体（Ａ）表面に共有結合を介し結合した構造を有すことを特徴とする成形体である。 The building material / civil engineering molded body according to the present invention is a molded body in which the surface of the polyolefin molded body (A) is coated with the polar polymer (B), and the polar polymer (B) is the surface of the polyolefin molded body (A). The molded body is characterized in that it has a structure bonded to each other through a covalent bond.
ポリオレフィン成形体（Ａ）
本発明の建材・土木用成形体を構成するポリオレフィン成形体（Ａ）は、以下の（Ｉ）〜(III)からなる群から選ばれる一種以上からなる樹脂の成形体である。
（Ｉ）以下の（Ａ１）〜（Ａ３）からなる群から選ばれるモノマーの単独重合体または共重合体樹脂。
（Ａ１）CH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物の単独重合体または共重合体。
（Ａ２）CH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物と芳香環を有するモノオレフィン化合物との共重合体。
（Ａ３）CH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物と下記一般式（１）で表される環状モノオレフィン化合物との共重合体。
Polyolefin molded product (A)
The polyolefin molded product (A) constituting the building material / civil engineering molded product of the present invention is a resin molded product comprising at least one selected from the group consisting of the following (I) to (III).
(I) A homopolymer or copolymer resin of a monomer selected from the group consisting of the following (A1) to (A3).
(A1) A homopolymer or copolymer of an α-olefin compound represented by CH 2 = CH—C x H 2x + 1 (x is 0 or a positive integer).
(A2) A copolymer of an α-olefin compound represented by CH 2 ═CH—C x H 2x + 1 (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring.
(A3) Copolymer of an α-olefin compound represented by CH 2 ═CH—C x H 2x + 1 (x is 0 or a positive integer) and a cyclic monoolefin compound represented by the following general formula (1) .
上記一般式（１）において、ｎは０または１であり、ｍは０または正の整数であり、ｑは０または１である。なおｑが１の場合には、ＲａおよびＲｂは、それぞれ独立に、下記の原子または炭化水素基を表し、ｑが０の場合には、それぞれの結合手が結合して５員環を形成する。 In the general formula (1), n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, each of R a and R b independently represents the following atom or hydrocarbon group. When q is 0, each bond is bonded to form a 5-membered ring. Form.
上記一般式（１）において、Ｒ１〜Ｒ１８ならびにＲａおよびＲｂは、それぞれ独立に、水素原子、ハロゲン原子および炭化水素基よりなる群から選ばれる原子または基を表す。 In the general formula (1), R 1 to R 18 and R a and R b each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
ここで、ハロゲン原子は、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。また炭化水素基としては、それぞれ独立に、通常、炭素原子数１〜２０のアルキル基、炭素原子数１〜２０のハロゲン化アルキル基、または炭素原子数３〜１５のシクロアルキル基が挙げられる。より具体的には、アルキル基としては、メチル基、エチル基、プロピル基、アミル基、ヘキシル基、オクチル基、デシル基、ドデシル基およびオクタデシル基が挙げられ、ハロゲン化アルキルとしては、上記のようなアルキル基を形成している水素原子の少なくとも一部がフッ素原子、塩素原子、臭素原子またはヨウ素原子で置換された基が挙げられ、シクロアルキル基としては、シクロヘキシル基が挙げられる。 Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, or a C3-C15 cycloalkyl group is mentioned normally each independently. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the halogenated alkyl include Examples include a group in which at least a part of hydrogen atoms forming such an alkyl group is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and examples of the cycloalkyl group include a cyclohexyl group.
これらの基は低級アルキル基を含有していてもよい。さらに上記一般式（Ｉ）において、Ｒ15とＲ16とが、Ｒ17とＲ18とが、Ｒ15とＲ17とが、Ｒ16とＲ18とが、Ｒ15とＲ18とが、あるいはＲ16とＲ17とがそれぞれ結合して（互いに共同して）、単環または多環を形成していてもよい。ここで形成される単環または多環としては、具体的に以下にようなものが挙げられる。 These groups may contain a lower alkyl group. In the general formula (I), R 15 and R 16 are R 17 and R 18 , R 15 and R 17 are R 16 and R 18 , R 15 and R 18 are R 16 and R 17 may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring. Specific examples of the monocyclic or polycyclic ring formed here include the following.
なお上記例示において、１および２の番号を賦した炭素原子は、上記一般式（１）において、それぞれＲ15（Ｒ16）またはＲ17（Ｒ18）が結合している炭素原子を表す。 In the above examples, the carbon atoms assigned numbers 1 and 2 represent carbon atoms to which R 15 (R 16 ) or R 17 (R 18 ) are bonded in the general formula (1).
上記一般式（１）で表される環状オレフィンとしては、具体的には、ビシクロ［2.2.1］ヘプト-2- エン誘導体、トリシクロ［4.3.0.12,5］-3- デセン誘導体、トリシクロ［4.3.0.12,5］-3- ウンデセン誘導体、テトラシクロ［4.4.0.12,5.17,10］-3- ドデセン誘導体、ペンタシクロ［7.4.0.12,5.19,12.08,13］-3- ペンタデセン誘導体、ペンタシクロ［6.5.1.13,6.02,7.09,13］-4- ペンタデセン誘導体、ペンタシクロ［8.4.0.12,3.19,12.08,13］-3- ヘキサデセン誘導体、ペンタシクロ［6.6.1.13,6.02,7.09,14］-4- ヘキサデセン誘導体、ペンタシクロペンタデカジエン誘導体、ヘキサシクロ［6.6.1.13,6.110,13.02,7.09,14］-4- ヘプタデセン誘導体、ヘプタシクロ［8.7.0.13,6.110,17.112,15.02,7.011,16 ］-4- エイコセン誘導体、ヘプタシクロ-5- エイコセン誘導体、ヘプタシクロ［8.8.0.14,7.111,18.113,16.03,8.012,17］-5- ヘンエイコセン誘導体、オクタシクロ［8.8.0.12,9.14,7.111,18.113,16.03,8.012,17］-5- ドコセン誘導体、ノナシクロ［10.9.1.14,7.113,20.115,18.03,8.02,10.012,21.014,19］-5- ペンタコセン誘導体、ノナシクロ［10.10.1.15,8.114,21.116,19.02,11.04,9.013,22.015,20］-5-ヘキサコセン誘導体などが挙げられる。 Specific examples of the cyclic olefin represented by the general formula (1) include bicyclo [2.2.1] hept-2-ene derivatives, tricyclo [4.3.0.1 2,5 ] -3-decene derivatives, and tricyclo [ 4.3.0.1 2, 5]-3-undecene derivative, tetracyclo [4.4.0.1 2,5 .1 7,10] -3- dodecene derivatives, pentacyclo [7.4.0.1 2,5 .1 9,12 .0 8, 13] -3-pentadecene derivatives, pentacyclo [6.5.1.1 3,6 .0 2,7 .0 9,13] -4- pentadecene derivatives, pentacyclo [8.4.0.1 2,3 .1 9,12 .0 8, 13] -3-hexadecene derivative, pentacyclo [6.6.1.1 3,6 .0 2,7 .0 9,14] -4- hexadecene derivatives, penta cyclopentadiene decadiene derivative, hexacyclo [6.6.1.1 3, 6 .1 10,13 .0 2,7 .0 9,14] -4-heptadecene derivatives, heptacyclo [8.7.0.1 3,6 .1 10,17 .1 12,15 .0 2,7 .0 11,16] - 4-eicosene derivatives, heptacyclo-5-eicosene derivatives, heptacyclo 8.8.0.1 4,7 .1 11,18 .1 13,16 .0 3,8 .0 12,17] -5- heneicosene derivatives, octacyclo [8.8.0.1 2,9 .1 4,7 .1 11, 18.1 13,16 .0 3,8 .0 12,17] -5-docosene derivatives, Nonashikuro [10.9.1.1 4,7 .1 13,20 .1 15,18 .0 3,8 .0 2, 10.0 12,21 .0 14,19] -5-pentacosene derivatives, Nonashikuro [10.10.1.1 5,8 .1 14,21 .1 16,19 .0 2,11 .0 4,9 .0 13, 22.0 15,20] -5-hexacosenoic derivatives.
上記のような一般式（Ｉ）で表される環状モノオレフィン化合物は、シクロペンタジエンと対応する構造を有するオレフィン類とを、ディールス・アルダー反応させることによって製造することができる。これらの環状オレフィンは、単独であるいは２種以上組み合わせて用いることができる。 The cyclic monoolefin compound represented by the general formula (I) as described above can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to Diels-Alder reaction. These cyclic olefins can be used alone or in combination of two or more.
（Ａ１）CH 2 ＝CH-C ｘ H 2ｘ+1 （ｘは０または正の整数）で示されるα-オレフィン化合物の単独重合体または共重合体
本発明で用いられるCH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物の単独重合体または共重合体(Ａ１)において、CH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物としては、具体的には、エチレン、プロピレン、1-ブテン、1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、3-メチル-1-ペンテン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセンなどの炭素数が４〜２０の直鎖状または分岐状のα-オレフィンが挙げられる。これらの例示オレフィン類の中では、エチレン、プロピレン、1-ブテン、1-ヘキセン、４-メチル-１-ペンテン、1-オクテンから選ばれる少なくても１種以上のオレフィンを使用することが好ましい。
(A1) Homopolymer or copolymer of α-olefin compound represented by CH 2 ═CH—C x H 2x + 1 (x is 0 or a positive integer) CH 2 ═CH—C x used in the present invention In a homopolymer or copolymer (A1) of an α-olefin compound represented by H 2x + 1 (x is 0 or a positive integer), CH 2 = CH—C x H 2x + 1 (x is 0 or positive) Specific examples of the α-olefin compound represented by an integer of ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, etc., linear or branched having 4 to 20 carbon atoms These α-olefins may be mentioned. Among these exemplified olefins, it is preferable to use at least one olefin selected from ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene.
本発明で用いられるCH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物の単独重合体または共重合体(Ａ１)としては、上記のα-オレフィン化合物を単独重合または共重合して得られるものであれば特に制限はないが、低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖状低密度ポリエチレン、超高分子量ポリエチレンなどのエチレン系重合体、プロピレンホモポリマー、プロピレンランダムコポリマー、プロピレンブロックコポリマーなどのプロピレン系重合体、ポリブテン、ポリ（４-メチル-１-ペンテン）、ポリ（１-ヘキセン）、エチレン-プロピレン共重合体、エチレン-ブテン共重合体、エチレン-ヘキセン共重合体、エチレン-オクテン共重合体、エチレン-（４-メチル-１-ペンテン）共重合体、プロピレン-ブテン共重合体、プロピレン-（４-メチル-１-ペンテン）共重合体、プロピレン-ヘキセン共重合体、プロピレン-オクテン共重合体などが好ましく挙げられる。 As the α-olefin compound homopolymer or copolymer (A1) represented by CH 2 ═CH—C x H 2x + 1 (x is 0 or a positive integer) used in the present invention, the above α- There is no particular limitation as long as it is obtained by homopolymerization or copolymerization of an olefin compound, but ethylene heavy polymers such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultrahigh molecular weight polyethylene, etc. Propylene polymers such as polymers, propylene homopolymers, propylene random copolymers, propylene block copolymers, polybutene, poly (4-methyl-1-pentene), poly (1-hexene), ethylene-propylene copolymers, ethylene-butene Copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, ethylene- (4-methyl-1-pentene) copolymer And propylene-butene copolymer, propylene- (4-methyl-1-pentene) copolymer, propylene-hexene copolymer, propylene-octene copolymer and the like.
（Ａ２）CH 2 ＝CH-C ｘ H 2ｘ+1 （ｘは０または正の整数）で示されるα-オレフィン化合物と芳香環を有するモノオレフィン化合物との共重合体
本発明で用いられるCH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物と芳香環を有するモノオレフィン化合物との共重合体(Ａ２)において、CH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物としては、上記(Ａ１)の項で記載したものと同様のα-オレフィン化合物が挙げられ、芳香環を有するモノオレフィン化合物としては、具体的には、スチレン、ビニルトルエン、α-メチルスチレン、クロルスチレン、スチレンスルホン酸及びその塩等のスチレン系化合物やビニルピリジンなどが挙げられる。
(A2) Copolymer of α-olefin compound represented by CH 2 ═CH—C x H 2x + 1 (x is 0 or a positive integer) and monoolefin compound having an aromatic ring CH 2 used in the present invention In the copolymer (A2) of an α-olefin compound represented by = CH-C x H 2x + 1 (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring, CH 2 = CH-C x Examples of the α-olefin compound represented by H 2x + 1 (x is 0 or a positive integer) include the same α-olefin compounds as described in the above section (A1), and a monoolefin having an aromatic ring Specific examples of the compound include styrene compounds such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof, and vinylpyridine.
本発明で用いられるCH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物と芳香環を有するモノオレフィン化合物との共重合体(Ａ２)としては、上記のα-オレフィン化合物と芳香環を有するモノオレフィン化合物とを共重合して得られるものであれば特に制限はない。 As a copolymer (A2) of an α-olefin compound represented by CH 2 ═CH—C x H 2x + 1 (x is 0 or a positive integer) and a monoolefin compound having an aromatic ring used in the present invention, As long as it is obtained by copolymerizing the above α-olefin compound and a monoolefin compound having an aromatic ring, there is no particular limitation.
（Ａ３）CH 2 ＝CH-C ｘ H 2ｘ+1 （ｘは０または正の整数）で示されるα-オレフィン化合物と下記一般式（II）で表される環状モノオレフィン化合物との共重合体
本発明で用いられるCH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物と上記一般式（I）で表される環状モノオレフィン化合物との共重合体（Ａ３）において、CH2＝CH-CｘH2ｘ+1（ｘは０または正の整数）で示されるα-オレフィン化合物としては、上記（Ａ１）の項で記載したものと同様のα-オレフィン化合物が挙げられ、上記環状モノオレフィン化合物から誘導される構成単位は、下記一般式（２）で示される。
(A3) Copolymer of α-olefin compound represented by CH 2 ═CH—C x H 2x + 1 (x is 0 or a positive integer) and cyclic monoolefin compound represented by the following general formula (II) The α-olefin compound represented by CH 2 = CH—C x H 2x + 1 (x is 0 or a positive integer) used in the present invention and the cyclic monoolefin compound represented by the above general formula (I) In the polymer (A3), the α-olefin compound represented by CH 2 = CH—C x H 2x + 1 (x is 0 or a positive integer) is the same as that described in the section (A1) above. An α-olefin compound is exemplified, and a structural unit derived from the cyclic monoolefin compound is represented by the following general formula (2).
式(２)において、ｎ、ｍ、ｑ、Ｒ1 〜Ｒ18ならびにＲa 、Ｒb は式（１）と同義である。
（II）エチレン-ビニルエステル系共重合体樹脂および(III)エチレン-（メタ）アクリル酸エステル系共重合体樹脂。
In the formula (2), n, m, q, R 1 to R 18 and R a and R b have the same meanings as in the formula (1).
(II) ethylene-vinyl ester copolymer resin and (III) ethylene- (meth) acrylic ester copolymer resin.
エチレン-ビニルエステル系共重合体樹脂、及びエチレン-（メタ）アクリル酸エステル系共重合体樹脂は、高圧ラジカル重合法で製造でき、エチレンとラジカル重合し得る単量体とを共重合して得られる。 Ethylene-vinyl ester copolymer resins and ethylene- (meth) acrylic ester copolymer resins can be produced by high-pressure radical polymerization, and are obtained by copolymerizing ethylene and a monomer capable of radical polymerization. It is done.
エチレン-ビニルエステル系共重合体のビニルエステルとしては、例えば酢酸ビニル、プロピオン酸ビニル、ネオ酸ビニルなどが挙げられる。 Examples of the vinyl ester of the ethylene-vinyl ester copolymer include vinyl acetate, vinyl propionate, and vinyl neonate.
エチレン-（メタ）アクリル酸エステル系共重合体の（メタ）アクリル酸エステルとしては、たとえばアクリル酸メチル、アクリル酸エチル、アクリル酸ｎ-プロピル、アクリル酸イソプロピル、アクリル酸ｎ-ブチル、アクリル酸ｔ-ブチル、アクリル酸イソブチルなどのアクリル酸エステル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ-プロピル、メタクリル酸イソプロピル、メタクリル酸ｎ-ブチル、メタクリル酸ｔ-ブチル、メタクリル酸イソブチルなどのメタクリル酸エステルであって炭素数４〜８の不飽和カルボン酸エステルなどが挙げられる。これらのコモノマーは一種又は二種以上用いることができる。 Examples of the (meth) acrylic acid ester of the ethylene- (meth) acrylic acid ester-based copolymer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, and acrylic acid t. -Acrylic acid esters such as butyl and isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate And an unsaturated carboxylic acid ester having 4 to 8 carbon atoms. These comonomers can be used alone or in combination of two or more.
上述した（Ｉ）〜(III)からなる群から選ばれる一種以上からなるポリオレフィン系樹脂の中でも、好ましいポリオレフィン系樹脂として、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−、プロピレン系エラストマー、イソタクチックポリポリプロピレン、シンジオタクチックポリプロピレン、高圧法低密度ポリエチレン及びそのアクリル酸、アクリル酸エステル、酢酸ビニルとのコポリマー、ポリオレフィン系アイオノマー、４−メチルペンテン−１重合体、エチレン−環状オレフィン共重合体などが挙げられる。また、過酸化物存在下、アクリル酸エステルや無水マレイン酸などで、グラフト変性されたポリオレフィン樹脂など、上述のポリオレフィン樹脂をあらゆる手法で変性させた樹脂も、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として適用される。 Among polyolefin resins consisting of one or more selected from the group consisting of (I) to (III) described above, preferred polyolefin resins include high density polyethylene, medium density polyethylene, ethylene elastomer, propylene elastomer, isotactic resin. Tick polypolypropylene, syndiotactic polypropylene, high-pressure low-density polyethylene and its acrylic acid, acrylate ester, copolymer with vinyl acetate, polyolefin ionomer, 4-methylpentene-1 polymer, ethylene-cycloolefin copolymer, etc. Is mentioned. In addition, a resin obtained by modifying the above-mentioned polyolefin resin by any technique, such as a polyolefin resin graft-modified with an acrylate ester or maleic anhydride in the presence of a peroxide, also constitutes the polyolefin molded article according to the present invention. Applicable as polyolefin resin.
本発明のポリオレフィン成形体は、これらのポリオレフィン樹脂を主成分とする成形体であり、他のあらゆる材料、例えば、上記のポリオレフィン樹脂以外の樹脂、難燃剤や無機フィラー成分等が含まれていてもよく、各種の添加剤、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、消泡剤等が添加されている組成物でも構わない。 The polyolefin molded body of the present invention is a molded body mainly composed of these polyolefin resins, and may contain any other materials, for example, resins other than the above polyolefin resins, flame retardants, inorganic filler components, and the like. Well, various additives such as softeners, stabilizers, fillers, antioxidants, crystal nucleating agents, waxes, thickeners, mechanical stability imparting agents, leveling agents, wetting agents, film-forming aids, crosslinking It may be a composition to which an agent, an antiseptic, a rust inhibitor, a pigment, a filler, a dispersant, an antifreezing agent, an antifoaming agent and the like are added.
極性重合体（Ｂ）
本発明に係るポリオレフィン系成形体を構成する極性重合体（Ｂ）とは、ヘテロ原子あるいは芳香族環を有するビニルモノマーの付加重合体あるいは、小員環化合物の開環重合体である。
Polar polymer (B)
The polar polymer (B) constituting the polyolefin-based molded product according to the present invention is an addition polymer of a vinyl monomer having a hetero atom or an aromatic ring or a ring-opening polymer of a small ring compound.
これら重合体からなる極性重合体（Ｂ）としては、炭素-炭素不飽和結合を少なくとも一つ有する有機化合物から選ばれる１種以上のモノマーの単独重合体または共重合体であり、ゲルパーミエーションクロマトグラフィー（GPC）で測定されるポリスチレン換算数平均分子量(Mn）：100〜1000000、好ましくは、500〜500000、更に好ましくは1000〜100000の極性重合体であることが好ましい。 The polar polymer (B) comprising these polymers is a homopolymer or copolymer of one or more monomers selected from organic compounds having at least one carbon-carbon unsaturated bond, and is a gel permeation chromatography. A polystyrene-reduced number average molecular weight (Mn) measured by chromatography (GPC): 100 to 100,000, preferably 500 to 500,000, more preferably 1,000 to 100,000.
これら炭素-炭素不飽和結合を少なくても一つ有する有機化合物から選ばれる１種以上のモノマーの具体例として、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸-ｎ-プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸-ｎ-ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸-ｔｅｒｔ-ブチル、（メタ）アクリル酸-ｎ-ペンチル、（メタ）アクリル酸-ｎ-ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸-ｎ-ヘプチル、（メタ）アクリル酸-ｎ-オクチル、（メタ）アクリル酸-２-エチルヘキシル、（メタ）アクリル酸ノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸トルイル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸-２-メトキシエチル、（メタ）アクリル酸-３-メトキシブチル、（メタ）アクリル酸-２-ヒドロキシエチル、（メタ）アクリル酸-２-ヒドロキシプロピル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸２-アミノエチル、（メタ）アクリル酸２-（ジメチルアミノ）エチル、γ-（メタクリロイルオキシプロピル）トリメトキシシラン、（メタ）アクリル酸のエチレンオキサイド付加物、（メタ）アクリル酸トリフルオロメチルメチル、（メタ）アクリル酸２-トリフルオロメチルエチル、（メタ）アクリル酸２-パーフルオロエチルエチル、（メタ）アクリル酸２-パーフルオロエチル-２-パーフルオロブチルエチル、（メタ）アクリル酸２-パーフルオロエチル、（メタ）アクリル酸パーフルオロメチル、（メタ）アクリル酸ジパーフルオロメチルメチル、（メタ）アクリル酸２-パーフルオロメチル-２-パーフルオロエチルメチル、（メタ）アクリル酸２-パーフルオロヘキシルエチル、（メタ）アクリル酸２-パーフルオロデシルエチル、（メタ）アクリル酸２-パーフルオロヘキサデシルエチル等の（メタ）アクリル酸系モノマー、スチレン、ビニルトルエン、α-メチルスチレン、クロルスチレン、スチレンスルホン酸及びその塩等のスチレン系モノマー、パーフルオロエチレン、パーフルオロプロピレン、フッ化ビニリデン等のフッ素含有ビニルモノマー、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のケイ素含有ビニル系モノマー、無水マレイン酸、マレイン酸、マレイン酸のモノアルキルエステル及びジアルキルエステル、フマル酸、フマル酸のモノアルキルエステルおよびジアルキルエステル、マレイミド、メチルマレイミド、エチルマレイミド、プロピルマレイミド、ブチルマレイミド、ヘキシルマレイミド、オクチルマレイミド、ドデシルマレイミド、ステアリルマレイミド、フェニルマレイミド、シクロヘキシルマレイミド等のマレイミド系モノマー、アクリロニトリル、メタクリロニトリル等のニトリル基含有ビニル系モノマー、（メタ）アクリルアミド、Ｎ-メチル（メタ）アクリルアミド、Ｎ-エチル（メタ）アクリルアミド、Ｎ-プロピル（メタ）アクリルアミド、Ｎ-イソプロピル（メタ）アクリルアミド、Ｎ-ブチル（メタ）アクリルアミド、Ｎ，Ｎ-ジメチル（メタ）アクリルアミド等のアミド基含有ビニル系モノマー、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、安息香酸ビニル、桂皮酸ビニル等のビニルエステル系モノマー、エチレン、プロピレン、ブテン等のオレフィン系モノマー、ブタジエン、イソプレン等のジエン系モノマー、塩化ビニル、塩化ビニリデン、塩化アリル、アリルアルコール等、更には、末端にアクロイル基、メタクロイル基やスチリル基などの炭素-炭素不飽和結合を有し、分子量が１００〜１０００００のマクロモノマー等が挙げられる。 Specific examples of one or more monomers selected from organic compounds having at least one carbon-carbon unsaturated bond include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, ( (Meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid-n -Pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, Benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, (meth ) Ethylene oxide adduct of acrylic acid, trifluoromethyl methyl (meth) acrylate, 2-trifluoromethyl ethyl (meth) acrylate, 2-perfluoroethyl ethyl (meth) acrylate, 2- (meth) acrylic acid 2- Perfluoroethyl-2-perfluorobutylethyl, (meth) acrylic acid 2-perfluoroethyl Perfluoromethyl (meth) acrylate, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate , (Meth) acrylic monomers such as 2-perfluorodecylethyl (meth) acrylate and 2-perfluorohexadecylethyl (meth) acrylate, styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfone Styrene monomers such as acids and their salts, fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride, silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane, maleic anhydride, maleic Acid, maleic acid monoa Alkyl and dialkyl esters, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide Maleimide monomers such as nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N Amide group-containing vinyl such as isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide Monomers, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and other olefin monomers, ethylene, propylene, butene and other olefin monomers, butadiene, isoprene and other diene monomers, vinyl chloride , Vinylidene chloride, allyl chloride, allyl alcohol, and the like, and further, a macromonomer having a carbon-carbon unsaturated bond such as an acroyl group, a methacryloyl group, or a styryl group at the terminal and having a molecular weight of 100 to 100,000.
本発明で用いられる付加重合体からなる極性重合体（Ｂ）としては、（メタ）アクリル酸およびその誘導体、（メタ）アクリロニトリル、スチレンおよびその誘導体から選ばれる１種以上の単量体を、（共）重合して得られる重合体が好ましく、（メタ）アクリル酸エステル、スチレン、（メタ）アクリルアミド、（メタ）アクリロニトリル、（メタ）アクリル酸の単独重合体および共重合体がより好ましく、特に、メタクリル酸メチル、スチレン、アクリル酸メチル、アクリロニトリル、アクリル酸ブチル、アクリルアミドの単独重合体あるいは、これらを主モノマーとした共重合体が好ましい。 As the polar polymer (B) comprising the addition polymer used in the present invention, one or more monomers selected from (meth) acrylic acid and derivatives thereof, (meth) acrylonitrile, styrene and derivatives thereof, Polymers obtained by copolymerization are preferred, (meth) acrylic acid esters, styrene, (meth) acrylamide, (meth) acrylonitrile, (meth) acrylic acid homopolymers and copolymers are more preferred, A homopolymer of methyl methacrylate, styrene, methyl acrylate, acrylonitrile, butyl acrylate and acrylamide, or a copolymer containing these as main monomers is preferred.
また、極性重合体（Ｂ）からなるコート層は、他の溶剤との親和性あるいは他樹脂との親和性が重要となる用途で使用する場合、平滑な表面を有す重合体であることが望ましい。この場合、有機溶媒に不溶な極性重合体（B）や、表面が非平滑となる極性重合体（Ｂ）は好ましくない。 In addition, the coat layer made of the polar polymer (B) may be a polymer having a smooth surface when used in applications where affinity with other solvents or affinity with other resins is important. desirable. In this case, the polar polymer (B) insoluble in the organic solvent and the polar polymer (B) having a non-smooth surface are not preferable.
一方、小員環化合物の開環重合体からなる極性重合体（Ｂ）としては、一種以上のラクトン類、ラクタム類、環状エーテル類、環状酸無水物または環状ホルマール類などの小員環化合物が開環して、それらが互いに付加した構造が好ましく挙げられる。 On the other hand, the polar polymer (B) composed of a ring-opening polymer of a small ring compound includes small ring compounds such as one or more lactones, lactams, cyclic ethers, cyclic acid anhydrides or cyclic formals. A structure in which the ring is opened and they are mutually added is preferred.
開環重合体を得るための小員環化合物としては、容易に開環重合するものであれば特に限定されるものではないが、開環重合のし易さからラクトン類、環状エーテル類が好ましい。 The small ring compound for obtaining the ring-opening polymer is not particularly limited as long as it easily undergoes ring-opening polymerization, but lactones and cyclic ethers are preferable because of the ease of ring-opening polymerization. .
ラクトン類として、具体的にはグリコリド、ラクチド、さらにα-ヒドロキシ酪酸、α-ヒドロキシ吉草酸、α-ヒドロキシイソ吉草酸、α-ヒドロキシカプロン酸、α-ヒドロキシイソカプロン酸、α-ヒドロキシ-β-メチル吉草酸、α-ヒドロキシヘプタン酸等の分子間環状ジエステルが挙げられる。これらのなかで、グリコリド、ラクチドは容易に入手することができ、これらのポリマーの物理的性質が望ましいものであり、好ましいラクトン類である。また、不斉炭素を有するものは、Ｌ体、Ｄ体、ラセミ体、メソ体のいずれでもよい。 Specific examples of lactones include glycolide, lactide, α-hydroxybutyric acid, α-hydroxyvaleric acid, α-hydroxyisovaleric acid, α-hydroxycaproic acid, α-hydroxyisocaproic acid, α-hydroxy-β- And intermolecular cyclic diesters such as methyl valeric acid and α-hydroxyheptanoic acid. Among these, glycolide and lactide are easily available, and the physical properties of these polymers are desirable, and are preferred lactones. Moreover, what has asymmetric carbon may be any of L-form, D-form, racemic form, and meso form.
環状エーテル類の具体的例としては、エチレンオキシド、プロピレンオキシド、イソブチレンオキシド、シス-１，２-ブチレンオキシド、トランス-１，２-ブチレンオキシド、スチレンオキシド、シクロペンテンオキシド、シクロヘキセンオキシド、エピクロロヒドリン、グリシドール、グリシジルフェニルエーテル、オキセタン、２-メチルオキセタン、２，２-ジメチルオキセタン、２-クロルメチルオキセタン、３，３-ジメチルオキセタン、３-メチル-３-クロロメチルオキセタン、３，３-ビス（クロロメチル）オキセタン、３-（トリメチルシリルオキシメチル）オキセタン、テトラヒドロフラン、２-メチル-テトラヒドロフラン、３-メチル-テトラヒドロフラン、２，５-ジメトキシテトラヒドロフラン、２-エトキシテトラヒドロフラン、メチルテトラヒドロフルフリルエーテル、２，３-ジヒドロベンゾフラン、２，３-ジヒドロフラン、２，５-ジヒドロフラン、テトラヒドロフランアセチックアシドエチルエステル、テトラヒドロフルフリルクロライド、テトラヒドロフルフリルアセテート、テトラヒドロフルフリルプロピオネート、テトラヒドロフルフリルｎ-ブチレート、テトラヒドロフルフリルメタクリレート等を挙げることができる。これらのうち、原料の入手しやすさからエチレンオキシド、プロピレンオキシド、オキセタン、テトラヒドロフランが好ましい。 Specific examples of cyclic ethers include ethylene oxide, propylene oxide, isobutylene oxide, cis-1,2-butylene oxide, trans-1,2-butylene oxide, styrene oxide, cyclopentene oxide, cyclohexene oxide, epichlorohydrin, Glycidol, glycidyl phenyl ether, oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 2-chloromethyloxetane, 3,3-dimethyloxetane, 3-methyl-3-chloromethyloxetane, 3,3-bis (chloro Methyl) oxetane, 3- (trimethylsilyloxymethyl) oxetane, tetrahydrofuran, 2-methyl-tetrahydrofuran, 3-methyl-tetrahydrofuran, 2,5-dimethoxytetrahydrofuran, 2-ethoxytetrahydrofuran, Til tetrahydrofurfuryl ether, 2,3-dihydrobenzofuran, 2,3-dihydrofuran, 2,5-dihydrofuran, tetrahydrofuran acetic acid ethyl ester, tetrahydrofurfuryl chloride, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, Examples thereof include tetrahydrofurfuryl n-butyrate, tetrahydrofurfuryl methacrylate, and the like. Among these, ethylene oxide, propylene oxide, oxetane, and tetrahydrofuran are preferable because of easy availability of raw materials.
発明で用いられる極性重合体（Ｂ）は末端にハロゲン原子や種々の分子を修飾したものでも良く、一部のモノマー単位が、加水分解を起こしたものや、金属、低分子や導入された反応性基を介し変性されたり、架橋されたものでも良い。 The polar polymer (B) used in the invention may be modified with a halogen atom or various molecules at the terminal, and some of the monomer units are hydrolyzed, metal, low molecule or introduced reaction. It may be modified or cross-linked via a functional group.
本発明の建材・土木用成形体
本発明の建材・土木用成形体は、前述したポリオレフィン成形体（Ａ）表面に極性重合体（Ｂ）がコーティングされた成形体であり、当該極性重合体（Ｂ）がポリオレフィン成形体（Ａ）表面に共有結合を介し結合した構造を有すことから、極性重合体（Ｂ）の剥離や各種有機溶剤などによる溶出などが起き難い事が特徴としてあげられる。
この共有結合様式について、当該極性重合体（Ｂ）はポリオレフィン成形体（Ａ）表面に存在するポリオレフィン成形体を構成するポリオレフィン鎖(a)と直接共有結合で結ばれていることが好ましいが、表面をコーティングする当該極性重合体（Ｂ）の性質を損なわない程度の短いスペーサー連結部（好ましくは、極性重合体（Ｂ）の重量に対し５重量％未満）を有していても構わない。
Building Material / Civil Engineering Molded Body of the Present Invention The building material / civil engineering molded body of the present invention is a molded body in which the surface of the polyolefin molded body (A) is coated with the polar polymer (B). Since B) has a structure in which the surface of the polyolefin molded body (A) is bonded via a covalent bond, the polar polymer (B) is hardly peeled off or eluted by various organic solvents.
For this covalent bond mode, the polar polymer (B) is preferably directly covalently bonded to the polyolefin chain (a) constituting the polyolefin molded body existing on the surface of the polyolefin molded body (A). It may have a short spacer connecting part (preferably less than 5% by weight based on the weight of the polar polymer (B)) that does not impair the properties of the polar polymer (B) that coats.
ただし、この場合、連結部はすべて共有結合の連鎖によることが必須である。
その結合様式は、光・熱・水分等の外的な刺激に対し化学的安定性に優れる共有結合のみからなることが好ましい。
However, in this case, it is essential that all the linking parts are based on a covalent bond chain.
The bonding mode is preferably composed only of a covalent bond that is excellent in chemical stability against external stimuli such as light, heat, and moisture.
この観点から、極性重合体（Ｂ）が、炭素-炭素不飽和結合を少なくとも一つ有するモノマーの付加重合体である場合、かつ、ポリオレフィン成形体（Ａ）表面との連結部が炭素-炭素共有結合またはその連鎖による共有結合にて連結していることが好ましい構造として挙げられる。 From this viewpoint, when the polar polymer (B) is an addition polymer of a monomer having at least one carbon-carbon unsaturated bond, and the connecting portion with the surface of the polyolefin molded body (A) is carbon-carbon sharing A preferred structure is that they are linked by a bond or a covalent bond formed by a chain thereof.
例えば、連結部に金属を介す結合が含まれる場合、本成形体の使用条件または、本成形体の積層体や塗装等のあらゆる用途への加工過程において、熱や水分等により容易に結合の解離を発生させ、当該極性重合体（Ｂ）の剥離を起こさせる原因となる場合がある。 For example, when the connection includes a metal-mediated bond, it can be easily bonded by heat, moisture, etc. in the usage conditions of the molded body or in the process of processing for any application such as a laminate or coating of the molded body. It may cause dissociation and cause peeling of the polar polymer (B).
本発明の建材・土木用成形体においては、ポリオレフィン成形体（Ａ）の表面が極性重合体（Ｂ）によりコーティングされているものであるが、用途に応じて部分的にコーティングされていても完全にコーティングされていても良い。また、コーティングされている部分とされていない部分が二次元的に規則的に配列していてもよい。 In the building material / civil engineering molded body of the present invention, the surface of the polyolefin molded body (A) is coated with the polar polymer (B), but it may be completely coated even if it is partially coated depending on the application. It may be coated. Further, the coated part and the non-coated part may be regularly arranged two-dimensionally.
また、本発明の建材・土木用成形体表面において、ポリオレフィン成形体（Ａ）表面にコーティングされる極性重合体（Ｂ）の厚みは、極性重合体の種類、分子量や分子数に起因するため目的の用途に応じて調整されるものであるが、１ｎｍ〜５ｍｍの範囲、好ましくは、１０ｎｍ〜１ｍｍである。コーティング層である極性重合体セグメント（Ｂ）のポリスチレン換算数平均分子量(Ｍｎ)は、５００〜５０００００であることが好ましい。 In addition, the thickness of the polar polymer (B) coated on the surface of the polyolefin molded body (A) on the surface of the building material / civil engineering molded body of the present invention is derived from the type, molecular weight, and number of molecules of the polar polymer. Although it is adjusted according to the use of, it is the range of 1 nm-5 mm, Preferably, it is 10 nm-1 mm. It is preferable that the polystyrene conversion number average molecular weight (Mn) of the polar polymer segment (B) which is a coating layer is 500-500000.
本発明の建材・土木用成形体の製造方法
本発明の建材・土木用成形体は、ポリオレフィン成形体（Ａ）表面に存在する重合開始基を開始反応点として極性化合物(モノマー)を重合させる方法により、ポリオレフィン成形体（Ａ）表面のみを極性重合体（Ｂ）でコーティングすることを可能にする。
Method for producing building material / civil engineering molded body of the present invention The building material / civil engineering molded body of the present invention is a method of polymerizing a polar compound (monomer) using a polymerization initiating group present on the surface of a polyolefin molded body (A) as an initiation reaction site. Thus, only the surface of the polyolefin molded body (A) can be coated with the polar polymer (B).
本発明に係わるポリオレフィン成形体（Ａ）を調製するための成形加工法は特に限定されるものではなく、熱可塑性樹脂について一般に用いられている成形法、すなわち射出成形、押出成形、中空成形、熱成形、プレス成形などの各種成形法が適応できる。 The molding method for preparing the polyolefin molded body (A) according to the present invention is not particularly limited, and is a molding method generally used for thermoplastic resins, that is, injection molding, extrusion molding, hollow molding, heat molding. Various molding methods such as molding and press molding can be applied.
重合開始基をポリオレフィン成形体（Ａ）に導入する方法は、特に限定されるものではないが、あらかじめ、重合開始基が導入されたポリオレフィン樹脂を成形しても、逆に、ポリオレフィン成形体に低分子あるいは高分子の重合開始基を表面修飾させても良い。また、フィルムやシートに成形された、重合開始基が導入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、木材などにコーティングした状態で、極性化合物(モノマー)を重合させてもよい。 The method for introducing the polymerization initiating group into the polyolefin molded body (A) is not particularly limited. However, even if the polyolefin resin having the polymerization initiating group introduced in advance is molded, A molecule or a polymerization initiating group of a polymer may be surface-modified. In addition, a polar compound (monomer) may be polymerized in a state where a polyolefin resin into which a polymerization initiating group has been introduced is coated on another resin film molded body, metal, paper, wood, etc., which is molded into a film or sheet. .
本発明の建材・土木用成形体、すなわち極性重合体（Ｂ）がコーティングされた成形体の製造方法として、重合開始基が導入されたポリオレフィン成形体（Ａ）表面での極性化合物(モノマー)の重合工程の違いにより、以下の二つの製造方法(P-1)および(P-2)が好ましく用いられる。 As a method for producing a molded article for building materials / civil engineering of the present invention, that is, a molded article coated with the polar polymer (B), the polar compound (monomer) on the surface of the polyolefin molded article (A) into which the polymerization initiation group has been introduced. Depending on the difference in the polymerization process, the following two production methods (P-1) and (P-2) are preferably used.
（P-1） ラジカル重合開始基を共有結合したポリオレフィンからなる成形体をコーティングする方法
（Ａ’）表面において、（Ａ’）の表面に存在するラジカル重合開始基を開始点として、炭素-炭素不飽和結合を少なくとも一つ有する有機化合物から選ばれる１種以上のモノマーを制御ラジカル重合することにより製造する方法。
(P-1) A method of coating a molded body comprising a polyolefin covalently bonded to a radical polymerization initiating group (A ′), on the surface, carbon-carbon starting from the radical polymerization initiating group present on the surface of (A ′) A method for producing a polymer by controlled radical polymerization of one or more monomers selected from organic compounds having at least one unsaturated bond.
（P-2） ヘテロ原子からなる基を共有結合したポリオレフィンからなる成形体をコーティングする方法
（Ａ”）表面において、（Ａ”）の表面に存在するヘテロ原子を開始点として、小員環化合物を開環重合することにより製造する方法。
(P-2) A method of coating a molded body made of polyolefin covalently bonded to a group consisting of heteroatoms (A ″) In the surface of (A ″), starting from the heteroatoms present on the surface of (A ″), the small ring compound Is produced by ring-opening polymerization.
まず、本発明に係る、(P-1)の製造方法について説明する。
ラジカル重合開始基を共有結合したポリオレフィンからなる成形体（Ａ’）表面において、制御ラジカル重合を用いモノマーを重合することで、極性重合体（Ｂ）の分子量、分子量分布および分子末端の制御など、一次構造を制御することが可能である。
First, the method for producing (P-1) according to the present invention will be described.
On the surface of the molded article (A ′) comprising a polyolefin covalently bonded to a radical polymerization initiating group, the monomer is polymerized using controlled radical polymerization, thereby controlling the molecular weight, molecular weight distribution and molecular end of the polar polymer (B), etc. It is possible to control the primary structure.
本発明においては、極性重合体（Ｂ）を導入するための制御ラジカル重合法の種類は特に限定されないが、ポリオレフィンへの重合開始基の導入の容易さ、極性重合体（Ｂ）の種類、重合条件のより適切な手法を選ぶことができる。 In the present invention, the type of the controlled radical polymerization method for introducing the polar polymer (B) is not particularly limited, but the ease of introduction of the polymerization initiating group into the polyolefin, the type of the polar polymer (B), the polymerization You can choose a more appropriate method of conditions.
例えば、Trend Polym. Sci., （1996）, 4, 456 に開示されているように、ニトロキシドを有する基を結合し熱的な開裂によりラジカルを発生させる方法や、原子移動ラジカル重合（ATRP）と呼ばれる方法、すなわち、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、特開2004-307872号公報で開示されているような、有機ハロゲン化物又はハロゲン化スルホニル化合物を開始剤、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が挙げられる。 For example, as disclosed in Trend Polym. Sci., (1996), 4, 456, a method in which a group having a nitroxide is bonded and a radical is generated by thermal cleavage, atom transfer radical polymerization (ATRP) and Method, namely, Science, (1996), 272,866, Chem. Rev., 101, 2921 (2001), WO96 / 30421 publication, WO97 / 18247 publication, WO98 / 01480 publication, WO98 / 40415 publication, WO00 No. 156795 or Sawamoto et al., Chem. Rev., 101, 3689 (2001), JP-A-8-41117, JP-A-9-208616, JP-A-2000-264914, JP-A-2001-316410 No., JP-A No. 2002-80523, JP-A No. 2004-307872, and an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. The method of radical polymerizing a radically polymerizable monomer is mentioned.
ラジカル重合重合開始末端の導入方法の容易さ、及び選択できるモノマー種の豊富さから、原子移動ラジカル重合法は、本発明に係る極性重合体（Ｂ）を導入するために有力な制御ラジカル重合法である。 The radical transfer polymerization polymerization method is an effective controlled radical polymerization method for introducing the polar polymer (B) according to the present invention because of the ease of introduction of the radical polymerization polymerization initiation terminal and the abundance of selectable monomer species. It is.
原子移動ラジカル重合開始剤をポリオレフィン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有効である。 As a method for introducing the atom transfer radical polymerization initiator into the polyolefin, a functional group conversion method or a direct halogenation method is effective.
官能基変換法とは、水酸基、酸無水物基、ビニル基、シリル基等の官能基が導入されたポリオレフィンの官能基部位を原子移動ラジカル開始剤構造に変換する方法、例えば、公開特許公報（特開2004-131620号公報）の如く、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様な低分子化合物で修飾する方法である。
直接ハロゲン化法とは、ハロゲン化剤をポリオレフィンに直接作用させ、炭素-ハロゲン結合を有すハロゲン化ポリオレフィンを得る方法である。
The functional group conversion method is a method of converting a functional group portion of a polyolefin into which a functional group such as a hydroxyl group, an acid anhydride group, a vinyl group, or a silyl group is introduced into an atom transfer radical initiator structure, for example, a published patent publication ( JP-A-2004-131620) is a method of modifying a hydroxyl group-containing polyolefin with a low molecular weight compound such as 2-bromoisobutyric acid bromide.
The direct halogenation method is a method of obtaining a halogenated polyolefin having a carbon-halogen bond by directly acting a halogenating agent on the polyolefin.
使用するハロゲン化剤や導入されたハロゲン原子の種類については特に限定されるものではないが、原子移動ラジカル開始骨格の安定性と開始効率のバランスより臭素原子を導入された臭素化ポリオレフィンが好ましい。 The halogenating agent to be used and the kind of the halogen atom introduced are not particularly limited, but brominated polyolefin into which a bromine atom is introduced is preferable from the balance between the stability of the atom transfer radical initiation skeleton and the initiation efficiency.
また、Science,(1996),272,866等に示されるように、原子移動ラジカル重合の開始構造としては、炭素−ハロゲン原子の結合解離エネルギーが低い構造が好ましく、そのためには、３級炭素原子に直接ハロゲン原子が導入された構造やビニル基やビニリデン基などの不飽和炭素―炭素結合に結合する炭素原子にハロゲン原子が導入された構造などを発現させやすいハロゲン化剤が好ましく用いられる。 Also, as shown in Science, (1996), 272,866, etc., the structure of atom transfer radical polymerization is preferably a structure having a low bond-dissociation energy of a carbon-halogen atom. A halogenating agent that easily develops a structure in which a halogen atom is introduced or a structure in which a halogen atom is introduced into a carbon atom bonded to an unsaturated carbon-carbon bond such as a vinyl group or vinylidene group is preferably used.
このような観点より、直接ハロゲン化法によるハロゲン化ポリオレフィンを製造するにあたって、ハロゲン化剤として好ましくは、臭素（ブロミン）やＮ−ブロモスクシンイミド（ＮＢＳ）が挙げられる。 From this point of view, bromine (bromine) and N-bromosuccinimide (NBS) are preferably used as the halogenating agent in producing a halogenated polyolefin by a direct halogenation method.
本発明に係わる制御ラジカル重合を行うに当たり、溶媒を使用してもしなくても良い。使用できる溶媒としては、重合反応を阻害せず、かつラジカル重合開始基が導入されたポリオレフィンからなる成形体（Ａ’）を溶解させるものでなければ何れでも使用することができるが、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ル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、iso-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あげることができる。また、水を溶媒とすることもできる。これらの溶媒は、単独でも２種以上を混合して使用してもよい。 In performing the controlled radical polymerization according to the present invention, a solvent may or may not be used. As the solvent that can be used, any solvent can be used as long as it does not inhibit the polymerization reaction and does not dissolve the molded article (A ′) made of polyolefin into which a radical polymerization initiating group is introduced. , Aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decahydronaphthalene Solvent, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol And tert-butanol Cole solvents, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate, ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole A solvent etc. can be mention | raise | lifted. Water can also be used as a solvent. These solvents may be used alone or in admixture of two or more.
重合温度は、ラジカル重合開始基が導入されたポリオレフィンからなる成形体（Ａ’）が溶融または膨潤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できる。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一様ではないが、通常、−５０℃〜１５０℃、好ましくは０℃〜８０℃であり、更に好ましくは０℃〜５０℃である。重合反応は場合によって減圧、常圧または加圧の何れでも実施できる。上記重合反応は、酸素を除去した後、副反応を抑えるため窒素やアルゴン等の不活性ガス雰囲気下で行うことが好ましい。 The polymerization temperature can be arbitrarily set as long as the temperature is such that the molded product (A ′) made of polyolefin having a radical polymerization initiating group introduced does not melt or swell and the radical polymerization reaction proceeds. Although it is not uniform depending on the degree of polymerization of the desired polymer and the kind and amount of the radical polymerization initiator and solvent used, it is usually -50 ° C to 150 ° C, preferably 0 ° C to 80 ° C, more preferably 0. It is 50 degreeC. In some cases, the polymerization reaction can be carried out under reduced pressure, normal pressure, or increased pressure. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon after oxygen is removed to suppress side reactions.
次に(P-2)について説明する。
本発明において、ヘテロ原子からなる基が共有結合されたポリオレフィンからなる成形体（Ａ”）のヘテロ原子からなる基とは、小員環化合物を開環重合を開始させる能力を有す基であり、つまり、特定の温度条件下、あるいは酸や塩基触媒の添加によりアニオンあるいはカチオンを発生し、開環重合の活性種を生成可能な基である。
具体的には、水酸基、カルボキシル基、酸無水物基、エポキシ基、アミノ基あるいは、それらと金属化合物との反応物が好例として挙げられる。
例えば、ラクトン類であるポリラクチドの開環重合を行う場合、水酸基が表面に共有結合したポリオレフィン成形体を用い、当該モノマー存在下、オクタン酸スズ等の金属系触媒を存在させることで表面にポリ乳酸をコーティングしたポリオレフィン系成形体を得ることができる。
Next, (P-2) will be described.
In the present invention, the group consisting of heteroatoms in the molded article (A ″) made of polyolefin to which a group consisting of heteroatoms is covalently bonded is a group having the ability to initiate ring-opening polymerization of a small ring compound. That is, it is a group capable of generating an anion or a cation under a specific temperature condition or by addition of an acid or a base catalyst to generate an active species of ring-opening polymerization.
Specific examples include a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, or a reaction product of these with a metal compound.
For example, when ring-opening polymerization of polylactide, which is a lactone, is performed by using a polyolefin molded body having a hydroxyl group covalently bonded to the surface, and in the presence of the monomer, a metal catalyst such as tin octoate is present on the surface to form polylactic acid. Can be obtained.
本発明の開環重合を行うに当たり、溶媒を使用してもしなくても良い。使用できる溶媒としては、重合反応を阻害せず、かつポリオレフィン成形体を溶解させるものでければ何れでも使用することができるが、非プロトン性溶媒が好ましい。例えば、具体例として、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ルエチレン等の塩素化炭化水素系溶媒、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あげることができる。これらの溶媒は、単独でもまたは２種以上を混合して使用してもよい。 In performing the ring-opening polymerization of the present invention, a solvent may or may not be used. Any solvent can be used as long as it does not inhibit the polymerization reaction and dissolves the polyolefin molded article, but an aprotic solvent is preferred. For example, specific examples include aromatic hydrocarbon solvents such as benzene, toluene and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane, cyclohexane, methylcyclohexane and decahydronaphthalene. Alicyclic hydrocarbon solvents, chlorinated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone Ester solvents such as ethyl acetate and dimethyl phthalate, ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran and dioxyanisole, etc. Kill. These solvents may be used alone or in admixture of two or more.
反応温度は、ヘテロ原子からなる基が共有結合されたポリオレフィン成形体（Ａ”）が溶融または膨潤しない温度でかつ開環重合反応が進行する温度であれば何れでも構わず、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一様ではないが、通常、−５０℃〜１５０℃である。好ましくは０℃〜８０℃であり、更に好ましくは０℃〜５０℃である。反応は場合によって減圧、常圧または加圧の何れでも実施できる。 The reaction temperature may be any temperature as long as the polyolefin molded product (A ″) to which a group consisting of heteroatoms is covalently bonded does not melt or swell and the ring-opening polymerization reaction proceeds. Although it is not uniform depending on the degree of polymerization and the type and amount of the radical polymerization initiator and solvent used, it is usually -50 ° C to 150 ° C, preferably 0 ° C to 80 ° C, more preferably 0 ° C to 50 ° C. In some cases, the reaction can be performed under reduced pressure, normal pressure, or increased pressure.
また、当該開環重合を実施するにあたり、使用する小員環化合物、溶媒、触媒成分は精製されていることが好ましく、特に開環ホモ重合体を副生させないために、十分に水分を除去した系で重合実施することが好ましい。 In carrying out the ring-opening polymerization, it is preferable that the small ring compound, the solvent, and the catalyst component to be used are purified. In particular, in order not to cause the ring-opening homopolymer as a by-product, water is sufficiently removed. The polymerization is preferably carried out in the system.
本成形体の用途
本発明に係る建材・土木成形体は、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、止水シート等の建材・土木用として広範な分野において有用である。
Uses of the present molded body The building material / civil engineering molded body according to the present invention is, for example, a floor material, a floor tile, a floor sheet, a sound insulation sheet, a heat insulating panel, a vibration insulating material, a decorative sheet, a baseboard, an asphalt modifier, a gasket It is useful in a wide range of fields as building materials and civil engineering such as sealing materials, roofing sheets, and water-proof sheets.
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、本発明はこれら実施例に限定されるものではない。本実施例中に示される成形体表面のＸ線光電子分光分析は、ＳＳＩ社製、ＳＳＸ−１００型Ｘ線光電子分光装置を用い、また、ＡＴＲ／ＩＲ分析は、Ｂｉｏｒａｄ社製、ＦＴＳ−６０００型赤外分光光度計を用いて行った。 EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. The X-ray photoelectron spectroscopic analysis of the surface of the molded body shown in this example uses an SSX-100 type X-ray photoelectron spectrometer manufactured by SSI, and ATR / IR analysis is made by Biorad, FTS-6000 type. This was done using an infrared spectrophotometer.
〔製造例１〕
[ラジカル重合開始基を表面に有すポリプロピレン成形体の調製(1)]
特開２００２-１４５９４４記載の方法に準じて製造したプロピレン／１０-ウンデセン-１-オール共重合ポリマー（高温ＧＰＣ測定によるポリプロピレン換算分子量 Ｍｗ＝２６４００，Ｍｗ／Ｍｎ＝１．７１，１Ｈ-ＮＭＲ測定より得られるコモノマー含量１．０ｍｏｌ％、） １７０ｇを、脱気窒素置換された２Ｌガラス製重合器に入れ、ヘキサン１７００ｍＬ、２-ブロモイソ酪酸ブロミド９．２ｍＬをそれぞれ添加し、６０℃に昇温し、２時間加熱撹拌した。室温に戻した反応スラリー状ポリマー溶液を、桐山ロートでろ過した後、ロート上のポリマーをメタノール２００ｍＬで３回リンスした。ポリマーを５０℃、１０Ｔｏｒｒの減圧条件下で１０時間乾燥させ、白色ポリマーが得られた。１Ｈ-ＮＭＲの結果、末端ＯＨ基の９４％が２-ブロモイソ酪酸基で修飾されたハロゲン原子含有ポリプロピレンであった。このハロゲン原子含有ポリプロピレンを圧縮成形機（１８０℃，１０ＭＰａ）により、厚さ３．０ｍｍのシートに成形した。
ＡＴＲ／ＩＲ測定により本ポリプロピレン成形体の表面解析を行った結果、１７３０ｃｍ-1にエステカルボニル伸縮振動の吸収を確認でき、ＸＰＳ測定により、０．３ ａｔｍ％の臭素原子が表面に存在することが明らかとなった。このことから、本ポリプロピレン成形体表面には、原子移動ラジカル重合開始末端が存在することが確認された。
[Production Example 1]
[Preparation of polypropylene moldings having radical polymerization initiating groups on the surface (1)]
Propylene / 10-undecene-1-ol copolymer produced according to the method described in JP-A-2002-145944 (high molecular weight in terms of polypropylene by high-temperature GPC measurement Mw = 26400, Mw / Mn = 1.71, 1 H-NMR measurement 170 g of comonomer content obtained from 1.0 mol%) was put into a 2 L glass polymerizer purged with nitrogen, 1700 mL of hexane and 9.2 mL of 2-bromoisobutyric acid bromide were added, and the temperature was raised to 60 ° C. The mixture was heated and stirred for 2 hours. After the reaction slurry-like polymer solution returned to room temperature was filtered with a Kiriyama funnel, the polymer on the funnel was rinsed with 200 mL of methanol three times. The polymer was dried at 50 ° C. under a reduced pressure of 10 Torr for 10 hours to obtain a white polymer. As a result of 1 H-NMR, it was a halogen atom-containing polypropylene in which 94% of the terminal OH groups were modified with 2-bromoisobutyric acid groups. This halogen atom-containing polypropylene was molded into a sheet having a thickness of 3.0 mm by a compression molding machine (180 ° C., 10 MPa).
As a result of performing surface analysis of this polypropylene molded body by ATR / IR measurement, absorption of estecarbonyl stretching vibration can be confirmed at 1730 cm −1 , and 0.3 atm% bromine atoms may be present on the surface by XPS measurement. It became clear. From this, it was confirmed that an atom transfer radical polymerization initiation terminal is present on the surface of the polypropylene molded body.
〔製造例２〕
[ラジカル重合開始基を表面に有すポリプロピレン成形体の調製(2)]
三井化学（株）社製ポリプロピレン（［η］＝２．６）を、圧縮成形機（１８０℃，１０ＭＰａ）により、厚さ１．０ｍｍ、４ｃｍ×４ｃｍのシート状に成形した。本成形体を、酢酸ブチル溶媒５０ｍＬに浸漬させ、窒素バブリングにより反応器内を窒素置換した後に、乾燥臭素（ブロミン）０．５ｍＬを加え、５０℃に加温し、スターラーチップでゆっくりと攪拌した。２４時間反応させた後、室温に冷却し、ポリプロピレンシートを引き上げ表面をアセトンで洗浄した。ＸＰＳ測定により、本ポリプロピレン成形体の表面解析を行った結果、０．５ ａｔｍ％の臭素原子が表面に存在することが明らかとなった。
[Production Example 2]
[Preparation of polypropylene molded body having radical polymerization initiation group on the surface (2)]
Polypropylene ([η] = 2.6) manufactured by Mitsui Chemicals, Inc. was molded into a sheet having a thickness of 1.0 mm and 4 cm × 4 cm using a compression molding machine (180 ° C., 10 MPa). The molded body was immersed in 50 mL of butyl acetate solvent, and the inside of the reactor was purged with nitrogen by nitrogen bubbling. Then, 0.5 mL of dry bromine (bromine) was added, heated to 50 ° C., and slowly stirred with a stirrer chip. . After reacting for 24 hours, it was cooled to room temperature, the polypropylene sheet was pulled up, and the surface was washed with acetone. As a result of conducting a surface analysis of the polypropylene molded body by XPS measurement, it was revealed that 0.5 atm% bromine atoms exist on the surface.
〔製造例３〕
[開環重合開始基を表面に有すポリエチレン成形体の調製(1)]
特開２００２-１４５９４４記載の方法に準じて製造したエチレン／１０-ウンデセン-１-オール共重合ポリマー（高温ＧＰＣ測定によるポリエチレン換算分子量 Ｍｗ＝９０４００，Ｍｗ／Ｍｎ＝２．５３，１Ｈ-ＮＭＲ測定より得られるコモノマー含量３．９ｍｏｌ％）を圧縮成形機（１５０℃，１０ＭＰａ）により、厚さ１．０ｍｍ、４ｃｍ×４ｃｍのシートに成形した。
ＡＴＲ／ＩＲ測定により本ポリエチレン成形体の表面解析を行った結果、３５００ｃｍ-1付近にブロードな吸収が観察されたことから、本成形体表面に水酸基が存在することが確認された。
[Production Example 3]
[Preparation of polyethylene molded product having ring-opening polymerization initiation group on the surface (1)]
Ethylene / 10-undecene-1-ol copolymer produced according to the method described in JP-A-2002-145944 (polyethylene equivalent molecular weight by high-temperature GPC measurement Mw = 90400, Mw / Mn = 2.53, 1 H-NMR measurement The comonomer content obtained from 3.9 mol% was molded into a sheet having a thickness of 1.0 mm and 4 cm × 4 cm by a compression molding machine (150 ° C., 10 MPa).
As a result of surface analysis of the polyethylene molded body by ATR / IR measurement, broad absorption was observed in the vicinity of 3500 cm −1 , confirming the presence of hydroxyl groups on the surface of the molded body.
〔製造例４〕
[ポリ（メタクリル酸（２-ヒドロキシエチル））（＝ＰＨＥＭＡ）がコーティングされたポリプロピレン系成形体]
製造例１で得られたラジカル重合開始基を表面に有すポリプロピレン成形体をガラス製反応器に入れ、十分に窒素バブリングしたエタノール２５０ｍLとメタクリル酸（２-ヒドロキシエチル）４０ｍLに浸漬し、更に反応器を窒素置換した。ここに、臭化第一銅（５４８ｍｇ）とＮ，Ｎ，Ｎ’，Ｎ”，Ｎ”-ペンタメチルジエチレントリアミンの２Ｍ キシレン溶液３．７５ｍＬとキシレン５．０ｍＬの均質溶液を加え、２５℃で２４時間ゆっくり攪拌した。浸漬しているポリプロピレン成形体を取り出しアセトンで数回表面を洗浄した後、１０Ｔｏｒｒの減圧下、５０℃で１０時間乾燥した。ＡＴＲ／ＩＲで得られたポリプロピレン成形体の表面を分析したところ３２００ｃｍ-1〜３６００ｃｍ-1に、ＯＨ伸縮振動に起因するブロード吸収体，１７３０ｃｍ-1付近にエステルカルボニル伸縮振動に起因する吸収体が観察されたことからポリプロピレン成形体の表面にポリ（メタクリル酸（２-ヒドロキシエチル））が存在していることが確認された。また，透過型電子顕微鏡（ＴＥＭ）の成形体断面の写真より、ポリ（メタクリル酸（２-ヒドロキシエチル））は、約１０μｍ〜２０μｍの厚みで完全にポリプロピレンシートの表面をコートしていることが確認された。このポリプロピレン成形体をＴＨＦ処理しても、重量変化は観察されないことから、ポリ（メタクリル酸（２-ヒドロキシエチル））は基盤表面に存在するポリプロピレン主鎖に共有結合を介しコーティングされていることが示された。表面の水接触角測定の結果（表１）より、ポリプロピレン成形体表面の親水性が著しく向上していることが明らかとなった。
[Production Example 4]
[Polypropylene molded product coated with poly (methacrylic acid (2-hydroxyethyl)) (= PHEMA)]
The polypropylene molded body having the radical polymerization initiating group obtained in Production Example 1 on the surface is placed in a glass reactor, immersed in 250 mL of ethanol and 40 mL of methacrylic acid (2-hydroxyethyl) sufficiently bubbled with nitrogen, and further reacted. The vessel was purged with nitrogen. To this was added a homogeneous solution of cuprous bromide (548 mg) and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine in 2M xylene solution 3.75 mL and xylene 5.0 mL. Stir slowly for hours. The immersed polypropylene molded body was taken out, washed with acetone several times, and then dried at 50 ° C. for 10 hours under a reduced pressure of 10 Torr. To 3200cm -1 ~3600cm -1 Analysis of the surface of the obtained polypropylene molded body ATR / IR, broad absorber due to OH stretching vibration absorber due to the ester carbonyl stretching vibration in the vicinity of 1730 cm -1 is From the observation, it was confirmed that poly (methacrylic acid (2-hydroxyethyl)) was present on the surface of the polypropylene molded body. Moreover, from the photograph of the cross section of the molded body of a transmission electron microscope (TEM), it is found that poly (methacrylic acid (2-hydroxyethyl)) completely coats the surface of the polypropylene sheet with a thickness of about 10 μm to 20 μm. confirmed. Even if this polypropylene molded body is treated with THF, no change in weight is observed. Therefore, poly (methacrylic acid (2-hydroxyethyl)) is coated on the polypropylene main chain existing on the substrate surface via a covalent bond. Indicated. From the results of the water contact angle measurement on the surface (Table 1), it was revealed that the hydrophilicity of the surface of the polypropylene molded body was remarkably improved.
〔製造例５〕
[ポリメタクリル酸メチル(＝ＰＭＭＡ)がコーティングされたポリプロピレン系成形体] 製造例１で得られたラジカル重合開始基を表面に有すポリプロピレン成形体をガラス製反応器に入れ、十分に窒素バブリングしたＴＨＦ１５０ｍＬとメタクリル酸メチル１５０ｍＬに浸漬し、更に反応器を窒素置換した。ここに、臭化第一銅（５４８ｍｇ）とＮ，Ｎ，Ｎ’，Ｎ”，Ｎ”-ペンタメチルジエチレントリアミンの２Ｍ キシレン溶液３．７５ｍＬとキシレン５．０ｍＬの均質溶液を加え、６０℃で１０時間ゆっくり攪拌した。重合溶液を室温に戻し浸漬しているポリプロピレン成形体を取り出しアセトンで数回表面を洗浄した後、１０Ｔｏｒｒの減圧下、５０℃で１０時間乾燥した。ＡＴＲ／ＩＲRで得られたポリプロピレン成形体の表面を分析したところ１７３０ｃｍ-1、１２７０ｃｍ-1、１２４２ｃｍ-1、１１９３ｃｍ-1、１１４９ｃｍ-1にＰＭＭＡの特徴的なピークが観測され、シート表面へのＰＭＭＡの存在が確認された。
また，透過型電子顕微鏡（ＴＥＭ）の成形体断面の写真より、ＰＭＭＡは、約４０μｍ〜６０μｍの厚みで完全にポリプロピレンシートの表面をコートしていることが確認された。
[Production Example 5]
[Polypropylene molded body coated with polymethyl methacrylate (= PMMA)] The polypropylene molded body having the radical polymerization initiating group obtained in Production Example 1 on the surface thereof was placed in a glass reactor and sufficiently bubbled with nitrogen. The reactor was immersed in 150 mL of THF and 150 mL of methyl methacrylate, and the reactor was further purged with nitrogen. To this was added a homogeneous solution of cuprous bromide (548 mg), 3.75 mL of 2M xylene solution of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and 5.0 mL of xylene. Stir slowly for hours. The polypropylene molded body in which the polymerization solution was returned to room temperature was taken out, the surface was washed several times with acetone, and then dried at 50 ° C. for 10 hours under a reduced pressure of 10 Torr. 1730 cm -1 Analysis of the surface of the obtained polypropylene molded body ATR / IRR, 1270cm -1, 1242cm -1, 1193cm -1, characteristic peaks of PMMA was observed at 1149cm -1, to the seat surface The presence of PMMA was confirmed.
Moreover, it was confirmed from the photograph of the cross section of the molded body of the transmission electron microscope (TEM) that PMMA completely coats the surface of the polypropylene sheet with a thickness of about 40 μm to 60 μm.
〔製造例６〕
[ポリメタクリル酸メチル(＝ＰＭＭＡ)がコーティングされたポリプロピレン系成形体]
製造例２で得られたラジカル重合開始基を表面に有すポリプロピレン成形体をガラス製反応器に入れ、十分に窒素バブリングしたＴＨＦ１５０ｍＬとメタクリル酸メチル１５０ｍＬに浸漬し、更に反応器を窒素置換した。ここに、臭化第一銅（５４８ｍｇ）とＮ，Ｎ，Ｎ’，Ｎ”，Ｎ”-ペンタメチルジエチレントリアミンの２Ｍ キシレン溶液３．７５5ｍＬとキシレン５．０ｍＬの均質溶液を加え、６０℃で１０時間ゆっくり攪拌した。重合溶液を室温に戻し浸漬しているポリプロピレン成形体を取り出しアセトンで数回表面を洗浄した後、１０Ｔｏｒｒの減圧下、５０℃で１０時間乾燥した。ＡＴＲ／ＩＲで得られたポリプロピレン成形体の表面を分析したところ１７３０ｃｍ-1、１２７０ｃｍ-1、１２４２ｃｍ-1、１１９３ｃｍ-1、１１４９ｃｍ-1にＰＭＭＡの特徴的なピークが観測され、シート表面へのＰＭＭＡの存在が確認された。
[Production Example 6]
[Polypropylene molded body coated with polymethyl methacrylate (= PMMA)]
The polypropylene molded body having the radical polymerization initiating group obtained in Production Example 2 on the surface was placed in a glass reactor, immersed in 150 mL of THF and 150 mL of methyl methacrylate sufficiently bubbled with nitrogen, and the reactor was further purged with nitrogen. To this was added a homogeneous solution of cuprous bromide (548 mg) and N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine in a 2M xylene solution (3.755 mL) and xylene (5.0 mL). Stir slowly for hours. The polypropylene molded body in which the polymerization solution was returned to room temperature was taken out, the surface was washed several times with acetone, and then dried at 50 ° C. for 10 hours under a reduced pressure of 10 Torr. 1730 cm -1 Analysis of the surface of the obtained polypropylene molded body ATR / IR, 1270cm -1, 1242cm -1, 1193cm -1, characteristic peaks of PMMA was observed at 1149cm -1, to the seat surface The presence of PMMA was confirmed.
〔製造例７〕
[ポリ乳酸がコーティングされたポリエチレン系成形体]
マグネチックスターラーを備えた２００ｍＬの平底セパラブルフラスコに脱水トルエン５０ｍＬを注ぎ、製造例３で得られたシート状ポリエチレン成形体１枚を静置させ、フラスコ中を十分に窒素置換した。このフラスコにトリエチルアルミニウムのトルエン溶液（１Ｍ）１ｍＬをシリンジを用いて静かに注ぎ込み、窒素雰囲気下、４０℃でゆっくり攪拌し、系内でポリエチレン成形体とトリエチルアルミニウムとを十分に接触させた。３０分後、窒素雰囲気のままフラスコ中のトルエンと過剰なトリエチルアルミニウムとをデカンテーションで取り除き、さらにポリエチレン成形体を脱水トルエン１００ｍＬで２回洗浄した。
フラスコ内の溶媒を十分に取り除いた後、脱水アセトン５０ｍＬを注ぎ、ＤＬ-ラクチド４．０ｇを加えて、窒素雰囲気下４０℃で２４時間反応させた。反応終了後、フラスコ中のポリエチレン成形体を取り出し、メタノール３００ｍＬで洗浄した。得られたポリエチレン成形体は４０℃、１０Ｔｏｒｒの減圧条件下で１０時間乾燥させ、ATR/IR測定により表面解析を行ったところ、１７６０ｃｍ-１にエステルカルボニル伸縮振動に起因する吸収が観測されたことから、本成形体表面にポリ乳酸が存在することが観察された。
[Production Example 7]
[Polylactic acid-coated polyethylene-based molded product]
50 mL of dehydrated toluene was poured into a 200 mL flat bottom separable flask equipped with a magnetic stirrer, and one sheet-like polyethylene molded product obtained in Production Example 3 was allowed to stand, and the flask was sufficiently purged with nitrogen. To this flask, 1 mL of a toluene solution of triethylaluminum (1M) was gently poured using a syringe, and the mixture was slowly stirred at 40 ° C. in a nitrogen atmosphere to sufficiently bring the polyethylene molded product and triethylaluminum into contact with each other in the system. After 30 minutes, toluene and excess triethylaluminum in the flask were removed by decantation in a nitrogen atmosphere, and the polyethylene molded article was washed twice with 100 mL of dehydrated toluene.
After sufficiently removing the solvent in the flask, 50 mL of dehydrated acetone was poured, and 4.0 g of DL-lactide was added, followed by reaction at 40 ° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, the polyethylene molded product in the flask was taken out and washed with 300 mL of methanol. The obtained polyethylene molded article was dried at 40 ° C. under a reduced pressure of 10 Torr for 10 hours, and subjected to surface analysis by ATR / IR measurement. As a result, absorption due to ester carbonyl stretching vibration was observed at 1760 cm −1. From this, it was observed that polylactic acid was present on the surface of the molded body.
〔製造例８〕
[ポリ（εカプロラクトン）がコーティングされたポリエチレン系成形体]
マグネチックスターラーを備えた２００ｍＬの平底セパラブルフラスコに脱水トルエン５０ｍＬを注ぎ、製造例３で得られたシート状ポリエチレン成形体１枚を静置させ、フラスコ中を十分に窒素置換した。このフラスコにトリエチルアルミニウムのトルエン溶液（１Ｍ）１ｍＬをシリンジを用いて静かに注ぎ込み、窒素雰囲気下、４０℃でゆっくり攪拌し、系内でポリエチレン成形体とトリエチルアルミニウムとを十分に接触させた。３０分後、窒素雰囲気のままフラスコ中のトルエンと過剰なトリエチルアルミニウムとをデカンテーションで取り除き、さらにポリエチレン成形体を脱水トルエン１００ｍＬで２回洗浄した。
フラスコ内の溶媒を十分に取り除いた後、脱水アセトン６０ｍＬを注ぎ、εカプロラクトン５．５ｇを加えて、窒素雰囲気下４０℃で２４時間反応させた。反応終了後、フラスコ中のポリエチレン成形体を取り出し、メタノール３００ｍＬで洗浄した。得られたポリエチレン成形体は４０℃、１０Ｔｏｒｒの減圧条件下で１０時間乾燥させた。得られた成形体の表面をＡＴＲ／ＩＲ測定により解析したところ、１７４０ｃｍ-１にエステルカルボニル伸縮振動に帰属される吸収が観測されたことから、本成形体表面にポリ（εカプロラクトン）が存在することが観察された。
[Production Example 8]
[Polyethylene molded body coated with poly (ε-caprolactone)]
50 mL of dehydrated toluene was poured into a 200 mL flat bottom separable flask equipped with a magnetic stirrer, and one sheet-like polyethylene molded product obtained in Production Example 3 was allowed to stand, and the flask was sufficiently purged with nitrogen. To this flask, 1 mL of a toluene solution of triethylaluminum (1M) was gently poured using a syringe, and the mixture was slowly stirred at 40 ° C. in a nitrogen atmosphere to sufficiently bring the polyethylene molded product and triethylaluminum into contact with each other in the system. After 30 minutes, toluene and excess triethylaluminum in the flask were removed by decantation in a nitrogen atmosphere, and the polyethylene molded article was washed twice with 100 mL of dehydrated toluene.
After sufficiently removing the solvent in the flask, 60 mL of dehydrated acetone was poured, 5.5 g of ε-caprolactone was added, and the mixture was reacted at 40 ° C. for 24 hours in a nitrogen atmosphere. After completion of the reaction, the polyethylene molded product in the flask was taken out and washed with 300 mL of methanol. The obtained polyethylene molding was dried at 40 ° C. under a reduced pressure of 10 Torr for 10 hours. When the surface of the obtained molded body was analyzed by ATR / IR measurement, absorption attributable to ester carbonyl stretching vibration was observed at 1740 cm −1 , so that poly (εcaprolactone) was present on the surface of the molded body. It was observed.
[耐傷付き性の測定]
製造例５で得られた成形体から試験片を作成し、東京衝機製のマルテンス硬度引掻硬度試験機を用いて、厚さ３ｍｍの試験片に引っ掻き圧子２０ｇの荷重を加え試料を引っ掻いた時に生じる溝幅を測定し、その逆数を算出したところ、１８（１／ｍｍ）であった。
[Measurement of scratch resistance]
When a test piece was prepared from the molded body obtained in Production Example 5 and a Martens hardness scratch hardness tester manufactured by Tokyo Shiki Co., Ltd. was used, a test indenter 20 g was applied to the 3 mm thick test piece and the sample was scratched. The resulting groove width was measured, and the reciprocal thereof was calculated to be 18 (1 / mm).
Claims (4)
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