JP6825239B2 - Acrylic resin and molded products of acrylic resin - Google Patents
Acrylic resin and molded products of acrylic resin Download PDFInfo
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- JP6825239B2 JP6825239B2 JP2016118598A JP2016118598A JP6825239B2 JP 6825239 B2 JP6825239 B2 JP 6825239B2 JP 2016118598 A JP2016118598 A JP 2016118598A JP 2016118598 A JP2016118598 A JP 2016118598A JP 6825239 B2 JP6825239 B2 JP 6825239B2
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- 239000004925 Acrylic resin Substances 0.000 title claims description 8
- 229920000178 Acrylic resin Polymers 0.000 title claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 49
- 229920006243 acrylic copolymer Polymers 0.000 claims description 31
- 230000009477 glass transition Effects 0.000 claims description 12
- 241000428199 Mustelinae Species 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 26
- 239000002994 raw material Substances 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- -1 2-[[(2-pyridinylamino) carbonyl] amino] ethyl Chemical group 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009749 continuous casting Methods 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- IQYMRQZTDOLQHC-ZQTLJVIJSA-N [(1R,4S)-2-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C=C)C[C@@H]1C2 IQYMRQZTDOLQHC-ZQTLJVIJSA-N 0.000 description 1
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 1
- PSGCQDPCAWOCSH-OPQQBVKSSA-N [(1s,3r,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@]2(C)[C@H](OC(=O)C=C)C[C@H]1C2(C)C PSGCQDPCAWOCSH-OPQQBVKSSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229920000431 shape-memory polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、熱可逆性を有するアクリル系共重合体樹脂組成物に関する。より具体的には、表面硬度、耐熱性が優れた多重水素結合性のアクリル系共重合体樹脂組成物に関するものである。 The present invention relates to an acrylic copolymer resin composition having thermal reversibility. More specifically, the present invention relates to a multi-hydrogen bond acrylic copolymer resin composition having excellent surface hardness and heat resistance.
アクリル樹脂は、架橋される場合、耐熱性、耐溶剤性、機械特性などの物性を獲得するため、自動車部品、建築部材等に幅広く使用される。架橋には共有結合からなる化学架橋と水素結合やイオン結合など非共有結合からなる物理架橋がある。化学架橋は一旦形成してしまうと、その結合を熱的、機械的に開裂することは困難であり、そのため化学架橋ポリマーを溶融成形することは困難である。そのため、熱的に可逆性を有する水素結合を導入することで、常温では化学架橋を有する樹脂のような機械特性を有しながらも、溶融成形時には水素結合が開裂し成形可能であるアクリル樹脂を提供することがある。 Acrylic resins are widely used in automobile parts, building materials, etc. in order to acquire physical properties such as heat resistance, solvent resistance, and mechanical properties when crosslinked. Crosslinks include chemical crosslinks consisting of covalent bonds and physical crosslinks consisting of non-covalent bonds such as hydrogen bonds and ionic bonds. Once the chemically crosslinked polymer is formed, it is difficult to thermally and mechanically cleave the bond, and therefore it is difficult to melt-mold the chemically crosslinked polymer. Therefore, by introducing a thermally reversible hydrogen bond, an acrylic resin that has mechanical properties like a resin having a chemical crosslink at room temperature but can be molded by cleaving the hydrogen bond during melt molding. May be provided.
このような背景のもと、水素結合を介する架橋ポリマーの研究が活発化している。特許文献１では、多重水素結合形成成分とポリエステルを加熱溶融あるいは溶液中で混合することで熱可逆的架橋を付与している。しかしながら、ポリマー主鎖中に水酸基がなければ多重水素結合形成官能基を導入することが出来ない上に、ピリミジン基を導入した（メタ）アクリレートの溶解性が極めて低いためにアクリル樹脂へ応用することは困難である。 Against this background, research on crosslinked polymers via hydrogen bonds has become active. In Patent Document 1, thermoreversible cross-linking is imparted by heating and melting the multiple hydrogen bond forming component and polyester in a solution. However, if there is no hydroxyl group in the polymer main chain, a multiple hydrogen bond forming functional group cannot be introduced, and the solubility of the (meth) acrylate introduced with a pyrimidine group is extremely low, so that it can be applied to an acrylic resin. It is difficult.
特許文献２に記載の技術は、感光層を形成する塗布液中に多重水素結合形成成分が含まれている。この技術は、多重水素結合が熱可逆性を示すこと、及び、良好な表面硬度と耐熱性を有することを示唆するものではなかった。 In the technique described in Patent Document 2, a multiple hydrogen bond forming component is contained in the coating liquid forming the photosensitive layer. This technique did not suggest that multiple hydrogen bonds exhibit thermoreversibility and have good surface hardness and heat resistance.
特許文献３に記載の技術は、多重水素結合を導入した形状記憶ポリマーが熱可逆性を有することを示唆していた。しかしながら、実施例に記載のポリマー状固体は、実用樹脂材料として使用できるものではなく、十分な表面硬度および耐熱性を有するものではなかった。 The technique described in Patent Document 3 has suggested that the shape memory polymer into which multiple hydrogen bonds have been introduced has thermoreversibility. However, the polymer-like solid described in the examples cannot be used as a practical resin material, and does not have sufficient surface hardness and heat resistance.
上記課題の下、本発明の目的は、表面硬度および耐熱性に優れた熱可逆性を有する多重水素結合性（メタ）アクリル系共重合体および樹脂組成物並びに成形体を提供することである。 Under the above problems, an object of the present invention is to provide a multi-hydrogen bonding (meth) acrylic copolymer having excellent surface hardness and heat resistance and thermal reversibility, a resin composition, and a molded product.
前記課題は、以下の［１］〜［５］のいずれかによって解決される。
［１］下記式（１）で表される水素結合性（メタ）アクリレート単位（ａ１）を１〜２０モル％、および、下記式（１）以外の構造を有する（メタ）アクリレート単位（ａ２）として、（メタ）アクリル酸メチル単位を８０〜９９モル％含みマルテンス硬度が１７０Ｎ／ｍｍ２以上である、（メタ）アクリル系共重合体。
［２］前記（メタ）アクリル系共重合体が、下記式（３）で表される水素結合性（メタ）アクリレート単量体と（メタ）アクリル酸メチル単量体を含む混合物のラジカル重合体である［１］に記載の樹脂組成物。
［３］Ｔｇが３０℃以上である［１］に記載の（メタ）アクリル系共重合体。
［４］［１］に記載の（メタ）アクリル系共重合体を含む（メタ）アクリル系樹脂組成物
。
［５］［４］に記載の（メタ）アクリル系樹脂組成物を成形して得られる成形体。
The problem is solved by any of the following [1] to [5].
[1] The hydrogen-bonding (meth) acrylate unit (a1) represented by the following formula (1) is 1 to 20 mol%, and the (meth) acrylate unit (a2) having a structure other than the following formula (1). A (meth) acrylic copolymer containing 80 to 99 mol% of methyl (meth) acrylate units and having a Martens hardness of 170 N / mm 2 or more.
[2] The (meth) acrylic copolymer, a radical polymer mixture comprising the following formula (3) with hydrogen bonding represented (meth) acrylate monomer and a (meth) acrylate monomer The resin composition according to [1].
[3] The (meth) acrylic copolymer according to [1], which has a Tg of 30 ° C. or higher.
[4] A (meth) acrylic resin composition containing the (meth) acrylic copolymer according to [1].
[5] A molded product obtained by molding the (meth) acrylic resin composition according to [4].
本発明により、表面硬度および耐熱性に優れた（メタ）アクリル系共重合体、および樹脂組成物が提供される。この（メタ）アクリル系共重合体は熱可逆性を有することから、リサイクル性の向上や成形加工時の省エネルギー化といった利点がある。また本発明の（メタ）アクリル系共重合体から得られる成形体は、外装材用途として幅広く使用することができる。 INDUSTRIAL APPLICABILITY The present invention provides a (meth) acrylic copolymer having excellent surface hardness and heat resistance, and a resin composition. Since this (meth) acrylic copolymer has thermal reversibility, it has advantages such as improved recyclability and energy saving during molding. Further, the molded product obtained from the (meth) acrylic copolymer of the present invention can be widely used as an exterior material.
＜（メタ）アクリル系共重合体＞
本発明の（メタ）アクリル系共重合体は、水素結合性（メタ）アクリレート単位（ａ１）と（メタ）アクリレート単位（ａ２）とを含む共重合体である。水素結合性（メタ）アクリレート単位（ａ１）としては、式（２）で表される単量体が挙げられる。式（２）で表される水素結合性（メタ）アクリレート単位は、１種単独でもよく、２種以上を組み合わせてもよい。（メタ）アクリル系共重合体は、前記各構成単位（ａ１）および（ａ２）のランダム共重合体およびブロック共重合体のいずれでもよい。好ましい（メタ）アクリル系共重合体は、単位（ａ１）および（ａ２）のランダム共重合体である。
（メタ）アクリル系共重合体のマルテンス硬度は１７０Ｎ／ｍｍ２以上であることが好ましい。
（メタ）アクリル系共重合体のガラス転移温度は、成形材料の強度の観点から、３０℃以上が好ましく、６０℃以上がより好ましい。
<(Meta) acrylic copolymer>
The (meth) acrylic copolymer of the present invention is a copolymer containing a hydrogen-bonding (meth) acrylate unit (a1) and a (meth) acrylate unit (a2). Examples of the hydrogen-bonding (meth) acrylate unit (a1) include a monomer represented by the formula (2). The hydrogen-bonding (meth) acrylate unit represented by the formula (2) may be used alone or in combination of two or more. The (meth) acrylic copolymer may be any of the random copolymers and block copolymers of the structural units (a1) and (a2). Preferred (meth) acrylic copolymers are random copolymers of units (a1) and (a2).
The Martens hardness of the (meth) acrylic copolymer is preferably 170 N / mm 2 or more.
The glass transition temperature of the (meth) acrylic copolymer is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of the strength of the molding material.
［水素結合性（メタ）アクリレート単位（ａ１）］
水素結合性（メタ）アクリレート単位（ａ１）は、下記式（１）で表される成分である。
[Hydrogen bondability (meth) acrylate unit (a1)]
The hydrogen-bonding (meth) acrylate unit (a1) is a component represented by the following formula (1).
（メタ）アクリル系共重合体中における式（１）で表される水素結合性（メタ）アクリレート単位（ａ１）は、下記の式（３）で表される水素結合性（メタ）アクリレートを原料として、形成することができる。なお、式（３）中のＲ１、Ｒ２、Ｒ３、Ｘ、ＹおよびＺは、前記式（１）の場合と同様である。 The hydrogen-bonding (meth) acrylate unit (a1) represented by the formula (1) in the (meth) acrylic copolymer is made from the hydrogen-bonding (meth) acrylate represented by the following formula (3). Can be formed as. In addition, R 1 , R 2 , R 3 , X, Y and Z in the formula (3) are the same as the case of the above formula (1).
式（３）で表される水素結合性（メタ）アクリレートとしては、例えば、２−［［（２−ピリジニルアミノ）カルボニル］アミノ］エチルアクリレート（以降、ＡＯＩ−ＡＰと表記）、２−［［（２−ピリジニルアミノ）カルボニル］アミノ］エチルメタクリレート（以降、ＭＯＩ−ＡＰと表記）、２−［［（２−フリルアミノ）カルボニル］アミノ］エチルアクリレート、２−［［（２−フリルアミノ）カルボニル］アミノ］エチルメタクリレート、等が挙げられる。
特に、ＡＯＩ−ＡＰ、ＭＯＩ−ＡＰは溶解性が高く取扱い性に優れ、（メタ）アクリル共重合体の表面硬度と耐熱性を向上させることから、好ましい。
Examples of the hydrogen-bonding (meth) acrylate represented by the formula (3) include 2-[[(2-pyridinylamino) carbonyl] amino] ethyl acrylate (hereinafter referred to as AOI-AP) and 2-[[(). 2-Pyridinylamino) carbonyl] amino] ethyl methacrylate (hereinafter referred to as MOI-AP) , 2-[[(2 -furylamino) carbonyl] amino] ethyl acrylate, 2-[[(2-furylamino) carbonyl] amino ] Ethyl methacrylate, etc. may be mentioned.
In particular, AOI-AP and MOI-AP are preferable because they have high solubility and excellent handleability, and improve the surface hardness and heat resistance of the (meth) acrylic copolymer.
前記式（１）で表される水素結合性（メタ）アクリレート単位（ａ１）は、（メタ）アクリル系共重合体中の水素結合性（メタ）アクリレート単位（ａ１）および（メタ）アクリレート単位（ａ２）の合計１００モル％に対して、１〜２０モル％含まれていることが好ましい。前記範囲内であれば、（メタ）アクリル系共重合体から得られる成形体は、耐熱性を維持しながら表面硬度を向上させることができる。 The hydrogen-bonding (meth) acrylate unit (a1) represented by the formula (1) is the hydrogen-bonding (meth) acrylate unit (a1) and the (meth) acrylate unit (meth) in the (meth) acrylic copolymer. It is preferable that 1 to 20 mol% is contained with respect to 100 mol% of the total of a2). Within the above range, the molded product obtained from the (meth) acrylic copolymer can improve the surface hardness while maintaining the heat resistance.
［（メタ）アクリレート単位（ａ２）］
（メタ）アクリル系共重合体中における（メタ）アクリレート単位（ａ２）は、アルキルアクリレート、アルキル（メタ）アクリレート等の、アクリレート、（メタ）アクリレートを原料として、形成することができる。
原料としてのアクリレートおよび（メタ）アクリレートは、それぞれ単独で、または組み合わせて用いることができる。その際、アクリレートは、１種単独でもよく、２種以上を組み合わせて用いることができる。同様に、（メタ）アクリレートは、１種単独でもよく、２種以上を組み合わせて用いることもできる。
[(Meta) acrylate unit (a2)]
The (meth) acrylate unit (a2) in the (meth) acrylic copolymer can be formed from an acrylate such as an alkyl acrylate or an alkyl (meth) acrylate or a (meth) acrylate as a raw material.
The acrylate and (meth) acrylate as raw materials can be used alone or in combination, respectively. At that time, the acrylate may be used alone or in combination of two or more. Similarly, the (meth) acrylate may be used alone or in combination of two or more.
（メタ）アクリレートとしては、以下の単量体が好ましい。（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸シクロへキシル、（メタ）アクリル酸ボルニル、（メタ）アクリル酸ノルボルニル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸、アクリル酸メチル、アクリル酸ｔ−ブチル、アクリル酸ｎ−ブチル、アクリル酸ｉ−ブチル、アクリル酸イソボルニル、またはこれらの混合物。 As the (meth) acrylate, the following monomers are preferable. Methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, i-butyl (meth) acrylate, n-butyl (meth) acrylate, (meth) ) Cyclohexyl acrylate, (meth) bornyl acrylate, (meth) norbornyl acrylate, (meth) isobornyl acrylate, adamantyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylate, acrylate Methyl, t-butyl acrylate, n-butyl acrylate, i-butyl acrylate, isobornyl acrylate, or mixtures thereof.
特に、（メタ）アクリル酸メチルを原料とする（メタ）アクリレート単位（ａ２）は、（メタ）アクリル系共重合体の表面硬度を向上させることから、好ましい。 In particular, the (meth) acrylate unit (a2) using methyl (meth) acrylate as a raw material is preferable because it improves the surface hardness of the (meth) acrylic copolymer.
前記（メタ）アクリル酸メチルを原料とする（メタ）アクリレート単位（ａ２）は、（メタ）アクリル系共重合体中の水素結合性（メタ）アクリレート単位（ａ１）および（メタ）アクリレート単位（ａ２）の合計１００モル％に対して、８０〜９９モル％含まれていることが好ましい。前記範囲内であれば、（メタ）アクリル系共重合体から得られる成形体は、耐熱性を向上させることができる。 The (meth) acrylate unit (a2) using the methyl (meth) acrylate as a raw material is a hydrogen-bonding (meth) acrylate unit (a1) and a (meth) acrylate unit (a2) in the (meth) acrylic copolymer. ) Is preferably contained in an amount of 80 to 99 mol% based on 100 mol% in total. Within the above range, the molded product obtained from the (meth) acrylic copolymer can improve the heat resistance.
＜樹脂組成物＞
本発明の（メタ）アクリル系共重合体は、公知各種添加剤を含む樹脂組成物として用いることができる。添加剤としては、離型剤、酸化防止剤、熱安定剤、紫外線吸収剤、帯電防止剤、界面活性剤、補強剤、着色剤等が挙げられる。
<Resin composition>
The (meth) acrylic copolymer of the present invention can be used as a resin composition containing various known additives. Examples of the additive include a mold release agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a surfactant, a reinforcing agent, a colorant and the like.
＜成形体＞
本発明の（メタ）アクリル系共重合体及び樹脂組成物は、成形体に成形加工して使用することができる。成形体としては、例えば、自動車、航空機等の部品、産業用機器、家電製品、食器や医療機器、ＯＡ、ＡＶ機器、電子部品、建築部材等が挙げられる。
<Molded body>
The (meth) acrylic copolymer and the resin composition of the present invention can be used by molding into a molded product. Examples of the molded body include parts such as automobiles and aircraft, industrial equipment, home appliances, tableware and medical equipment, OA, AV equipment, electronic parts, building materials and the like.
［注型重合法］
注型重合法としては、例えば、所定間隔で対向配置された２枚の板状体とその縁部に配置された封止材料とによって形成された鋳型を用い、鋳型内に重合性原料を注入して重合させる方法が挙げられる。鋳型内に注入する重合性原料としては、単量体混合物または、単量体と重合体の混合物を用いることができる。
[Casting polymerization method]
As the casting polymerization method, for example, a mold formed by two plate-like bodies arranged to face each other at predetermined intervals and a sealing material arranged at the edge thereof is used, and a polymerizable raw material is injected into the mold. And there is a method of polymerizing. As the polymerizable raw material to be injected into the mold, a monomer mixture or a mixture of a monomer and a polymer can be used.
［鋳型重合工程］
鋳型重合工程は、重合性原料を鋳型の中に注入して重合し、成形体を得る工程である。鋳型としては、例えば、セルキャスト用の鋳型および連続キャスト用の鋳型が挙げられる。
[Mold polymerization process]
The mold polymerization step is a step of injecting a polymerizable raw material into a mold and polymerizing the mixture to obtain a molded product. Examples of the mold include a mold for cell casting and a mold for continuous casting.
セルキャスト用の鋳型としては、例えば、無機ガラス、クロムメッキ金属板、ステンレス鋼板等の２枚の板状体を所定間隔で対向配置し、その縁部にガスケットを挟み込んで、板状体とガスケットにより密封空間を形成させたものが挙げられる。
セルキャスト用の板状体には、成形体を剥離しやすくするためにフィルムを被覆してもよい。フィルムとしては、ポリエチレンテレフタレート（ＰＥＴ）製のフィルムを用いることができる。
As a mold for cell casting, for example, two plate-shaped bodies such as inorganic glass, chrome-plated metal plate, and stainless steel plate are arranged to face each other at predetermined intervals, and a gasket is sandwiched between the edges of the plate-shaped bodies and the gasket. A sealed space is formed by the above.
The plate-shaped body for cell casting may be coated with a film in order to facilitate peeling of the molded body. As the film, a film made of polyethylene terephthalate (PET) can be used.
連続キャスト用の鋳型としては、例えば、同一方向へ同一速度で走行する一対のクロムメッキ金属板、ステンレス鋼板等のエンドレスベルトの相対する面と、その両側辺部においてエンドレスベルトと同一速度で走行するガスケットとにより密封空間を形成させたものが挙げられる。 As a mold for continuous casting, for example, a pair of chrome-plated metal plates, stainless steel plates, or the like traveling in the same direction at the same speed and the opposite surfaces of the endless belt and both side portions thereof travel at the same speed as the endless belt. An example is one in which a sealed space is formed by a gasket.
鋳型重合工程における重合温度及び重合時間は、重合性原料中の単量体の種類を考慮して適宜設定される。鋳型内の重合性原料を所定温度で所定時間加熱して、重合性原料中の単量体を重合させる。セルキャスト法の場合は、重合完了後、鋳型を解体して成形体を得ることができる。連続キャスト法の場合は、エンドレスベルトから搬送された重合体の板状物を切断することによって成形体を得ることができる。 The polymerization temperature and the polymerization time in the template polymerization step are appropriately set in consideration of the type of the monomer in the polymerizable raw material. The polymerizable raw material in the mold is heated at a predetermined temperature for a predetermined time to polymerize the monomers in the polymerizable raw material. In the case of the cell cast method, after the polymerization is completed, the mold can be disassembled to obtain a molded product. In the case of the continuous casting method, a molded product can be obtained by cutting a plate-like product of the polymer conveyed from the endless belt.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではなく、本発明の精神を逸脱しない範囲で種々の変更が加えられてもよい。成形体の評価を以下の方法で行った。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto, and various modifications may be made without departing from the spirit of the present invention. The molded product was evaluated by the following method.
（ａ）表面硬度の評価
表面硬度は、成形体を６０℃で１６時間真空乾燥した後、２５℃で湿度５０％を１６時間保持した厚さ１ｍｍのキャスト試片を用いて、マルテンス硬度を測定することで評価した。測定装置はフィッシャー・インストルメンツ社製表面皮膜物性試験機フィッシャースコープ ＨＭ−２０００ＸＹｐを用いた。測定条件は、最大試験荷重３００ｍＮ／１０ｓ、クリープ各１０ｓとし、５回の平均値を採用した。表面硬度の評価は以下の基準で表示した。
○：１７０Ｎ／ｍｍ２以上である。
×：１７０Ｎ／ｍｍ２未満である。
(A) Evaluation of surface hardness The surface hardness is measured by measuring the Martens hardness using a cast specimen having a thickness of 1 mm, which is obtained by vacuum-drying the molded product at 60 ° C. for 16 hours and then maintaining the humidity at 25 ° C. at 50% for 16 hours. Evaluated by doing. As a measuring device, a surface film physical property tester Fisherscope HM-2000XYp manufactured by Fisher Instruments was used. The measurement conditions were a maximum test load of 300 mN / 10s and creep of 10s each, and the average value of 5 times was adopted. The evaluation of surface hardness was shown according to the following criteria.
◯: 170 N / mm 2 or more.
X: 170 N / mm less than 2 .
（ｂ）耐熱性評価
耐熱性は、ＤＭＳ測定により評価した。１Ｈｚにおけるｔａｎδのピークトップよりガラス転移温度（Ｔｇ）を決定し、以下の基準で表示した。
○：ガラス転移温度（Ｔｇ）が３０℃以上である。
×：ガラス転移温度（Ｔｇ）が３０℃未満である。
(B) Evaluation of heat resistance The heat resistance was evaluated by DMS measurement. The glass transition temperature (Tg) was determined from the peak top of tan δ at 1 Hz and displayed according to the following criteria.
◯: The glass transition temperature (Tg) is 30 ° C. or higher.
X: The glass transition temperature (Tg) is less than 30 ° C.
（ｃ）架橋の熱可逆性の評価
架橋の熱可逆性は、厚さ１ｍｍのキャスト試片および、キャスト試片を凍結粉砕し熱プレス成形して得た厚さ０．５〜１ｍｍのプレスフィルムを用いて評価した。キャスト試片およびプレスフィルムを１５ｍｍ×５ｍｍに切り出し、１０ｍＬバイアル瓶中でクロロホルムに浸漬した。室温で２４時間静置し、膨潤した場合は架橋を有すると判断した。架橋の熱可逆性の評価は以下の基準で表示した。
○：キャスト試片がクロロホルムに対して膨潤し、プレスフィルムもクロロホルムに対して膨潤する。
×：キャスト試片がクロロホルムに対して溶解し、プレスフィルムもクロロホルムに対して溶解する。
(C) Evaluation of thermal reversibility of cross-linking The thermal reversibility of cross-linking is obtained by freeze-crushing a cast specimen having a thickness of 1 mm and a press film having a thickness of 0.5 to 1 mm obtained by hot press molding. Was evaluated using. The cast specimen and press film were cut into 15 mm × 5 mm pieces and immersed in chloroform in a 10 mL vial. It was allowed to stand at room temperature for 24 hours, and when it swelled, it was judged to have crosslinks. The evaluation of the thermal reversibility of the crosslinks was shown according to the following criteria.
◯: The cast specimen swells with respect to chloroform, and the press film also swells with respect to chloroform.
X: The cast specimen dissolves in chloroform, and the press film also dissolves in chloroform.
（ｄ）ポリマー組成比の決定方法
１Ｈ液体高分解能ＮＭＲのケミカルシフトから、ポリマー組成比を決定した。具体的には、ポリマーをＤＭＳＯ−ｄ６に溶解させ、測定温度５０℃、積算回数３２回で１Ｈ−ＮＭＲを測定し、３．５ｐｐｍのピーク（ＭＭＡのメトキシ基（−ＯＭｅ）のプロトン由来）を基準として、６．９−８．２ｐｐｍのピーク（水素結合性（メタ）アクリレートの芳香族プロトン由来）との比を求めた。この比により、（メタ）アクリル系共重合体中の、水素結合性（メタ）アクリレート単位（ａ１）と（メタ）アクリレート単位（ａ２）の組成比を決定した。
(D) Method for determining polymer composition ratio
The polymer composition ratio was determined from the chemical shift of 1H liquid high resolution NMR. Specifically, the polymer was dissolved in DMSO-d6, 1 H-NMR was measured at a measurement temperature of 50 ° C. and the number of integrations was 32, and a peak of 3.5 ppm (derived from the proton of the methoxy group (-OMe) of MMA). The ratio with the peak of 6.9-8.2 ppm (derived from the aromatic proton of hydrogen-bonding (meth) acrylate) was determined based on the above. From this ratio, the composition ratio of the hydrogen-bonding (meth) acrylate unit (a1) and the (meth) acrylate unit (a2) in the (meth) acrylic copolymer was determined.
［実施例１］
１．重合性原料の調整
ＡＯＩ−ＡＰ ３質量部とアクリエステルＭ（三菱レイヨン（株）製、メチルメタクリレート） ９７質量部の合計１００質量部に対し、重合開始剤パーへキシルＰＶ（日油（株）製、商品名）０．３質量部、連鎖移動剤１−オクタンチオール（東京化成（株）製、商品名）０．１質量部、離型剤ＡＯＴ（アメリカンシアナミド社製、商品名）０．０８質量部を配合して、ディスポカップ内において、撹拌して、重合開始剤及び離型剤を溶解させて重合性原料を得た。
[Example 1]
1. 1. Adjustment of Polymerizable Raw Material AOI-AP 3 parts by mass and Acryester M (Methylmethacrylate, manufactured by Mitsubishi Rayon Co., Ltd.) 97 parts by mass, for a total of 100 parts by mass, the polymerization initiator Perhexyl PV (Nichiyu Co., Ltd.) Manufactured by, trade name) 0.3 parts by mass, chain transfer agent 1-octanethiol (manufactured by Tokyo Kasei Co., Ltd., trade name) 0.1 parts by mass, mold initiator AOT (manufactured by American Cyanamide, trade name) 0. 08 parts by mass was blended and stirred in the disposable cup to dissolve the polymerization initiator and the mold release agent to obtain a polymerizable raw material.
２．キャスト板の製造
次いで、重合性原料を、真空脱泡ミキサー（（株）シンキー製、商品名「泡とり錬太郎」、型番：ＡＲＶ−３１０）内に供給して、１５００ｒｐｍ、１０ｋＰａの条件下で、２分間脱泡した。セル内部にＰＥＴフィルムが面するよう設置された２枚の厚み５ｍｍ、１５０ｍｍ角のガラス板と塩化ビニル製ガスケットにより、内部のサイズが縦１２ｍｍ、横１２ｍｍ、高さ１ｍｍの重合用セルを準備した。このセル内に、脱泡したシラップを注入した。このセルを６０℃の水浴中に３時間浸漬し、次いで１３０℃の乾燥機内に４５分間置いて、重合を行った。重合完了後、セルを解体して厚さ１ｍｍのキャスト板を得た。評価結果を表１に示す。キャスト板のマルテンス硬度は１９０Ｎ／ｍｍ２であり、ガラス転移温度は１２４℃、クロロホルム溶媒に対して膨潤した。
2. 2. Manufacture of cast plate Next, the polymerizable raw material was supplied into a vacuum defoaming mixer (manufactured by Shinky Co., Ltd., trade name "Awatori Rentaro", model number: ARV-310) under the conditions of 1500 rpm and 10 kPa. Defoamed for 2 minutes. A polymerization cell having an internal size of 12 mm in length, 12 mm in width, and 1 mm in height was prepared by using two 5 mm thick, 150 mm square glass plates and a vinyl chloride gasket installed so that the PET film faces the inside of the cell. .. Defoamed syrup was injected into this cell. The cell was immersed in a water bath at 60 ° C. for 3 hours and then placed in a dryer at 130 ° C. for 45 minutes for polymerization. After the polymerization was completed, the cell was disassembled to obtain a cast plate having a thickness of 1 mm. The evaluation results are shown in Table 1. The Martens hardness of the cast plate was 190 N / mm 2 , the glass transition temperature was 124 ° C., and the cast plate swelled with respect to a chloroform solvent.
３．架橋の熱可逆性の確認
このキャスト板を凍結粉砕して得られた粉末状の共重合体を、６０℃で１２時間にわたり真空乾燥させた。ＳＵＳ板の上に１ｍｍ厚のテフロンシートを載せ、その上に１〜２ｇ程度の粉末状共重合体を山型に盛り、さらにテフロンシートとＳＵＳ板を順番に重ねた。このＳＵＳ板を、１８０℃に昇温したプレス成形機（ミニテストプレス、（株）東洋精機製作所製、１０型）へ設置し、０ＭＰａを２０分間保持した。続いて２ＭＰａを２０分間保持し、最後に５ＭＰａを６０分間保持した。プレス成形完了後、テフロンシートから剥がして０．５〜１ｍｍ厚のプレスフィルムを得た。このプレスフィルムをクロロホルム溶媒に浸漬したところ、膨潤した。
3. 3. Confirmation of Thermal Reversibility of Crosslinking The powdery copolymer obtained by freeze-milling this cast plate was vacuum-dried at 60 ° C. for 12 hours. A 1 mm-thick Teflon sheet was placed on the SUS plate, and about 1 to 2 g of a powdery copolymer was placed on the SUS plate in a chevron shape, and the Teflon sheet and the SUS plate were stacked in order. This SUS plate was placed in a press molding machine (mini test press, 10 type manufactured by Toyo Seiki Seisakusho Co., Ltd.) whose temperature was raised to 180 ° C., and 0 MPa was held for 20 minutes. Subsequently, 2 MPa was held for 20 minutes, and finally 5 MPa was held for 60 minutes. After the press molding was completed, it was peeled off from the Teflon sheet to obtain a press film having a thickness of 0.5 to 1 mm. When this press film was immersed in a chloroform solvent, it swelled.
［実施例２〜３］
実施例１の「重合性原料の調整」において、ＡＯＩ−ＡＰとアクリエステルＭの使用量を表１に示す値に変更し、重合開始剤パーへキシルＰＶの使用量を０．２質量部へ変更し、連鎖移動剤１−オクタンチオールを使用しなかった。また、実施例１の「キャスト板の製造」において水浴中でのセルの加熱温度と加熱時間を８０℃、１時間に変更した以外は実施例１と同様にしてキャスト板およびプレスフィルムを得た。評価結果を表１に示す。
実施例２では、キャスト板のマルテンス硬度は２１４Ｎ／ｍｍ２であり、ガラス転移温度は１２３℃、キャスト板およびプレスフィルムはクロロホルムに対して膨潤した。
実施例３では、キャスト板のマルテンス硬度は２００Ｎ／ｍｍ２であり、ガラス転移温度は９４℃、キャスト板およびプレスフィルムはクロロホルムに対して膨潤した。
[Examples 2 to 3]
In "Adjustment of Polymerizable Raw Material" of Example 1, the amounts of AOI-AP and Acryester M used were changed to the values shown in Table 1, and the amount of the polymerization initiator perhexyl PV used was reduced to 0.2 parts by mass. Changed and did not use the chain transfer agent 1-octanethiol. Further, a cast plate and a press film were obtained in the same manner as in Example 1 except that the heating temperature and heating time of the cell in the water bath were changed to 80 ° C. and 1 hour in "Production of cast plate" of Example 1. .. The evaluation results are shown in Table 1.
In Example 2, the Martens hardness of the cast plate was 214 N / mm 2 , the glass transition temperature was 123 ° C., and the cast plate and the press film swelled with respect to chloroform.
In Example 3, the Martens hardness of the cast plate was 200 N / mm 2 , the glass transition temperature was 94 ° C., and the cast plate and the press film swelled with respect to chloroform.
［実施例４］
実施例２の「重合性原料の調整」において、ＡＯＩ−ＡＰをＭＯＩ−ＡＰに変更した以外は、同様にしてキャスト板およびプレスフィルムを得た。
[Example 4]
A cast plate and a press film were obtained in the same manner except that AOI-AP was changed to MOI-AP in "Preparation of Polymerizable Raw Material" of Example 2.
評価結果を表１に示す。キャスト板のマルテンス硬度は２１３Ｎ／ｍｍ２であり、ガラス転移温度は１２３℃、キャスト板およびプレスフィルムはクロロホルムに対して膨潤した。 The evaluation results are shown in Table 1. The Martens hardness of the cast plate was 213 N / mm 2 , the glass transition temperature was 123 ° C., and the cast plate and the press film swelled with respect to chloroform.
［参考例］
実施例２の「重合性原料の調整」において、ＡＯＩ−ＡＰを５質量部、アクリエステルＭを７１．２５質量部、アクリル酸ブチル（三菱化学（株）製）を２３．７５質量部用いた以外は、同様にしてキャスト板およびプレスフィルムを得た。評価結果を表１に示す。キャスト板のマルテンス硬度は１８０Ｎ／ｍｍ２であり、ガラス転移温度は６５℃、キャスト板およびプレスフィルムはクロロホルムに対して膨潤した。
[ Reference example ]
In "Preparation of Polymerizable Raw Material" of Example 2, 5 parts by mass of AOI-AP, 71.25 parts by mass of Acryester M, and 23.75 parts by mass of butyl acrylate (manufactured by Mitsubishi Chemical Corporation) were used. A cast plate and a press film were obtained in the same manner except for the above. The evaluation results are shown in Table 1. The Martens hardness of the cast plate was 180 N / mm 2 , the glass transition temperature was 65 ° C., and the cast plate and the press film swelled with respect to chloroform.
［比較例１］
実施例２の「重合性原料の調整」において、ＡＯＩ−ＡＰを使用しなかった以外は、同様にしてキャスト板およびプレスフィルムを得た。評価結果を表１に示す。キャスト板のマルテンス硬度は１６９Ｎ／ｍｍ２であり、ガラス転移温度は１２５℃であった。しかしながら、水素結合性架橋を持たないためにキャスト板およびプレスフィルムはクロロホルムに対して溶解した。
[Comparative Example 1]
A cast plate and a press film were obtained in the same manner except that AOI-AP was not used in "Preparation of Polymerizable Raw Material" of Example 2. The evaluation results are shown in Table 1. The Martens hardness of the cast plate was 169 N / mm 2 , and the glass transition temperature was 125 ° C. However, the cast plate and press film were dissolved in chloroform because they did not have hydrogen bonding crosslinks.
［比較例２］
実施例２の「重合性原料の調整」において、ＡＯＩ−ＡＰをアクリエステルＢＺ（三菱レイヨン（株）製、ベンジルメタクリレート）に変更した以外は、同様にしてキャスト板およびプレスフィルムを得た。評価結果を表１に示す。キャスト板のマルテンス硬度は１１８Ｎ／ｍｍ２であり、ガラス転移温度は１１５℃であった。しかしながら、アクリエステルＢＺは水素結合を形成するウレア基を持たないためにキャスト板およびプレスフィルムはクロロホルムに対して膨潤した。
[Comparative Example 2]
A cast plate and a press film were obtained in the same manner except that AOI-AP was changed to acrylic ester ZZ (manufactured by Mitsubishi Rayon Co., Ltd., benzyl methacrylate) in "Preparation of Polymerizable Raw Material" of Example 2. The evaluation results are shown in Table 1. The Martens hardness of the cast plate was 118 N / mm 2 , and the glass transition temperature was 115 ° C. However, since the acrylic ester BZ does not have a urea group forming a hydrogen bond, the cast plate and the press film swelled with respect to chloroform.
［比較例３］
実施例６の「重合性原料の調整」において、アクリエステルＭを用いず、アクリル酸ブチルを９３質量部、架橋剤アクリエステルＥＤ（三菱レイヨン（株）製、エチレングリコールジメタクリラート）を２質量部用いた以外は、同様にして重合を実施したが、共重合体はゲル状でキャスト板として回収することができなかった。評価結果を表１に示す。表面硬度および耐熱性の評価は実施できなかった。
[Comparative Example 3]
In "Preparation of Polymerizable Raw Material" of Example 6, 93 parts by mass of butyl acrylate and 2 parts by mass of cross-linking agent Acryester ED (ethylene glycol dimethacrylate manufactured by Mitsubishi Rayon Co., Ltd.) were used without using Acryester M. Polymerization was carried out in the same manner except for the part used, but the copolymer was in the form of a gel and could not be recovered as a cast plate. The evaluation results are shown in Table 1. The surface hardness and heat resistance could not be evaluated.
重合条件「１」：離型剤 ０．０８質量部、開始剤 ０．３質量部、連鎖移動剤 ０．１質量部／６０℃・３時間→１３０℃・４５分間
重合条件「２」：離型剤 ０．０８質量部、開始剤 ０．２質量部／８０℃・１時間→１３０℃・４５分間
Polymerization condition "1": Molder 0.08 part by mass, initiator 0.3 part by mass, chain transfer agent 0.1 part by mass / 60 ° C., 3 hours → 130 ° C., 45 minutes Polymerization condition "2": Release Molding agent 0.08 parts by mass, initiator 0.2 parts by mass / 80 ° C., 1 hour → 130 ° C., 45 minutes
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