JP2014098116A - Polymer composition - Google Patents
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- JP2014098116A JP2014098116A JP2012251550A JP2012251550A JP2014098116A JP 2014098116 A JP2014098116 A JP 2014098116A JP 2012251550 A JP2012251550 A JP 2012251550A JP 2012251550 A JP2012251550 A JP 2012251550A JP 2014098116 A JP2014098116 A JP 2014098116A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000002608 ionic liquid Substances 0.000 claims abstract description 97
- 150000002148 esters Chemical class 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012071 phase Substances 0.000 claims abstract description 7
- 125000000129 anionic group Chemical group 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 4
- 108010000020 Platelet Factor 3 Proteins 0.000 claims 1
- 241000894007 species Species 0.000 description 24
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 238000005259 measurement Methods 0.000 description 18
- 229920005604 random copolymer Polymers 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 10
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 10
- 239000004094 surface-active agent Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 239000002216 antistatic agent Substances 0.000 description 8
- 230000000740 bleeding effect Effects 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 8
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 7
- -1 acrylic ester Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 5
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 4
- 150000004693 imidazolium salts Chemical class 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 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
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005011 alkyl ether group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- JFZKOODUSFUFIZ-UHFFFAOYSA-N trifluoro phosphate Chemical compound FOP(=O)(OF)OF JFZKOODUSFUFIZ-UHFFFAOYSA-N 0.000 description 2
- DSIZWXRKCNMRRB-UHFFFAOYSA-N 1-(2-methoxyethyl)-1-methylpiperidin-1-ium Chemical compound COCC[N+]1(C)CCCCC1 DSIZWXRKCNMRRB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 241000982822 Ficus obtusifolia Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 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
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 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
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Abstract
Description
本発明は、重合体組成物に関する。 The present invention relates to a polymer composition.
近年、溶媒を用いずに液状を示す塩であるイオン液体が注目されている。イオン液体は、一般に、不揮発性で、難燃性および耐熱性に優れることから、反応溶媒、キャパシタや電池等の電解液、潤滑剤、触媒、帯電防止剤等として用いるために、種々の開発が行われている。 In recent years, an ionic liquid which is a salt that shows a liquid state without using a solvent has attracted attention. Since ionic liquids are generally nonvolatile and excellent in flame retardancy and heat resistance, various developments have been made to use them as reaction solvents, electrolytic solutions for capacitors and batteries, lubricants, catalysts, antistatic agents, etc. Has been done.
例えば、色相や透明性が損なわれることなく帯電防止性能が付与された樹脂組成物を得るために、組成物に熱可塑性樹脂（Ａ）１００重量部、およびイオン液体、詳しくは窒素原子またはリン原子をイオン中心とするカチオンを有し、且つ１００℃以下の温度で液体のイオン液体（Ｂ）０．００１〜１５重量部を含有すること（例えば、特許文献１参照）や、特定構造のアンモニウム塩（１）および特定構造のスルホニウム塩（２）から選ばれる１種以上のオニウム化合物を含有すること（例えば、特許文献２参照）が開示されている。 For example, in order to obtain a resin composition imparted with antistatic performance without impairing hue and transparency, 100 parts by weight of the thermoplastic resin (A) and an ionic liquid, specifically a nitrogen atom or a phosphorus atom, are added to the composition. Containing an ionic liquid (B) in an amount of 0.001 to 15 parts by weight (for example, see Patent Document 1), and an ammonium salt having a specific structure (1) and containing 1 or more types of onium compounds chosen from the sulfonium salt (2) of a specific structure are disclosed (for example, refer patent document 2).
また、剥離した際に帯電防止されていない被着体の帯電防止が図れ、被着体への汚染が低減された、接着信頼性に優れる粘着剤組成物を得るために、組成物に、脂環族イオン液体、およびベースポリマーとしてガラス転移温度Ｔｇが０℃以下のポリマーを含有することが開示されている（例えば、特許文献３参照）。
押出成形において、成形機壁面への添加剤の付着（プレートアウト）や液垂れがなく、適度な滑性が付与され、吐出安定性や成形品の外観、導電性に優れ、導電性のばらつきが小さく、長期間にわたって効果を持続させる長期性が良好な押出成形用熱可塑性樹脂組成物を得るために、熱可塑性樹脂（Ａ）１００重量部に対し、特定構造のイミダゾリウム塩（Ｂ）と特定構造のイミダゾリウム塩（Ｃ）とを総量で０．１〜１０重量部含み、イミダゾリウム塩（Ｂ）とイミダゾリウム塩（Ｃ）との質量比を８／２〜３／７とすることが開示されている（例えば、特許文献４参照）。
In addition, in order to obtain a pressure-sensitive adhesive composition having excellent adhesion reliability in which the adherend that is not antistatic when peeled can be prevented from being charged and the contamination of the adherend is reduced. It is disclosed that a cyclic ionic liquid and a polymer having a glass transition temperature Tg of 0 ° C. or lower are contained as a base polymer (see, for example, Patent Document 3).
In extrusion molding, there is no adhesion (plate-out) or dripping of additives to the molding machine wall surface, moderate lubricity is imparted, excellent discharge stability, appearance of the molded product, conductivity, and variation in conductivity. In order to obtain a thermoplastic resin composition for extrusion molding that is small and has a long-lasting effect with a long-lasting effect, it is identified as an imidazolium salt (B) having a specific structure with respect to 100 parts by weight of the thermoplastic resin (A). The total amount of the imidazolium salt (C) having a structure is 0.1 to 10 parts by weight, and the mass ratio of the imidazolium salt (B) and the imidazolium salt (C) is 8/2 to 3/7. It is disclosed (for example, see Patent Document 4).
透明性が損なわれること無く、ブリードによる被着体への汚染が低減され、帯電防止性能（特に表面抵抗率が１０１０Ω／ｓｑ．以下）が付与されたポリエステル樹脂組成物を得るために、組成物に、主たる繰り返し単位の９０モル％以上がエチレンテレフタレートからなるポリステル重縮合体（Ａ）と、少なくとも一成分として脂環式炭化水素基を有するモノマー成分を含有するポリエステル重縮合体（Ｂ）と、イオン液体（Ｃ）とを含有することが開示されている（例えば、特許文献５参照）。 In order to obtain a polyester resin composition in which the contamination of the adherend due to bleeding is reduced and the antistatic performance (particularly the surface resistivity is 10 10 Ω / sq. Or less) is imparted without loss of transparency. Polyester polycondensate (B) containing a polyester polycondensate (A) in which 90 mol% or more of main repeating units are composed of ethylene terephthalate and a monomer component having an alicyclic hydrocarbon group as at least one component in the composition And ionic liquid (C) are disclosed (for example, refer to Patent Document 5).
また、耐汚染性、透明性、光沢性および帯電防止性に優れた熱可塑性樹脂組成物を得るために、組成物を、熱可塑性樹脂（Ａ）８０〜１００質量部、ポリオレフィン樹脂が不飽和ポリカルボン酸あるいはその誘導体（Ｅ）及び特定構造の（メタ）アクリル酸エステル（Ｆ）でグラフト変性され、変性ポリオレフィン樹脂に（Ｅ）、（Ｆ）が各々０．１〜２０重量％、０．１〜３０重量％含有され、かつ重量平均分子量が１５，０００〜１５０，０００である変性ポリオレフィン樹脂（Ｂ）０．１〜１０質量部およびイオン液体（Ｃ）０．１〜１０質量部を含有する熱可塑性樹脂組成物とすることが開示されている（例えば、特許文献６参照）。
そのほか、ポリオレフィン、イオン液体、カーボンナノファイバーを含むポリマーブレンド等も開示されている（例えば、特許文献７参照）。
In addition, in order to obtain a thermoplastic resin composition excellent in stain resistance, transparency, glossiness and antistatic property, the composition is composed of 80 to 100 parts by mass of the thermoplastic resin (A), and the polyolefin resin is unsaturated poly Graft-modified with carboxylic acid or its derivative (E) and (meth) acrylic ester (F) having a specific structure, and (E) and (F) are 0.1 to 20% by weight, 0.1 0.1 to 10 parts by mass of a modified polyolefin resin (B) having a weight average molecular weight of 15,000 to 150,000 and 0.1 to 10 parts by mass of an ionic liquid (C). Disclosed is a thermoplastic resin composition (for example, see Patent Document 6).
In addition, polymer blends containing polyolefin, ionic liquid, carbon nanofibers, and the like are also disclosed (for example, see Patent Document 7).
しかし、特許文献１〜７に示される手法では、不飽和エステル由来の構成単位を含む重合体に対する帯電防止性が不十分であった。
本発明者等は、不飽和エステル由来の構成単位を含む重合体と疎水性のイオン液体とを組み合わせることで、両者を含む組成物が優れた帯電防止性を示すことを見出し、この知見に基づいて本発明を完成するに至った。
すなわち、本発明の目的は、帯電防止性に優れる重合体組成物を提供することにある。
However, the methods disclosed in Patent Documents 1 to 7 have insufficient antistatic properties for a polymer containing a structural unit derived from an unsaturated ester.
Based on this finding, the present inventors have found that a composition containing both of a unit containing a structural unit derived from an unsaturated ester and a hydrophobic ionic liquid show excellent antistatic properties in a composition containing both. The present invention has been completed.
That is, an object of the present invention is to provide a polymer composition having excellent antistatic properties.
＜１＞ 不飽和エステル由来の構成単位を含む重合体と、イオン液体（Ｌ）および水（Ｗ）を容積比（Ｌ：Ｗ）＝１：１で混合し、２３℃で２４時間攪拌した後４８時間静置して分取したイオン液体相中の水分量が１０万ｐｐｍ以下となるイオン液体とを含む重合体組成物である。 <1> A polymer containing a structural unit derived from an unsaturated ester, an ionic liquid (L) and water (W) are mixed at a volume ratio (L: W) = 1: 1 and stirred at 23 ° C. for 24 hours. It is a polymer composition containing an ionic liquid having a water content of 100,000 ppm or less in an ionic liquid phase that is allowed to stand for 48 hours and collected.
＜２＞ 前記イオン液体の含有量が、前記重合体１００質量部に対して、０．００１質量部〜２０質量部である前記＜１＞に記載の重合体組成物である。 <2> The polymer composition according to <1>, wherein the content of the ionic liquid is 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymer.
＜３＞ 前記水分量が１万ｐｐｍ以下である前記＜１＞または前記＜２＞に記載の重合体組成物である。 <3> The polymer composition according to <1> or <2>, wherein the water content is 10,000 ppm or less.
＜４＞ 前記イオン液体のアニオン種が［（Ｃ２Ｆ５）３ＰＦ３］−である前記＜１＞〜前記＜３＞のいずれか１つに記載の重合体組成物である。 <4> The polymer composition according to any one of <1> to <3>, wherein the anionic species of the ionic liquid is [(C 2 F 5 ) 3 PF 3 ] — .
＜５＞ 前記重合体１ｋｇ中の前記不飽和エステル由来の構成単位量が２モル以上である前記＜１＞〜前記＜４＞のいずれか１つに記載の重合体組成物である。 <5> The polymer composition according to any one of <1> to <4>, wherein the amount of the structural unit derived from the unsaturated ester in 1 kg of the polymer is 2 mol or more.
本発明によれば、帯電防止性に優れる重合体組成物が提供される。 According to the present invention, a polymer composition having excellent antistatic properties is provided.
以下に、本発明の重合体組成物に係る実施形態について詳細且つ具体的に説明する。但し、本発明はこれらの例によって何ら制限されるものではない。 Hereinafter, embodiments according to the polymer composition of the present invention will be described in detail and specifically. However, the present invention is not limited to these examples.
＜重合体組成物＞
本発明の重合体組成物は、不飽和エステル由来の構成単位を含む重合体と、イオン液体（Ｌ）および水（Ｗ）を容積比（Ｌ：Ｗ）＝１：１で混合し、２３℃で２４時間攪拌した後４８時間静置して分取したイオン液体相中の水分量が１０万ｐｐｍ以下となるイオン液体とを含む。
本発明の重合体組成物は、不飽和エステル由来の構成単位を含む重合体と、イオン液体とを含む。
本発明で用いるイオン液体は、イオン液体の容積をＬ、水の容積をＷとしたとき、イオン液体と水とを容積比（Ｌ：Ｗ）＝１：１で混合し、２３℃で２４時間攪拌した後４８時間静置して分取したイオン液体相中の水分量が１０万ｐｐｍ以下となる物性であり、すなわち、高い疎水性の化合物である。以下、イオン液体について疎水性というときは、イオン液体が上記物性であることをいう。かかる疎水性のイオン液体を、特定イオン液体ともいう。
また、不飽和エステル由来の構成単位を含む重合体を単に、特定重合体とも称する。
本発明の重合体組成物は、本発明の効果を損なわない限度において、界面活性剤、紫外線吸収剤等、種々の添加物を、さらに含んでいてもよい。
<Polymer composition>
In the polymer composition of the present invention, a polymer containing a structural unit derived from an unsaturated ester, an ionic liquid (L) and water (W) are mixed at a volume ratio (L: W) = 1: 1, and 23 ° C. And the ionic liquid in which the water content in the ionic liquid phase, which was allowed to stand for 48 hours after being stirred for 4 hours, was 100,000 ppm or less.
The polymer composition of this invention contains the polymer containing the structural unit derived from unsaturated ester, and an ionic liquid.
The ionic liquid used in the present invention is a mixture of ionic liquid and water at a volume ratio (L: W) = 1: 1, where L is the volume of the ionic liquid and W is the volume of water, and 24 hours at 23 ° C. It is a physical property in which the water content in the ionic liquid phase collected after standing for 48 hours after stirring is 100000 ppm or less, that is, a highly hydrophobic compound. Hereinafter, when the ionic liquid is hydrophobic, it means that the ionic liquid has the above physical properties. Such a hydrophobic ionic liquid is also referred to as a specific ionic liquid.
Moreover, the polymer containing the structural unit derived from unsaturated ester is also only called a specific polymer.
The polymer composition of the present invention may further contain various additives such as a surfactant and an ultraviolet absorber as long as the effects of the present invention are not impaired.
本発明の重合体組成物が、不飽和エステル由来の構成単位を含む重合体（特定重合体）と、疎水性のイオン液体（特定イオン液体）とを含むことで、理由は定かではないが、公知の樹脂型の帯電防止剤に比べ、表面抵抗率が低く、帯電防止性に優れる。 Although the polymer composition of the present invention contains a polymer (specific polymer) containing a structural unit derived from an unsaturated ester and a hydrophobic ionic liquid (specific ionic liquid), the reason is not clear, Compared with known resin-type antistatic agents, it has a low surface resistivity and excellent antistatic properties.
また、一般に、界面活性剤等の公知の帯電防止剤は、樹脂に添加して成形品とした場合に、表面に浸み出し、成形品表面に帯電防止剤が付着したり、成形品が白濁する等のブリードと呼ばれる現象が生じることがある。特に、ブリードは、帯電防止剤が低分子化合物である場合に顕著であった。しかし、本発明の重合体組成物は、理由は定かではないが、ブリードを生じにくい。
本発明の重合体組成物は、特定イオン液体の含有量が少量でも優れた帯電防止性を発現するため、透明な樹脂に添加し、成形品とした場合でも、成形品の透明性を損ねにくく、光学特性の低下を抑制することができる。
さらに、本発明の湿度環境に関わらず、優れた帯電防止性を維持することができ、湿度依存性の低い、安定した帯電防止性を発現することができる。
In general, when a known antistatic agent such as a surfactant is added to a resin to form a molded product, it oozes out to the surface and the antistatic agent adheres to the surface of the molded product, or the molded product becomes cloudy. A phenomenon called bleeding may occur. In particular, bleeding was significant when the antistatic agent was a low molecular compound. However, the polymer composition of the present invention is less likely to cause bleeding, although the reason is not clear.
Since the polymer composition of the present invention exhibits excellent antistatic properties even when the content of the specific ionic liquid is small, even when added to a transparent resin to form a molded product, it is difficult to impair the transparency of the molded product. It is possible to suppress a decrease in optical characteristics.
Furthermore, regardless of the humidity environment of the present invention, excellent antistatic properties can be maintained, and stable antistatic properties with low humidity dependence can be expressed.
〔イオン液体〕
イオン液体とは、多くの場合、１００℃〜１５０℃にて液状のイオン性化合物であり、カチオン種とアニオン種との組み合わせで構成される塩である。なお、イオン液体は、単一の化合物で液状である物質であり、溶媒との組み合わせにより液状となっている混合物ではない。
本発明で用いられる特定イオン液体は、かかる構成の塩であって、既述の物性を有する疎水性の化合物であれば、特に制限されない。
[Ionic liquid]
In many cases, the ionic liquid is an ionic compound that is liquid at 100 ° C. to 150 ° C., and is a salt composed of a combination of a cationic species and an anionic species. Note that the ionic liquid is a substance that is a single compound and is in a liquid state, and is not a mixture that is in a liquid state in combination with a solvent.
The specific ionic liquid used in the present invention is not particularly limited as long as it is a salt having such a structure and is a hydrophobic compound having the above-described physical properties.
−カチオン種−
特定イオン液体を構成し得るカチオン種としては、例えば、メチルイミダゾリウム系、ピリジニウム系、メチルピロリジニウム系、アンモニウム系等が挙げられる。
メチルイミダゾリウム系カチオン種としては、下記Ｃ−１で表されるイオン種が挙げられる。ピリジニウム系カチオン種としては、下記Ｃ−２で表されるイオン種が挙げられる。メチルピロリジニウム系カチオン種としては、下記Ｃ−３で表されるイオン種が挙げられる。アンモニウム系カチオン種としては、下記Ｃ−４で表されるイオン種が挙げられる。そのほか、下記Ｃ−５で示されるイオン種を用いてもよい。
-Cationic species-
Examples of the cationic species that can constitute the specific ionic liquid include methylimidazolium-based, pyridinium-based, methylpyrrolidinium-based, and ammonium-based compounds.
Examples of the methylimidazolium-based cation species include ionic species represented by the following C-1. Examples of the pyridinium-based cation species include ionic species represented by the following C-2. Examples of the methylpyrrolidinium-based cation species include ionic species represented by the following C-3. Examples of the ammonium-based cation species include ionic species represented by the following C-4. In addition, an ionic species represented by C-5 below may be used.
Ｃ−１におけるＲ１およびＲ２、Ｃ−２におけるＲ１およびＲ２、Ｃ−３におけるＲ、Ｃ−４におけるＲ１、Ｒ２、Ｒ３、およびＲ４、ならびに、Ｃ−５におけるＲ１、Ｒ２、およびＲ３は、各々独立に、水素原子または置換基である。
置換基は、アルキル基、アリール基、アルコキシ基、ヒドロキシアルキル基、アルキルエーテル基等が挙げられ、中でも、アルキル基、アルコキシ基、ヒドロキシアルキル基、または、アルキルエーテル基が好ましい。
R 1, R 2, R 3 in R 1 and R 2, C-3 in R 1 and R 2, C-2 in the C-1 R, the C-4, and R 4, and, R in the C-5 1 , R 2 and R 3 are each independently a hydrogen atom or a substituent.
Examples of the substituent include an alkyl group, an aryl group, an alkoxy group, a hydroxyalkyl group, and an alkyl ether group. Among them, an alkyl group, an alkoxy group, a hydroxyalkyl group, or an alkyl ether group is preferable.
Ｃ−１〜Ｃ−５の具体例としては、下記Ｃ−６〜Ｃ−１４等が挙げられる。 Specific examples of C-1 to C-5 include the following C-6 to C-14.
その他、Ｇｕａｎｉｄｉｎｉｕｍ（ＧＵＡ）、Ｎ−（Ｍｅｔｈｏｘｙｅｔｈｙｌ）−Ｎｍｅｔｈｙｌｍｏｒｐｈｏｌｉｎｉｕｍ（ＭＯＥＭＭＯ）、１−（２−Ｍｅｔｈｏｘｙｅｔｈｙｌ）−１−ｍｅｔｈｙｌ−ｐｉｐｅｒｉｄｉｎｉｕｍ（ＭＯＥＭＰＩＰ）、Ｔｒｉｈｅｘｙｌ（ｔｅｔｒａｄｅｃｙｌ）−ｐｈｏｓｐｈｏｎｉｕｍ（ＰＨ３Ｔ）等が挙げられる。 In addition, Guanidinium (GUA), N- (Methoxyethyl) -Nmethylmorpholinium (MOEMMO), 1- (2-Methoxyethyl) -1-methyl-piperidinium (MOEMPIP), Trihexyl3 (Tetradicyl), etc.
カチオン種としては、Ｃ−１〜Ｃ−５で表されるイオン種が好ましく、Ｃ−６〜Ｃ−１１４で表されるイオン種がより好ましい。 As the cationic species, ionic species represented by C-1 to C-5 are preferable, and ionic species represented by C-6 to C-114 are more preferable.
−アニオン種−
特定イオン液体を構成し得るアニオン種としては、例えば、下記Ａ−１〜Ａ−５で示されるイオン種が挙げられる。ただし、本発明におけるアニオン種は、これらに限定されない。
-Anion species-
Examples of the anionic species that can constitute the specific ionic liquid include ionic species represented by the following A-1 to A-5. However, the anion species in the present invention is not limited to these.
Ａ−３におけるｎは、１以上の整数を表す。
Ａ−１はＯｔｆとも称され、Ａ−２はＮＴＦまたはＴＦＳＩとも称され、Ａ−４はＢＦ４とも称される。また、Ａ−３で表されるイオン種のうち、ｎが２であるイオン種（Ａ−５）をＦＡＰとも称する。
アニオン種は、以上の中でも、Ａ−１〜Ａ−４で表されるイオン種が好ましく、Ａ−３で表されるイオン種がより好ましく、Ａ−５で表されるイオン種〔ＦＡＰ；トリス（ペンタフルオロエチル）トリフルオロフォスフェート〕がさらに好ましい。アニオン種としてＦＡＰを用いると、特に帯電防止性が湿度依存しにくく、ブリード発生をし易い。
N in A-3 represents an integer of 1 or more.
A-1 is also called Otf, A-2 is also called NTF or TFSI, and A-4 is also called BF4. Of the ionic species represented by A-3, the ionic species (A-5) in which n is 2 is also referred to as FAP.
Among the above, the anion species are preferably ion species represented by A-1 to A-4, more preferably an ion species represented by A-3, and an ion species represented by A-5 [FAP; (Pentafluoroethyl) trifluorophosphate] is more preferable. When FAP is used as the anionic species, the antistatic property is not particularly dependent on humidity, and bleeding is likely to occur.
イオン液体の疎水性は、既述のように、イオン液体と水とを容積比（Ｌ：Ｗ）＝１：１で混合し、２３℃で２４時間攪拌した後４８時間静置して分取したイオン液体相中の水分量で判断する。
水分量は、より具体的には、次のように測定する。
イオン性液体と水との混合物を攪拌し、静置したのち、イオン性液体の層を分取し、これを水分値測定サンプルとする。水分測定はカールフィッシャー水分計（京都電子工業株式会社製ＭＫＣ−２１０）を用いて測定する。
イオン性液体と水との混合物を攪拌した後、４８時間以上静置しても二層に分離しないイオン性液体は、水に溶解すると判断する。
As described above, the hydrophobicity of the ionic liquid is determined by mixing the ionic liquid and water at a volume ratio (L: W) = 1: 1, stirring at 23 ° C. for 24 hours, and then allowing to stand for 48 hours. Judged by the amount of water in the ionic liquid phase.
More specifically, the water content is measured as follows.
The mixture of the ionic liquid and water is stirred and allowed to stand, and then the layer of the ionic liquid is separated and used as a moisture value measurement sample. The moisture measurement is performed using a Karl Fischer moisture meter (MKC-210, manufactured by Kyoto Electronics Industry Co., Ltd.).
After stirring the mixture of the ionic liquid and water, it is determined that the ionic liquid that does not separate into two layers even after standing for 48 hours or more is dissolved in water.
本発明では、イオン液体相中の水分量が１０万ｐｐｍ以下であるイオン液体（特定イオン液体）を用いるが、特定イオン液体は疎水性がより高いことが好ましい。すなわち、水分量は、さらに小さいことが好ましく、具体的には、１万ｐｐｍ以下であることが好ましく、５０００ｐｐｍ以下であることがより好ましい。
アニオン種として、ＦＡＰを用いると、イオン液体は、より高い疎水性を示し、水分量も５０００ｐｐｍ以下となる。
In the present invention, an ionic liquid (specific ionic liquid) having a water content in the ionic liquid phase of 100,000 ppm or less is used, but the specific ionic liquid is preferably more hydrophobic. That is, the moisture content is preferably even smaller, specifically 10,000 ppm or less, and more preferably 5000 ppm or less.
When FAP is used as the anionic species, the ionic liquid exhibits higher hydrophobicity and the water content is 5000 ppm or less.
特定イオン液体において、カチオン種とアニオン種との好ましい組み合わせは、カチオン種の好ましい態様とアニオン種の好ましい態様との組み合わせであり、カチオン種のより好ましい態様とアニオン種のより好ましい態様との組み合わせが、より好ましい。
特に、アニオン種として、ＦＡＰを用い、カチオン種として、Ｃ−６〜Ｃ−１４の各イオン種を用いることが好ましい。
In the specific ionic liquid, a preferred combination of the cationic species and the anionic species is a combination of a preferred embodiment of the cationic species and a preferred embodiment of the anionic species, and a combination of a more preferred embodiment of the cationic species and a more preferred embodiment of the anionic species. More preferable.
In particular, it is preferable to use FAP as the anion species and C-6 to C-14 ion species as the cation species.
重合体組成物中の特定イオン液体の含有量は、特に制限されないが、より帯電防止性を向上する観点から、特定重合体１００質量部に対し、０．００１質量部〜２０質量部であることが好ましい。特定重合体１００質量部に対し、０．０５質量部〜１５質量部であることがより好ましく、０．５質量部〜１０質量部であることがさらに好ましい。
重合体組成物からの特定イオン液体の浸み出し（ブリード）を抑制する観点からは、重合体組成物中の特定イオン液体の含有量は、特定重合体１００質量部に対し、９質量部以下であることが好ましい。
The content of the specific ionic liquid in the polymer composition is not particularly limited, but is 0.001 part by mass to 20 parts by mass with respect to 100 parts by mass of the specific polymer from the viewpoint of further improving the antistatic property. Is preferred. The amount is more preferably 0.05 parts by mass to 15 parts by mass, and further preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the specific polymer.
From the viewpoint of suppressing the bleeding (bleeding) of the specific ionic liquid from the polymer composition, the content of the specific ionic liquid in the polymer composition is 9 parts by mass or less with respect to 100 parts by mass of the specific polymer. It is preferable that
〔不飽和エステル由来の構成単位を含む重合体〕
本発明の重合体組成物は、不飽和エステル由来の構成単位を含む重合体（特定重合体）を含有する。
特定重合体は、不飽和エステル由来の構成単位を含んでいれば、特に制限されない。例えば、不飽和エステル由来の構成単位のみを有する不飽和エステルの単独重合体であってもよいし、さらに、α−オレフィン由来の構成単位、不飽和脂肪酸由来の構成単位を含んでいてもよい。
[Polymer containing structural unit derived from unsaturated ester]
The polymer composition of this invention contains the polymer (specific polymer) containing the structural unit derived from unsaturated ester.
The specific polymer is not particularly limited as long as it contains a structural unit derived from an unsaturated ester. For example, the homopolymer of the unsaturated ester which has only the structural unit derived from unsaturated ester may be sufficient, and also the structural unit derived from an alpha olefin and the unsaturated fatty acid may be included.
不飽和エステル由来の構成単位を構成する不飽和エステルとしては、不飽和カルボン酸のアルキルエステルが挙げられる。
例えばアクリル酸アルキルエステル、メタクリル酸アルキルエステル、クロトン酸アルキルエステル、マレイン酸アルキルエステル等が例示される。また、酢酸ビニルであってもよい。
As unsaturated ester which comprises the structural unit derived from unsaturated ester, the alkyl ester of unsaturated carboxylic acid is mentioned.
For example, an acrylic acid alkyl ester, a methacrylic acid alkyl ester, a crotonic acid alkyl ester, a maleic acid alkyl ester and the like are exemplified. Vinyl acetate may also be used.
アルキルエステルのアルキル部位としては、炭素数１〜１２のものを挙げることができ、より具体的には、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、セカンダリーブチル、２−エチルヘキシル、イソオクチル等のアルキル基を例示することができる。
本発明では、アルキルエステルのアルキル部位の炭素数は、１〜８が好ましい。
Examples of the alkyl moiety of the alkyl ester include those having 1 to 12 carbon atoms, and more specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, 2-ethylhexyl, An alkyl group such as isooctyl can be exemplified.
In the present invention, the number of carbon atoms in the alkyl moiety of the alkyl ester is preferably 1-8.
不飽和カルボン酸は、１分子中に２つ以上のカルボキシ基を有するものであってもよい。１分子中に２つ以上のカルボキシ基を有する不飽和カルボン酸は、複数あるカルボキシ基の少なくとも１つがアルキルエステルとなっていればよく、例えば、マレイン酸アルキルエステルとしては、マレイン酸モノアルキルエステルであっても、マレイン酸ジアルキルエステルであってもよい。 The unsaturated carboxylic acid may have two or more carboxy groups in one molecule. An unsaturated carboxylic acid having two or more carboxy groups in one molecule is sufficient if at least one of a plurality of carboxy groups is an alkyl ester. For example, maleic acid alkyl esters include maleic acid monoalkyl esters. Alternatively, it may be a maleic acid dialkyl ester.
不飽和エステルは、上記の中でも、アクリル酸又はメタクリル酸のメチルエステル、エチルエステル、ノルマルブチルエステル、イソブチルエステルが好ましい。
不飽和エステル由来の構成単位は、１種単独でもよいし、複数種を組み合わせて用いてもよい。
特定重合体は、単一の不飽和エステル由来の構成単位を有する不飽和エステルの単独重合体でもよい。このような単独重合体としては、メタクリル酸エチル重合体（ＥＭＡとも称する）、アクリル酸エチル重合体（ＥＡとも称する）等が挙げられる。
また、２種以上の不飽和エステル由来の構成単位を有する不飽和エステルの２元以上の共重合体であってもよい。このとき、２種以上の不飽和エステル由来の構成単位を有する共重合体は、ランダム共重合体であっても、ブロック共重合体であっても、グラフト共重合体であってもよいが、ランダム共重合体であることが好ましい。
Among the above, the unsaturated ester is preferably methyl ester, ethyl ester, normal butyl ester, or isobutyl ester of acrylic acid or methacrylic acid.
As the structural unit derived from the unsaturated ester, one type may be used alone, or a plurality of types may be used in combination.
The specific polymer may be a homopolymer of an unsaturated ester having a structural unit derived from a single unsaturated ester. Examples of such a homopolymer include ethyl methacrylate polymer (also referred to as EMA), ethyl acrylate polymer (also referred to as EA), and the like.
Moreover, the binary or more copolymer of the unsaturated ester which has a structural unit derived from 2 or more types of unsaturated ester may be sufficient. At this time, the copolymer having a structural unit derived from two or more unsaturated esters may be a random copolymer, a block copolymer, or a graft copolymer, A random copolymer is preferred.
特定重合体は、さらに、α−オレフィン由来の構成単位や、不飽和脂肪酸由来の構成単位等の、不飽和エステル由来の構成単位とは異なる他の構成単位をさらに含んでいてもよい。
α−オレフィン由来の構成単位を構成するα−オレフィンとしては、エチレン、プロピレン、ブチレン等が挙げられ、中でも、エチレンまたはプロピレンが好ましい。α−オレフィン由来の構成単位は、１種単独でもよいし、複数種を組み合わせて用いてもよい。
不飽和脂肪酸由来の構成単位を構成する不飽和脂肪酸としては、例えばアクリル酸、メタクリル酸、エタクリル酸、クロトン酸、フマル酸、マレイン酸、無水マレイン酸、イタコン酸、又は無水イタコン酸等が挙げられる。不飽和脂肪酸は、これらの中でも、アクリル酸およびメタクリル酸の少なくとも一方であることが好ましい。不飽和脂肪酸由来の構成単位は、１種単独でもよいし、複数種を組み合わせて用いてもよい。
特定重合体が、他の構成単位を含む共重合体である場合、共重合体は、ランダム共重合体であっても、ブロック共重合体であっても、グラフト共重合体であってもよいが、ランダム共重合体であることが好ましい。
The specific polymer may further include another structural unit different from the structural unit derived from the unsaturated ester, such as the structural unit derived from the α-olefin and the structural unit derived from the unsaturated fatty acid.
Examples of the α-olefin constituting the α-olefin-derived structural unit include ethylene, propylene, butylene, and among them, ethylene or propylene is preferable. The structural unit derived from α-olefin may be used alone or in combination of two or more.
Examples of the unsaturated fatty acid constituting the structural unit derived from the unsaturated fatty acid include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride. . Among these, the unsaturated fatty acid is preferably at least one of acrylic acid and methacrylic acid. The structural unit derived from the unsaturated fatty acid may be used alone or in combination of two or more.
When the specific polymer is a copolymer containing other structural units, the copolymer may be a random copolymer, a block copolymer, or a graft copolymer. Is preferably a random copolymer.
特定重合体が、他の構成単位をさらに含む場合、例えば、不飽和エステル由来の構成単位と、α−オレフィン由来の構成単位または不飽和脂肪酸由来の構成単位とを含む２元共重合体であってもよい。このような共重合体としては、例えば、エチレン／アクリル酸エチル共重合体（ＥＥＡとも称する）、エチレン／メタクリル酸メチル共重合体（ＥＭＭＡとも称する）等が挙げられる。
また、不飽和エステル由来の構成単位と、α−オレフィン由来の構成単位と、不飽和脂肪酸由来の構成単位とを含む３元共重合体であってもよい。このような共重合体としては、例えば、エチレン／メタクリル酸／メタクリル酸エステル共重合体等が挙げられる。
When the specific polymer further includes another structural unit, for example, it is a binary copolymer including a structural unit derived from an unsaturated ester and a structural unit derived from an α-olefin or an unsaturated fatty acid. May be. Examples of such a copolymer include an ethylene / ethyl acrylate copolymer (also referred to as EEA) and an ethylene / methyl methacrylate copolymer (also referred to as EMMA).
Moreover, the ternary copolymer containing the structural unit derived from unsaturated ester, the structural unit derived from (alpha) -olefin, and the structural unit derived from unsaturated fatty acid may be sufficient. Examples of such a copolymer include an ethylene / methacrylic acid / methacrylic acid ester copolymer.
特定重合体は、重合体組成物の帯電防止性を実用的な性能範囲とする観点から、特定重合体１ｋｇ中の不飽和エステル由来の構成単位量が２モル以上であることが好ましく、重合体組成物の透明詩を維持する観点らは、さらに３モル以上であることが好ましい。 From the viewpoint of setting the antistatic property of the polymer composition to a practical performance range, the specific polymer preferably has a constituent unit amount derived from an unsaturated ester in 1 kg of the specific polymer of 2 mol or more. From the viewpoint of maintaining the transparent poetry of the composition, it is preferably 3 mol or more.
特定重合体は、実用的な機械的強度や成形加工性の面から２３０℃、１０ｋｇ荷重（ＪＩＳ Ｋ７２１０−１９９９に準拠）におけるメルトフローレート（ＭＦＲ）が０．０１ｇ／１０分〜１０００ｇ／１０分、特に０．１ｇ／１０分〜５００ｇ／１０分のものが好適である。 The specific polymer has a melt flow rate (MFR) of 0.01 g / 10 min to 1000 g / 10 min at 230 ° C. and 10 kg load (conforming to JIS K7210-1999) from the viewpoint of practical mechanical strength and moldability. Particularly preferred are those of 0.1 g / 10 min to 500 g / 10 min.
〔他の成分〕
本発明の重合体組成物は、本発明の効果を損なわない限度において、さらに、界面活性剤、褪色防止剤、乳化安定剤、浸透促進剤、紫外線吸収剤、防腐剤、防黴剤等の他の成分を含有していてもよい。
[Other ingredients]
The polymer composition of the present invention can be used in addition to surfactants, antifading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, antiseptics, antifungal agents, etc., as long as the effects of the present invention are not impaired. The component may be contained.
＜重合体組成物の製造方法＞
本発明の重合体組成物の製造方法は、特定重合体をベース樹脂とし、特定イオン液体と共に混合すればよい。帯電防止性を向上する観点から、特定重合体１００質量部に対し、０．００１質量部〜２０質量部の範囲で、両者を混合することが好ましい。
特定重合体と、特定イオン液体とのほかに、さらに、他の成分を混合して重合体組成物を製造してもよい。
<Method for producing polymer composition>
In the method for producing the polymer composition of the present invention, the specific polymer may be used as a base resin and mixed with the specific ionic liquid. From the viewpoint of improving the antistatic property, it is preferable to mix both in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the specific polymer.
In addition to the specific polymer and the specific ionic liquid, other components may be further mixed to produce a polymer composition.
本発明の重合体組成物を用いて、さらに押出し成形、プレス成形、射出成形等して、成形体としてもよい。
本発明の重合体組成物は、既述のとおり、帯電防止性に優れており、本発明の重合体組成物は、具体的には、天井材、床材等の建築、土木材料、自動車部品、ＯＡ機器、家電製品部品、あるいはその保管・収納ケース、文具、日用品などに広く使用することができる。
Using the polymer composition of the present invention, a molded body may be formed by extrusion molding, press molding, injection molding, or the like.
As described above, the polymer composition of the present invention is excellent in antistatic properties. Specifically, the polymer composition of the present invention is specifically designed for buildings such as ceiling materials and floor materials, civil engineering materials, and automobile parts. It can be widely used for office automation equipment, home appliance parts, storage / storage cases, stationery, daily necessities, and the like.
次に、本発明を実施例により更に詳細に説明する。但し、本発明は、これらの例によって何ら制限されるものではない。 Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by these examples.
〔イオン液体〕
イオン液体は、以下の製品を用いた。
カチオン種とアニオン種とを、それぞれ「［カチオン種］［アニオン種］」として表す。なお、下記カチオン種およびアニオン種の化学構造は、既述の具体例Ｃ−６〜Ｃ−１４またはＡ−１〜Ａ−５として示したとおりである。
・[EMIM][FAP]：メルク社製、
1-Ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate
・[EMIM][OTf]：メルク社製
・[EMIM][NTF]：メルク社製
・[HMIM][FAP]：メルク社製
・[BMPL][FAP]：メルク社製
・[NM4][FAP] ：メルク社製
[Ionic liquid]
The following products were used as the ionic liquid.
The cationic species and the anionic species are represented as “[cationic species] [anionic species]”, respectively. The chemical structures of the following cation species and anion species are as shown in the specific examples C-6 to C-14 or A-1 to A-5 described above.
・ [EMIM] [FAP]: Merck
1-Ethyl-3-methylimidazolium tris (pentafluoroethyl) trifluorophosphate
・ [EMIM] [OTf]: Merck ・ [EMIM] [NTF]: Merck ・ [HMIM] [FAP]: Merck ・ [BMPL] [FAP]: Merck ・ [NM4] [FAP ]: Merck
〔重合体（ベース樹脂）〕
１）特定重合体
・エチレン・アクリル酸エチルランダム共重合体（ＥＥＡ-１）
アクリル酸エチル（ＥＡ）含量；３４質量％、ＭＦＲ；２５ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠）
・エチレン・アクリル酸エチルランダム共重合体（ＥＥＡ-２）
アクリル酸エチル（ＥＡ）含量；１６質量％、ＭＦＲ；１ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠）
・エチレン・アクリル酸エチルランダム共重合体組成物（ＥＥＡ-３）
ＥＥＡ−２と、下記ＬＤＰＥ（ミラソン１６Ｐ）とを、ＥＥＡ−２濃度が３質量％となる量で混合した組成物
・エチレン・アクリル酸エチルランダム共重合体（ＥＥＡ-４）
アクリル酸エチル（ＥＡ）含量；１９質量％、ＭＦＲ；５ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠）
・エチレン・アクリル酸エチルランダム共重合体（ＥＥＡ-５）
アクリル酸エチル（ＥＡ）含量；２５質量％、ＭＦＲ；２０ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠）
[Polymer (base resin)]
1) Specific polymer / ethylene / ethyl acrylate random copolymer (EEA-1)
Ethyl acrylate (EA) content: 34% by mass, MFR: 25 g / 10 min (190 ° C., 2160 g load, according to JIS K7210-1999)
・ Ethylene acrylate random copolymer (EEA-2)
Ethyl acrylate (EA) content: 16% by mass, MFR: 1 g / 10 min (190 ° C., 2160 g load, according to JIS K7210-1999)
・ Ethylene acrylate random copolymer composition (EEA-3)
A composition in which EEA-2 and the following LDPE (Mirason 16P) are mixed in an amount such that the EEA-2 concentration is 3% by mass. Ethylene / ethyl acrylate random copolymer (EEA-4)
Ethyl acrylate (EA) content: 19% by mass, MFR; 5 g / 10 min (190 ° C., 2160 g load, according to JIS K7210-1999)
・ Ethylene acrylate random copolymer (EEA-5)
Ethyl acrylate (EA) content: 25% by mass, MFR; 20 g / 10 min (190 ° C., 2160 g load, according to JIS K7210-1999)
・エチレン・アクリル酸メチルランダム共重合体（ＥＭＡ-１）
アクリル酸メチル（ＭＡ）含量；３０質量％、ＭＦＲ；１５ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠）
・ Ethylene / methyl acrylate random copolymer (EMA-1)
Methyl acrylate (MA) content: 30% by mass, MFR: 15 g / 10 min (190 ° C., 2160 g load, according to JIS K7210-1999)
・エチレン・酢酸ビニルランダム共重合体（ＥＶＡ-１）
酢酸ビニル（ＶＡ）含量；３３質量％、ＭＦＲ；１４ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠）
・エチレン・酢酸ビニルランダム共重合体（ＥＶＡ-２）
酢酸ビニル（ＶＡ）含量；４６質量％、ＭＦＲ；２．５ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠）
・ Ethylene / vinyl acetate random copolymer (EVA-1)
Vinyl acetate (VA) content: 33% by mass, MFR: 14 g / 10 min (190 ° C., 2160 g load, according to JIS K7210-1999)
・ Ethylene / vinyl acetate random copolymer (EVA-2)
Vinyl acetate (VA) content: 46% by mass, MFR: 2.5 g / 10 min (190 ° C., 2160 g load, according to JIS K7210-1999)
・エチレン・メタクリル酸メチルランダム共重合体（ＥＭＭＡ-１）
メタクリル酸メチル（ＭＭＡ）含量；２５質量％、ＭＦＲ；２０ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠）
・ Ethylene / methyl methacrylate random copolymer (EMMA-1)
Methyl methacrylate (MMA) content: 25% by mass, MFR; 20 g / 10 min (190 ° C., 2160 g load, according to JIS K7210-1999)
２）比較用重合体
・低密度ポリエチレン（ＬＤＰＥ）
〔ＭＦＲ；３．７ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠〕
・エチレン・メタクリル酸共重合体（ＥＭＡＡ）
〔ＭＦＲ；２５ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠〕
・ナトリウムアイオノマー（Ｎａ−ＩＯ）
〔エチレン・メタクリル酸共重合体（メタクリル酸含量１５質量％）の金属架橋体、金属カチオン源：ナトリウム、中和度：５４％、ＭＦＲ；０．９ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠〕
・亜鉛アイオノマー（Ｚｎ−ＩＯ−１）
〔エチレン・メタクリル酸共重合体（メタクリル酸含量１５質量％）の金属架橋体、金属カチオン源：亜鉛、中和度：２１％、ＭＦＲ；１６ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠〕
・亜鉛アイオノマー（Ｚｎ−ＩＯ−２）
〔エチレン・メタクリル酸共重合体（メタクリル酸含量１５質量％）の金属架橋体、金属カチオン源：亜鉛、中和度：５９％、ＭＦＲ；０．９ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠〕
・マグネシウムアイオノマー（Ｍｇ−ＩＯ）
〔エチレン・メタクリル酸共重合体（メタクリル酸含量１５質量％）の金属架橋体、金属カチオン源：マグネシウム、中和度：５４％、ＭＦＲ；０．７ｇ／１０分（１９０℃、２１６０ｇ荷重、ＪＩＳ Ｋ７２１０−１９９９に準拠〕
2) Comparative polymer / low density polyethylene (LDPE)
[MFR: 3.7 g / 10 min (190 ° C., 2160 g load, conforming to JIS K7210-1999)
・ Ethylene / methacrylic acid copolymer (EMAA)
[MFR: 25 g / 10 min (190 ° C., 2160 g load, conforming to JIS K7210-1999)
・ Sodium ionomer (Na-IO)
[Crosslinked metal of ethylene / methacrylic acid copolymer (methacrylic acid content 15 mass%), metal cation source: sodium, neutralization degree: 54%, MFR; 0.9 g / 10 min (190 ° C., 2160 g load, JIS Conforms to K7210-1999)
・ Zinc ionomer (Zn-IO-1)
[Ethylene / methacrylic acid copolymer (methacrylic acid content 15% by mass) cross-linked metal, metal cation source: zinc, neutralization degree: 21%, MFR; 16 g / 10 min (190 ° C., 2160 g load, JIS K7210- (According to 1999)
・ Zinc ionomer (Zn-IO-2)
[Ethylene / methacrylic acid copolymer (methacrylic acid content 15% by mass), crosslinked metal, metal cation source: zinc, neutralization degree: 59%, MFR; 0.9 g / 10 min (190 ° C., 2160 g load, JIS Conforms to K7210-1999)
・ Magnesium ionomer (Mg-IO)
[Crosslinked metal of ethylene / methacrylic acid copolymer (methacrylic acid content 15% by mass), metal cation source: magnesium, neutralization degree: 54%, MFR; 0.7 g / 10 min (190 ° C., 2160 g load, JIS Conforms to K7210-1999)
〔界面活性剤〕
・アミート３２０
〔花王社製、ノニオン系界面活性剤、ポリ（オキシエチレン）アルキルアミン〕
〔樹脂型帯電防止剤〕
・ペレスタット２３０
〔三洋化成工業社製、高分子型ノニオン系界面活性剤、ポリエーテル系〕
[Surfactant]
・ Amate 320
[Kao Corporation, nonionic surfactant, poly (oxyethylene) alkylamine]
[Resin-type antistatic agent]
・ Pelestat 230
[Manufactured by Sanyo Chemical Industries, polymer type nonionic surfactant, polyether type]
＜重合体組成物の調製および成形体の作製＞
ベース樹脂と、イオン液体または界面活性剤とを、下記ブレンド方法により混合して重合体組成物を調製し、得られた重合体組成物を用い、下記プレスシート作製方法により成形して、成形体（プレスシート）を得た。
なお、各成分の混合比率は、後述する。
<Preparation of polymer composition and production of molded article>
A base resin and an ionic liquid or a surfactant are mixed by the following blending method to prepare a polymer composition, and the obtained polymer composition is used for molding by the following press sheet manufacturing method. (Press sheet) was obtained.
The mixing ratio of each component will be described later.
−ブレンド方法−
・装置
東洋精機製作所製、ラポプラストミル４Ｃ１５０
・条件
ベース樹脂の種類により下記に表１の「加熱温度」欄に示す温度で、ベース樹脂（後述する実施例１〜６に示す各ベース樹脂）とイオン液体（後述する実施例１〜６に示す各イオン液体）を１５分間溶融混練した。
-Blending method-
・ Equipment: Toyo Seiki Seisakusho, Lapoplast Mill 4C150
-Conditions At the temperature shown in the "heating temperature" column of Table 1 below according to the type of base resin, the base resin (each base resin shown in Examples 1 to 6 described later) and the ionic liquid (in Examples 1 to 6 described later) Each ionic liquid shown) was melt kneaded for 15 minutes.
−プレスシート作製方法−
上記ブレンド方法で得られたブレンド物（重合体組成物）を、ベース樹脂の種類により表１の「プレス温度」欄に示す温度で３分間加熱し、加圧２分、冷却（２０℃）４分の条件下で成形し、プレスシート（成形体）とした。
-Press sheet manufacturing method-
The blend (polymer composition) obtained by the above blending method is heated for 3 minutes at the temperature shown in the "Pressing temperature" column of Table 1 depending on the type of base resin, pressurized for 2 minutes, and cooled (20 ° C) 4 It was molded under the conditions of minutes to obtain a press sheet (molded body).
＜評価＞
後述する実施例１〜実施例６では、用意したイオン液体、および、上記のようにして得られたプレスシートを用いて、下記の手法で測定または評価を行った。
<Evaluation>
In Examples 1 to 6 to be described later, measurement or evaluation was performed by the following method using the prepared ionic liquid and the press sheet obtained as described above.
１．イオン液体飽和水分量測定方法
１の１．〔２３℃で液体状のイオン液体の場合〕
イオン液体と水を容積比１：１で混合し、２３℃で２４時間攪拌した。混合物を４８時間以上静置した後、イオン液体の層を分取し、これを水分値測定サンプルとした。水分測定はカールフィッシャー水分計（京都電子工業株式会社製、ＭＫＣ−２１０）を用いて測定した。４８時間以上静置しても二層に分離しないイオン液体は、水に溶解すると判断した。
１の２．〔２３℃で固体状のイオン液体の場合〕
イオン液体と水を容積比１：１で混合し、２３℃で２４時間攪拌した。固体のイオン液体を取り出し、その固体表面の水分を、ろ紙で拭き取り、２３℃で３０分静置したものを水分値測定サンプルとした。水分測定はカールフィッシャー水分計（京都電子工業株式会社製、ＭＫＣ−２１０）を用いて測定した。
1. Ionic liquid saturated water content measurement method 1-1. [In the case of liquid ionic liquid at 23 ° C.]
The ionic liquid and water were mixed at a volume ratio of 1: 1 and stirred at 23 ° C. for 24 hours. After the mixture was allowed to stand for 48 hours or longer, an ionic liquid layer was separated and used as a moisture value measurement sample. Moisture measurement was performed using a Karl Fischer moisture meter (MKC-210, manufactured by Kyoto Electronics Industry Co., Ltd.). The ionic liquid that did not separate into two layers even after standing for 48 hours or more was judged to be dissolved in water.
1 of 2. [In the case of solid ionic liquid at 23 ° C.]
The ionic liquid and water were mixed at a volume ratio of 1: 1 and stirred at 23 ° C. for 24 hours. A solid ionic liquid was taken out, the moisture on the solid surface was wiped off with a filter paper, and the sample was allowed to stand at 23 ° C. for 30 minutes to obtain a moisture value measurement sample. Moisture measurement was performed using a Karl Fischer moisture meter (MKC-210, manufactured by Kyoto Electronics Industry Co., Ltd.).
２．表面抵抗率測定方法
高抵抗率計（株式会社三菱化学アナリテック製、ハイレスタ−ＵＰ）を用い、作製したプレスシートの表面抵抗率〔Ω／ｓｑ〕（Ω／ｓｑｕａｒｅ）を測定した。プローブはＵＲＳプローブを使用し、レジテーブルＵＦＬのテフロン（登録商標）面側に測定サンプルを載せて測定した。
測定条件は以下のとおりである。
印加電圧：５００Ｖ
測定時間：１０秒
測定環境：２３℃×５０％ＲＨ、２３℃×３０％ＲＨ、２３℃×１２％ＲＨ
サンプルは測定環境で４８時間以上静置した後に測定した。
2. Surface resistivity measurement method The surface resistivity [Ω / sq] (Ω / square) of the produced press sheet was measured using a high resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Hiresta UP). A URS probe was used as a probe, and measurement was performed by placing a measurement sample on the Teflon (registered trademark) surface side of the registration table UFL.
The measurement conditions are as follows.
Applied voltage: 500V
Measurement time: 10 seconds Measurement environment: 23 ° C. × 50% RH, 23 ° C. × 30% RH, 23 ° C. × 12% RH
The sample was measured after standing for 48 hours or more in a measurement environment.
用いた高抵抗率計（株式会社三菱化学アナリテック製、ハイレスタ−ＵＰ）の測定限界は、１．０×１０７Ω／ｓｑであった。
以下「×１０ｎ」を『Ｅ＋ｎ』とも表す。
例えば、ｎ＝７のとき、「×１０７」は『Ｅ＋７」で表される。
The measurement limit of the high resistivity meter used (Hiresta UP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was 1.0 × 10 7 Ω / sq.
Hereinafter, “× 10 n ” is also expressed as “E + n”.
For example, when n = 7, “× 10 7 ” is represented by “E + 7”.
３．シート外観
作製したプレスシートの外観を目視で観察した。
3. Sheet appearance The appearance of the produced press sheet was visually observed.
４．ブリード評価（ガラス汚染試験）
作製したプレスシートとガラス板とを重ね合わせ、２３℃で４８時間放置した後、プレスシートとガラス板とを剥離し、ガラス板の表面外観を目視で観察し、下記評価基準により評価した。
4). Bleed evaluation (glass contamination test)
The produced press sheet and the glass plate were overlapped and allowed to stand at 23 ° C. for 48 hours, and then the press sheet and the glass plate were peeled off, the surface appearance of the glass plate was visually observed, and evaluated according to the following evaluation criteria.
−評価基準−
○：ガラスへの付着物が全く無い。
×：付着物が見られるか付着物でガラスが曇っている。
-Evaluation criteria-
○: There is no deposit on the glass.
X: Adhered matter is seen or glass is clouded with the adhering matter.
＜実施例１＞−イオン液体の疎水性確認試験−
上記のイオン液体飽和水分量測定方法の１の１に示す方法に基づき、[EMIM][OTf]、[EMIM][NTF]、[EMIM][FAP]、[HMIM][FAP]、および[BMPL][FAP]の飽和水分量を測定した。いずれも、測定を２回行い、その平均値を、表２に示す。
また、ＥＥＡ−１（１００質量部）に対し、各イオン液体０．５質量部を混合して得られたプレスシートについて、表面抵抗率測定およびブリード評価を行い、結果を表２に示した。
<Example 1>-Hydrophobicity confirmation test of ionic liquid-
[EMIM] [OTf], [EMIM] [NTF], [EMIM] [FAP], [HMIM] [FAP], and [BMPL] based on the method shown in 1 of the above ionic liquid saturated water content measurement method ] The saturated water content of [FAP] was measured. In any case, the measurement was performed twice, and the average value is shown in Table 2.
Further, with respect to the press sheet obtained by mixing 0.5 parts by mass of each ionic liquid with respect to EEA-1 (100 parts by mass), surface resistivity measurement and bleed evaluation were performed, and the results are shown in Table 2.
表２からわかるように、水に溶解する[EMIM][OTf]に比べ、水分量が１０万ｐｐｍ以下となる[EMIM][NTF]、[EMIM][FAP]、[HMIM][FAP]、および[BMPL][FAP]は、表面抵抗率が低く、帯電防止性に優れることが分かった。さらに、アニオン種としてＦＡＰを用いると、イオン液体の水分量は５０００ｐｐｍを下回り、イオン液体の疎水性が高いことがわかる。このような水分量が小さな疎水性の高いイオン性液体を用いると、表面抵抗率も大きく下がり、特に優れた帯電防止性を示すことが分かった。 As can be seen from Table 2, [EMIM] [NTF], [EMIM] [FAP], [HMIM] [FAP], which has a water content of 100,000 ppm or less compared to [EMIM] [OTf] And [BMPL] [FAP] were found to have low surface resistivity and excellent antistatic properties. Furthermore, when FAP is used as the anionic species, the water content of the ionic liquid is less than 5000 ppm, indicating that the ionic liquid is highly hydrophobic. It has been found that when such a highly hydrophobic ionic liquid with a small amount of water is used, the surface resistivity is greatly reduced and particularly excellent antistatic properties are exhibited.
＜実施例２＞
ベース樹脂１００質量部に対し、イオン液体を、表３に示す量（質量部）で混合して得られたプレスシートについて、表面抵抗率（２３℃、５０％ＲＨ）を測定し、表３に示した。
<Example 2>
With respect to 100 parts by mass of the base resin, the surface resistivity (23 ° C., 50% RH) of the press sheet obtained by mixing the ionic liquid in the amount (parts by mass) shown in Table 3 was measured. Indicated.
表３からわかるように、水に溶解するイオン液体を用いると、ベース樹脂として不飽和エステル由来の構成単位を含む重合体を用いても、プレスシートは帯電防止性に優れないことが分かった。 As can be seen from Table 3, when an ionic liquid that dissolves in water is used, even if a polymer containing a structural unit derived from an unsaturated ester is used as the base resin, the press sheet is not excellent in antistatic properties.
＜実施例３＞
ベース樹脂１００質量部に対し、イオン液体を、表４に示す量（質量部）で混合して得られたプレスシートについて、表面抵抗率を測定した。また、ブリード評価およびシート外観評価も行い、それぞれ、結果を表４に示した。
また、実施例で用いたイオン液体の飽和水分量（２回測定の平均値）も表４に示した。
なお、今後示す表中、「−」は未測定であることを意味する。
<Example 3>
The surface resistivity of the press sheet obtained by mixing the ionic liquid in an amount (parts by mass) shown in Table 4 with respect to 100 parts by mass of the base resin was measured. In addition, bleed evaluation and sheet appearance evaluation were also performed, and the results are shown in Table 4, respectively.
Table 4 also shows the saturated water content (average value of two measurements) of the ionic liquid used in the examples.
In the tables shown below, “-” means not measured.
表４からわかるように、水分量が小さい（疎水性の高い）イオン液体と不飽和エステル由来の構成単位を含む重合体との組み合わせで表面低効率が低下して、高い帯電防止性を示すことがわかる。 As can be seen from Table 4, the combination of an ionic liquid with a small amount of water (high hydrophobicity) and a polymer containing a structural unit derived from an unsaturated ester reduces surface low efficiency and exhibits high antistatic properties. I understand.
＜実施例４＞
ベース樹脂１００質量部に対し、イオン液体または界面活性剤を、表５に示す量（質量部）で混合して得られたプレスシートについて、表面抵抗率を測定した。また、ブリード評価も行い、それぞれ、結果を表５に示した。
なお、実施例４で用いたイオン液体のうち、[NM4][FAP]のイオン液体飽和水分量を、上記のイオン液体飽和水分量測定方法の１の２に示す方法に基づき測定したところ、飽和水分量は５１０ｐｐｍであることが確認された。
<Example 4>
The surface resistivity was measured for a press sheet obtained by mixing an ionic liquid or a surfactant in an amount (parts by mass) shown in Table 5 with respect to 100 parts by mass of the base resin. Bleed evaluation was also performed, and the results are shown in Table 5, respectively.
In addition, among the ionic liquids used in Example 4, the ionic liquid saturated water content of [NM4] [FAP] was measured based on the method shown in 1-2 of the ionic liquid saturated water content measuring method described above. The water content was confirmed to be 510 ppm.
表５からわかるように、公知の帯電防止剤として一般的に用いられる界面活性剤や樹脂型帯電防止剤とベース樹脂とを用いて得たプレスシートに比べ、本発明のイオン液体を用いて得られたプレスシートの方が、帯電防止性に優れ、さらに、ブリードの抑制にも優れた。 As can be seen from Table 5, it is obtained using the ionic liquid of the present invention as compared with a press sheet obtained using a surfactant or a resin-type antistatic agent and a base resin that are generally used as known antistatic agents. The obtained press sheet was superior in antistatic property and further in suppressing bleeding.
＜実施例５＞
ベース樹脂１００質量部に対し、イオン液体または界面活性剤を、表６に示す量(質量分)で混合して得られたプレスシートについて、表面抵抗率を測定した。また、ブリード評価も行い、それぞれ、結果を表６に示した。
なお、ベース樹脂単独の表面低効率の測定器は、前述のハイレスターではなく高表面低効率を測定できるアジレント（Agilent）４３３９Ｂ（Agilent Technologies社製）を用いて測定した。なお、本発明品の一部をハイレスターとアジレントの両方で測定し両者で測定された表面低効率が誤算範囲であることを確認した。
<Example 5>
The surface resistivity was measured for a press sheet obtained by mixing an ionic liquid or a surfactant in an amount (mass) shown in Table 6 with respect to 100 parts by mass of the base resin. Bleed evaluation was also performed, and the results are shown in Table 6, respectively.
In addition, the measurement apparatus of the surface low efficiency of the base resin alone was measured using Agilent 4339B (manufactured by Agilent Technologies) that can measure the high surface low efficiency instead of the above-mentioned high-restorer. A part of the product of the present invention was measured by both Hirester and Agilent, and it was confirmed that the surface low efficiency measured by both was within the miscalculation range.
表６からわかるように、不飽和エステル由来の構成単位を含む重合体に水分量が小さい（疎水性の高い）イオン液体を組み合わせると表面低効率が低下することがわかる。重合体１ｋｇ中の不飽和エステル由来の構成単位量が２モル以上であると表面低効率が更に低下し、さらに３モル以上であると樹脂組成物の透明性も向上することがわかった。 As can be seen from Table 6, it can be seen that when the polymer containing the unsaturated ester-derived structural unit is combined with an ionic liquid having a small water content (high hydrophobicity), the surface low efficiency is lowered. It was found that when the amount of the structural unit derived from the unsaturated ester in 1 kg of the polymer is 2 mol or more, the surface low efficiency is further lowered, and when it is 3 mol or more, the transparency of the resin composition is also improved.
表６からイオン液体を０．５質量部配合した系を選び、ベース樹脂のエステル含量［ｍｏｌ／ｋｇ］に対するｌｏｇ（表面抵抗率［Ω／ｓｑ］）の相関を図１に示した。図１中、黒丸のプロット（●）が、ベース樹脂のみのデータであり、四角形のプロット（■）が重合体組成物のデータである。前述した不飽和エステル由来の構成単位を含む重合体に水分量が小さい（疎水性の高い）イオン液体を組み合わせると表面低効率が低下することがこの図からもわかる。 A system containing 0.5 part by mass of the ionic liquid was selected from Table 6, and the correlation of the log (surface resistivity [Ω / sq]) against the ester content [mol / kg] of the base resin is shown in FIG. In FIG. 1, the black circle plot (●) is the data for only the base resin, and the square plot (■) is the data for the polymer composition. It can also be seen from this figure that the surface low efficiency is lowered when an ionic liquid having a low water content (high hydrophobicity) is combined with the above-described polymer containing a structural unit derived from an unsaturated ester.
＜実施例６＞
ベース樹脂１００質量部に対し、イオン液体または界面活性剤を、表７に示す量（質量部）で混合して得られたプレスシートについて、表面抵抗率を測定した。また、ブリード評価も行い、それぞれ、結果を表７および図２に示した。
<Example 6>
The surface resistivity of the press sheet obtained by mixing the ionic liquid or the surfactant in an amount (parts by mass) shown in Table 7 with respect to 100 parts by mass of the base resin was measured. Bleed evaluation was also performed, and the results are shown in Table 7 and FIG.
表７および図２からわかるように、疎水性のイオン液体[EMIM][FAP]を少量含有するだけで表面抵抗率は大きく下がる。
なお、図２において、白抜きのプロット（○）は、イオン液体を含まないベース樹脂の値を示す。
As can be seen from Table 7 and FIG. 2, the surface resistivity is greatly lowered only by containing a small amount of the hydrophobic ionic liquid [EMIM] [FAP].
In FIG. 2, the white plot (◯) indicates the value of the base resin not containing the ionic liquid.
Claims (5)
イオン液体（Ｌ）および水（Ｗ）を容積比（Ｌ：Ｗ）＝１：１で混合し、２３℃で２４時間攪拌した後４８時間静置して分取したイオン液体相中の水分量が１０万ｐｐｍ以下となるイオン液体と
を含む重合体組成物。 A polymer containing a structural unit derived from an unsaturated ester;
Moisture content in the ionic liquid phase obtained by mixing ionic liquid (L) and water (W) at a volume ratio (L: W) = 1: 1, stirring at 23 ° C. for 24 hours, and then allowing to stand for 48 hours. A polymer composition containing an ionic liquid having a concentration of 100,000 ppm or less.
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