JPS6368614A - Production of methacrylic resin cast plate excellent in antistatic property - Google Patents
Production of methacrylic resin cast plate excellent in antistatic propertyInfo
- Publication number
- JPS6368614A JPS6368614A JP61211890A JP21189086A JPS6368614A JP S6368614 A JPS6368614 A JP S6368614A JP 61211890 A JP61211890 A JP 61211890A JP 21189086 A JP21189086 A JP 21189086A JP S6368614 A JPS6368614 A JP S6368614A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- monomer
- cast plate
- formula
- methacrylic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000113 methacrylic resin Substances 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 11
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims abstract 3
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 abstract description 3
- 150000003863 ammonium salts Chemical group 0.000 abstract description 3
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000005395 methacrylic acid group Chemical group 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000002216 antistatic agent Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-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
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 150000003459 sulfonic acid esters Chemical class 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- OBMRSUNAEQGDLK-UHFFFAOYSA-N 2-(dipropylamino)ethyl 2-methylprop-2-enoate Chemical compound CCCN(CCC)CCOC(=O)C(C)=C OBMRSUNAEQGDLK-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000219104 Cucurbitaceae Species 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical group CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920000550 glycopolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- QZIQJVCYUQZDIR-UHFFFAOYSA-N mechlorethamine hydrochloride Chemical compound Cl.ClCCN(C)CCCl QZIQJVCYUQZDIR-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、良好且つ恒久的な帯電防止性を有するメタク
リル樹脂キャスト板の製造方法及びそれによって得られ
たメタクリル樹脂キャスト板に関連するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a methacrylic resin cast board having good and permanent antistatic properties, and the methacrylic resin cast board obtained thereby. be.
メタクリル樹脂キャスト板は、その優れた透明性、表面
光沢、美しい外観、良好な機械的性質等により、照明器
具、看板、建材、各種銘板、装飾品などに広く利用され
ているが、(イ)表面抵抗値が高いため容易に帯電し、
ゴミ、はこり等を吸引して外観を損ねる、(ロ)キズが
つく、(ハ)人体や工Vクトロニクス部品に対して電撃
を与える等の問題を起こしている。Methacrylic resin cast boards are widely used in lighting equipment, signboards, building materials, various nameplates, decorative items, etc. due to their excellent transparency, surface gloss, beautiful appearance, and good mechanical properties. Easily charged due to high surface resistance,
This causes problems such as attracting dust, clumps, etc., damaging the appearance, (b) causing scratches, and (c) applying electric shock to the human body and industrial parts.
メタクリル樹脂キャスト板に帯電防止性を付与する方法
としては
(1)界面活性剤の内部添加
(2) ケ の表面塗布
(3) シリコン系化合物の表面塗布(4) プフ
ズマ処理による表面改質があげられる。これらのうち(
3)、(4)はいずれもコスト的に高価となるので、一
般には(1)、(2)の方法が用いられる。Methods for imparting antistatic properties to methacrylic resin cast plates include (1) internal addition of surfactants, (2) surface coating, (3) surface coating of silicone compounds, and (4) surface modification by Pfusma treatment. It will be done. Among these (
Since both methods 3) and (4) are expensive, methods (1) and (2) are generally used.
使用される界面活性剤としては、アニオン系、カチオン
系、ノニオン系のものがあるが、特にカチオン系の第4
級アンモニウム塩を含んだ化合物が優れた帯電防止性能
を与えるものとして知られている。The surfactants used include anionic, cationic, and nonionic surfactants, especially cationic quaternary surfactants.
Compounds containing ammonium salts are known to provide excellent antistatic properties.
これらの界面活性剤を表面塗布処理する場合、メタクリ
ル樹脂キャスト板の表面状態を損わないようにするには
微妙な操作が要求され、且つこのように処理したメタク
リ/V樹脂キャスト板においては、水洗や摩擦等によシ
表面に付着した帯電防止剤が容易に脱落し、帯電防止性
能が失われてしまう問題点がある。When applying these surfactants to the surface, delicate operations are required to avoid damaging the surface condition of the methacrylic resin cast board, and in the methacrylic/V resin cast board treated in this way, There is a problem in that the antistatic agent attached to the surface easily falls off due to water washing, friction, etc., and the antistatic performance is lost.
界面活性剤を内部添加する方法は、重合前の樹脂原料に
帯電防止剤を混合又は分散するので製造工程が簡単とな
るが、充分な帯電防止性能を得るためには、一般に添加
量を多くする必要があり、そうするとメタクリル樹脂の
透明性や機械的物性を損い、且つ得られた帯電防止性能
が水洗や摩擦等により容易に失なわれてしまう問題点が
ある。The method of internally adding a surfactant simplifies the manufacturing process because the antistatic agent is mixed or dispersed into the resin raw material before polymerization, but in order to obtain sufficient antistatic performance, it is generally necessary to increase the amount added. If this is done, the transparency and mechanical properties of the methacrylic resin will be impaired, and the obtained antistatic performance will be easily lost due to washing with water, friction, etc.
内部添加法の上記のような欠点を克服するために、帯電
防止剤として重合性の単量体を使用する試みがなされた
(特公昭4B−15471号、特公昭54−25595
号)。しかしながらこの種のものは帯電防止性能が不充
分であったシ、キャスト重合によって得られた板と鋳型
の接着性が強くなり、安定した製造が難かしくなる欠点
を有していた。In order to overcome the above-mentioned drawbacks of the internal addition method, attempts were made to use polymerizable monomers as antistatic agents (Japanese Patent Publication No. 4B-15471, Japanese Patent Publication No. 54-25595).
issue). However, this type of product had drawbacks such as insufficient antistatic performance and strong adhesion between the plate obtained by cast polymerization and the mold, making stable production difficult.
〔発明が解決しようとする問題点3
以上のように、特別な製造工程を必要とせず、良好な帯
電防止性能を恒久的に示し、且つメタクIJ/l/樹脂
本来の物性を保持しているようなメタクリル樹脂キャス
ト板は従来提案されていない。[Problem to be solved by the invention 3 As mentioned above, Metac IJ/L/resin does not require any special manufacturing process, permanently exhibits good antistatic performance, and maintains the original physical properties of the resin. Such a methacrylic resin cast plate has not been proposed so far.
本発明者等は、上記問題点について鋭意検討の結果、メ
チルメタクリレートをキャスト重合させる際にある種の
四級アンモニウム塩基を持つ(共)重合体を脂肪酸、ア
クリル酸及びその誘導体、アルキレングリコ−μ類より
選ばれた化合物とともに少量添加することにより良好で
且つ恒久的な帯電防止性能を有し、メタクリμ樹脂本来
の物性を保持しているようなメタクリル樹脂キャスト板
が得られることを見出した。As a result of intensive studies on the above-mentioned problems, the present inventors have determined that when cast polymerizing methyl methacrylate, a (co)polymer having a certain type of quaternary ammonium base should be used with fatty acids, acrylic acid and its derivatives, alkylene glyco-μ It has been found that by adding a small amount of methacrylic resin along with a compound selected from the following group, a methacrylic resin cast plate having good and permanent antistatic properties and retaining the physical properties inherent to methacrylic μ resin can be obtained.
すなわち本発明は、エチルメタクリレート又はメチルメ
タクリレート50重量−以上とこれと共重合可能な少な
くとも一種の単量体50重1に一原子とからなる単量体
混合物或いはそれらの部分重合体(I) 100重量部
に対し、一般式
%式%
(R1は水素原子又はメチfi/基、R8−R4は水素
原子又は炭素数1〜9の置換基を含んでいてもよいアル
キμ基、mは1〜10の整数、X−は四級化剤のアニオ
ン)
で表わされる四級アンモニウム塩基を有する単量体30
〜100重量%及びこれと共重合可能な少なくとも一種
の単量体0〜70重量−からなる単量体又は単量体混合
物を重合させて得られた(共)重合体(II) (11
〜20重量部、及び一般式
%式%)
(R5は水素原子又は炭素数1〜22の脂肪族炭化水素
残基)で表される脂肪酸、
一般式
%式%()
(−は水素原子又は炭素数1〜4の脂肪族炭化水素残基
、A1は炭素数2〜乙の1μキレン基、nは0又は1以
上の整数)で表されるアクリル酸又は、その誘導体及び
一般式
%式%()
(Asは炭素数2〜4のアルキレン基、pは1以上の整
数)で表されるアルキレングリコ−!の中から選ばれる
化合物(■)をQ、1〜20重量部
を添加混合して重合させることを特徴とする帯電防止性
に優れたメタクリIVvi脂キャスト板及びその製造方
法に関するものである。That is, the present invention provides a monomer mixture consisting of 50 weight or more of ethyl methacrylate or methyl methacrylate and one atom per 50 weight of at least one monomer copolymerizable therewith, or a partial polymer thereof (I) 100 Based on the weight part, the general formula % formula % (R1 is a hydrogen atom or a methyfi/group, R8-R4 is a hydrogen atom or an alkyl μ group which may contain a substituent having 1 to 9 carbon atoms, m is 1 to 10, X- is an anion of a quaternizing agent) Monomer 30 having a quaternary ammonium base represented by
(Co)polymer (II) obtained by polymerizing a monomer or a monomer mixture consisting of ~100% by weight and 0 to 70% by weight of at least one monomer copolymerizable therewith
~20 parts by weight, and a fatty acid represented by the general formula % formula %) (R5 is a hydrogen atom or an aliphatic hydrocarbon residue having 1 to 22 carbon atoms), the general formula % formula % () (- is a hydrogen atom or Acrylic acid or its derivatives represented by an aliphatic hydrocarbon residue having 1 to 4 carbon atoms, A1 is a 1μ kylene group having 2 to 2 carbon atoms, and n is an integer of 0 or 1 or more, and the general formula % formula % () (As is an alkylene group having 2 to 4 carbon atoms, p is an integer of 1 or more) Alkylene glyco-! This invention relates to a methacrylic IVvi resin cast plate with excellent antistatic properties, which is characterized by adding and mixing 1 to 20 parts by weight of Q, a compound (■) selected from the following, and polymerizing it, and a method for producing the same.
本発明においてメチルメタクリレート単量体混合物又は
それらの部分重合体に用いられる共重合可能な単量体と
しては、エチルメタクリレート、ブチμメタクリレート
、2−エチ〃ヘキV/I/メタクリレート等のメタクリ
ル酸エステル類、メチμアクリレート、エチμアクリレ
ート、ブチμアクリV−ト、2−エチμヘキシ〃アクリ
V−)等のアクリμ酸エステμ類、アクリル酸、メタク
リル酸、マレイン酸、イタコン酸等の不飽和力〃ボン酸
、無水マレイン酸、無水イタコン酸等の酸無水物、N−
フエ二μマレイミド、N−シクロヘキシルマレイミド、
N−を−ブチμマレイミド等のマレイミド誘導体、2−
ヒドロキVエチμアクリレート、2−ヒドロキシブロピ
μアクリレート、2−ヒドロキシメチルメタクリレート
、2−ヒドロキシプロピルメタクリレート等のヒドロキ
シ基含有単量体、アクリルアミド、メタクリμアミド、
アクリレートリ〜、メタクリレートリ!、ジアセトンア
クリルアミド、ジメチルアミノエチルメタクリレート等
の窒素含有単量体、アリμグlJz/ジμエーテル、グ
リシジルアクリレート、グリシジルメタクリレート等の
エポキシ基含有単量体、スチレン、α−メチμスチレン
等のスf V :/系単量体、エチレングリコ−μシア
クリレート、アリμアクリv−ト、エチレングリコ−μ
ジメタクリレート、アリルメタクリレート、ジビニルベ
ンゼン、トリメチロールプロパントリアクリレート等の
架橋剤等が挙げられる。In the present invention, the copolymerizable monomers used in the methyl methacrylate monomer mixture or partial polymer thereof include methacrylic acid esters such as ethyl methacrylate, butyμ methacrylate, and 2-ethyhexV/I/methacrylate. acrylic acid esters such as methacrylate, ethyl acrylate, buty acrylate, 2-ethylhexyacrylic Saturation power Acid anhydrides such as bonic acid, maleic anhydride, itaconic anhydride, N-
Feniμmaleimide, N-cyclohexylmaleimide,
Maleimide derivatives such as N-butymu maleimide, 2-
Hydroxy group-containing monomers such as hydroxy V ethyl μ acrylate, 2-hydroxybropy μ acrylate, 2-hydroxymethyl methacrylate, 2-hydroxypropyl methacrylate, acrylamide, methacryl μ amide,
Acrylate tri, methacrylate tri! Nitrogen-containing monomers such as diacetone acrylamide and dimethylaminoethyl methacrylate, epoxy group-containing monomers such as aliμglJz/diμether, glycidyl acrylate and glycidyl methacrylate, and styrene and α-methyleneμstyrene. fV:/system monomer, ethylene glyco-μ cyacrylate, aliμ acrylate, ethylene glyco-μ
Examples include crosslinking agents such as dimethacrylate, allyl methacrylate, divinylbenzene, and trimethylolpropane triacrylate.
共重合可能な単量体の種類と添加量は、目的とするキャ
スト板の性質により適宜選ぶことができる。The type and amount of the copolymerizable monomer can be appropriately selected depending on the properties of the intended cast plate.
本発明において(共)重合体(n)を構成する四級アン
モニウム塩基を有する単量体は、一般式
%式%
(Rs〜R4及びmは前述した通シである)で表わされ
、これはアミノ基を有するアクリレートもしくはメタク
リレートを四級化剤により四級化することによシ得られ
る。アミノ基を有するメタクリレートもしくはアクリレ
ートとしては、ジメチルアミノエチルメタクリレート、
ジエチルアミノエチルメタクリレート、ジメチルアミノ
プロピルメタクリレート、ジメチルアミノエチルアクリ
レート、ジエチpアミノエチμアクリレート、ジメチ〃
アミノブチ〜メタクリレート、ジヒドロキシェチ〃アミ
ノエチμメタクリレート、ジプロピルアミノエチルメタ
クリレート、ジブチ〃アミノエチルメタクリV−ト等が
挙げられる。In the present invention, the monomer having a quaternary ammonium base constituting the (co)polymer (n) is represented by the general formula % (Rs to R4 and m are the same as above), and this is obtained by quaternizing an acrylate or methacrylate having an amino group using a quaternizing agent. As the methacrylate or acrylate having an amino group, dimethylaminoethyl methacrylate,
Diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminoethyl acrylate, diethyp-aminoethyl acrylate, dimethy
Examples thereof include aminobuty-methacrylate, dihydroxyethyl aminoethyl methacrylate, dipropylaminoethyl methacrylate, dibutyaminoethyl methacrylate, and the like.
四級化剤としては、ジエチル硫酸、ジエチル硫酸、ジデ
ロビlv硫酸等のアルキμ硫酸類、p−トルエンスルホ
ン酸メチル、ベンゼンスルホン酸メチp等のスルホン酸
エステ〃、トリメチルホスフェイト等のアルキルリン酸
、アpキμベンジμクロフィト、ベンジルクロフィト、
アルキルクロフィト、アルキルブロマイド等の各種ハラ
イドが用いられ、特にアμキμ硫酸、スルホン酸エステ
ルが耐熱分解性の点よシ好ましい。一般式中のmは1〜
10であるが、2〜6が特に好ましい。Examples of quaternizing agents include alkyl μ sulfuric acids such as diethyl sulfate, diethyl sulfate, and diderobylv sulfate, sulfonic acid esters such as methyl p-toluenesulfonate and methi-p benzenesulfonate, and alkyl phosphoric acids such as trimethyl phosphate. , apkiμbenziμcrophyte, benzylcrophyte,
Various halides such as alkyl chlorophytes and alkyl bromides are used, and alkyl sulfuric acid and sulfonic acid esters are particularly preferred in terms of heat decomposition resistance. m in the general formula is 1~
10, but 2 to 6 are particularly preferred.
なお、四級アンモニウム塩基のカウンターアニオンとし
ては、
一般式
%式%
(山は水素原子又は炭素数1〜20のフエニル基を含ん
でいてもよいアμキy基)
で表わされるものが好ましい。The counter anion of the quaternary ammonium base is preferably one represented by the general formula % (the crest is a hydrogen atom or an a[mu]ky group which may contain a phenyl group having 1 to 20 carbon atoms).
四級アンモニウム塩基を有する単量体と共重合可能な単
量体としては、公知の単量体が使用できる。例えばメチ
ルメタクリレート、エチルメタクリV−)等のメタクリ
ル酸エステμ類、メチルアクリレート、エチルアクリレ
ート等のアクリ〃酸エステル類、アクリル酸メタクリ〜
酸等の不飽和力μボン酸、無水マレイン酸、無水イタコ
ン酸等の酸無水物、N−フエ二μマレイミド等のマンイ
ミド誘導体、2−ヒドロキシメチルアクリレート、2−
ヒドロキシプロピルメタクリレート等のヒドロキシ基含
有単量体、アクリルアミド、アクリロニトリル等の窒素
含有単を体、アリルグリシジルニーf /l/ 、グリ
シジルアクリレート等のエポキシ基含有単量体がある。As the monomer copolymerizable with the monomer having a quaternary ammonium base, known monomers can be used. For example, methacrylic acid esters μ such as methyl methacrylate and ethyl methacrylate V-), acrylic acid esters such as methyl acrylate and ethyl acrylate, and acrylic acid methacrylate
Unsaturated forces such as acids μ acid, acid anhydrides such as maleic anhydride, itaconic anhydride, manimide derivatives such as N-pheniμmaleimide, 2-hydroxymethyl acrylate, 2-
There are hydroxy group-containing monomers such as hydroxypropyl methacrylate, nitrogen-containing monomers such as acrylamide and acrylonitrile, and epoxy group-containing monomers such as allylglycidylnyf/l/ and glycidyl acrylate.
これらのうち下記一般式
%式%
(&は水素原子又はメチル基、鳥は水素原子又は炭素原
子数1〜18のアμキ/l/基、アリル基、アv−A/
基、アフpキy基、〜は炭素数2〜4のアルキレン基、
qは0〜500)
で表わされる化合物より選ばれたものを使用することか
好ましい。Among these, the following general formula % formula % (& is a hydrogen atom or a methyl group, a bird is a hydrogen atom or a C 1-18 aμ/l/ group, an allyl group, an av-A/
group, affpky group, ~ is an alkylene group having 2 to 4 carbon atoms,
It is preferable to use a compound selected from the following (q is 0 to 500).
本発明における(共)重合体(n)の組成は、四級アン
モニウム塩基を有する単量体30〜100重量%、好ま
しくは50〜9■iチ、共重合可能な単量体0〜70重
致チ、好ましくは10〜70重量%である。(共)重合
体(II)中の四級アンモニウム塩基を有する単量体が
30重量−未満では、得られるメタクリル樹脂キャスト
板に良好な制電性が付与できない。The composition of the (co)polymer (n) in the present invention is 30 to 100% by weight of a monomer having a quaternary ammonium base, preferably 50 to 9% by weight, and 0 to 70% by weight of a copolymerizable monomer. The content is preferably 10 to 70% by weight. If the amount of the monomer having a quaternary ammonium base in the (co)polymer (II) is less than 30% by weight, good antistatic properties cannot be imparted to the obtained methacrylic resin cast plate.
(共)重合体(II)を調製する方法は、特に限定され
ないが、通常のフジカμ重合開始剤及び連鎖移動剤の存
在下、溶液重合、塊状重合等の手法を用いることができ
る。特に溶液重合が均−系のまま重合できるので好まし
い。又、溶液重合の場合、単量体の一括添加、分割添加
、滴下添加等種々の添加方法を採用できる。The method for preparing (co)polymer (II) is not particularly limited, but techniques such as solution polymerization and bulk polymerization in the presence of a usual Fujika μ polymerization initiator and chain transfer agent can be used. In particular, solution polymerization is preferable because polymerization can be carried out in a homogeneous system. In the case of solution polymerization, various addition methods such as bulk addition, divided addition, and dropwise addition of monomers can be employed.
本発明における(共)重合体(It)の分子量は、10
00以上であることが好ましい。1000未満であれば
、良好な恒久帯電防止性能が得られない場合が6J)、
又可塑化効果によりメタクリル樹脂本来の耐熱性を低下
させる傾向がある。The molecular weight of the (co)polymer (It) in the present invention is 10
It is preferable that it is 00 or more. If it is less than 1000, good permanent antistatic performance may not be obtained (6J),
Furthermore, the plasticizing effect tends to reduce the inherent heat resistance of the methacrylic resin.
(共)重合体(n)のメチμメタク!JL/−ト単量体
(混合物)又はその部分重合物(I) 100重量部に
対する添加量は11〜20重量部が好ましく、特に好ま
しくは15〜10重量部である。(Co)polymer (n) mechiμmetaku! The amount added is preferably 11 to 20 parts by weight, particularly preferably 15 to 10 parts by weight, per 100 parts by weight of the JL/-to monomer (mixture) or its partial polymer (I).
この添加量が11重量部未満であると良好な帯電防止性
能を付与できず、20重量部を超えるとメタクリル樹脂
本来の物性を大きく損ねる上にコスト高となる。If the amount added is less than 11 parts by weight, good antistatic performance cannot be imparted, and if it exceeds 20 parts by weight, the original physical properties of the methacrylic resin will be greatly impaired and the cost will increase.
本発明において用いられる化合物(■)のうち、脂肪酸
(5L)としては、例えば蟻酸、酢酸、ステアリン酸等
の飽和脂肪酸又はオレイン酸等の不飽和脂肪酸が挙げら
れ、アクリル酸又はその誘導体(1))としては、例え
ばアクリル酸、メタクリル酸、とドロキシエチルメタク
リレート又はヒドロキシプロピルメタクリレートが挙げ
られる。Among the compounds (■) used in the present invention, examples of fatty acids (5L) include saturated fatty acids such as formic acid, acetic acid, and stearic acid, and unsaturated fatty acids such as oleic acid, and acrylic acid or its derivatives (1). ) include, for example, acrylic acid, methacrylic acid, and droxyethyl methacrylate or hydroxypropyl methacrylate.
アルキレングリコ−A/ (c)としては、例えばエチ
レングリコ−μ、プロピレングリコ−μ、ジエチレング
リコール、ジプロピレングリコ−μ、ポリエチレングリ
コ艷ヘポリデロビソングリコーμが挙げられる。Examples of the alkylene glyco-A/(c) include ethylene glyco-μ, propylene glyco-μ, diethylene glycol, dipropylene glyco-μ, and polyethylene glycopolymers and polyderobison glycol-μ.
化合物(III)の添加量は、共重合体(If)の組成
によシ異なるので一概には決められないが、0.1〜2
0重量部の範囲内で得られる帯電防止性能と、透明性そ
の他の物性のバランスにより決めることができる。一般
に、化合物(m)の量が多くなると、得られる板の透明
性は良くなるが、帯電防止性能が低下する傾向にある。The amount of compound (III) to be added varies depending on the composition of the copolymer (If), so it cannot be determined unconditionally, but it is between 0.1 and 2.
It can be determined based on the balance between the antistatic performance obtained within the range of 0 parts by weight and the transparency and other physical properties. Generally, as the amount of compound (m) increases, the transparency of the obtained plate improves, but the antistatic performance tends to decrease.
本発明における帯電防止性の優れたメタクリル樹脂キャ
スト板は、轟該業者によって普通に行われている鋳込重
合法によって製造するのが好ましい。すなわちメチルメ
タクリレート又はメチルメタクリレート50重量−以上
と共獄舎可能な少なくとも一種の単址体50重aS以下
とからなる単量体混合物或いはそれらの部分重合物(I
)に所定量の共重合体(n)を添加して均一に溶解させ
、得られた混合物にさらにヲジカμ重合開始剤を添加し
て鋳込原料とする。該原料を周辺をガスケットでシー!
した対向させた2枚の無機ガラス板又は金属板の間に注
入して加熱するセルキャスト法か又は、同一方向に同シ
ー〜された空間の上流から連続的に上記の鋳込原料を注
入して加熱する連続キャスト法が具体的な重合方法とし
て挙げられる。The methacrylic resin cast plate having excellent antistatic properties in the present invention is preferably manufactured by a cast polymerization method commonly practiced by manufacturers. That is, methyl methacrylate or a monomer mixture consisting of 50 weight or more of methyl methacrylate and 50 weight or less of at least one monomer that can be combined, or a partial polymer thereof (I
), a predetermined amount of the copolymer (n) is added thereto and uniformly dissolved, and a Ojika μ polymerization initiator is further added to the resulting mixture to obtain a casting raw material. Seat the raw material around it with a gasket!
Either the cell casting method involves injecting the casting material between two facing inorganic glass plates or metal plates, or heating the casting material by continuously injecting the above casting material from upstream in a space spaced in the same direction. A specific polymerization method is a continuous casting method.
上述した本発明の重合性原料(I)を重合させるには、
アゾ化合物あるいは、有機過酸化物等のヲジカμ重合開
始剤を用いるのが好ましい。To polymerize the above-mentioned polymerizable raw material (I) of the present invention,
It is preferable to use an azo compound or an organic peroxide polymerization initiator.
アゾ化合物の具体例としては、2.2′−アゾビス(イ
ソブチロニトリル)、2.2’−アゾビス(2,4−ジ
メチ〃パv’ロ=トリA/ )、2.2’−アゾビス(
2,4−ジメチ*−4−メトキシバレロニトリ/L/)
等を挙げることができ、他方有機過酸化物の具体例とし
ては、ベンゾイルパーオキサイド、ツウロイルパーオキ
サイド等が挙げられる。又Vドックス系の重合開始剤、
例えば有機過酸化物とアミン類との組み合わせも用いる
ことができる。Specific examples of azo compounds include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethytriA/), 2,2'-azobis (
2,4-dimethy*-4-methoxyvaleronitri/L/)
On the other hand, specific examples of organic peroxides include benzoyl peroxide, diuroyl peroxide, and the like. Also, V-dox type polymerization initiator,
For example, combinations of organic peroxides and amines can also be used.
本発明のメタクリル樹脂キャスト板を重合によって製造
する際の重合温度は、使用するラジオ/L/?を合間始
剤の種類によって異なるが、一般には10〜150℃で
ある。The polymerization temperature when producing the methacrylic resin cast plate of the present invention by polymerization is radio/L/? The temperature varies depending on the type of initiator, but is generally 10 to 150°C.
鋳込重合法によって得られるキャスト板の厚さは特に制
限はないが、通常市販されている厚み、すなわち[12
〜65mの範囲内であることが好ましい。There is no particular limit to the thickness of the cast plate obtained by the cast polymerization method, but the thickness that is usually commercially available, that is, [12
It is preferably within the range of ~65 m.
さらに本発明の好都合な工程のいずれかに着色剤、紫外
線吸収剤、熱安定剤、他の帯電防止剤、各種充てん剤等
の添加剤を混合して用いることができる。Furthermore, additives such as colorants, ultraviolet absorbers, heat stabilizers, other antistatic agents, various fillers, etc. can be mixed and used in any of the convenient steps of the invention.
次に、実施例によってさらに具体的に本発明を説明する
が、本発明はこれらによって限定されるものではない。Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
なお、すべての試料の電気的性質は、23℃65%相対
湿度で1日間調湿した後測定した。The electrical properties of all samples were measured after being conditioned at 23° C. and 65% relative humidity for one day.
電荷半減時間は、スタティックオネストメーター(宍戸
屑会製)を使用し、印加電圧1aaaav1試料回転速
度1300 rpm、印加時間30秒、測定湿度23℃
、測定湿度65−の条件で測定し、電圧印加時の試料電
圧を初期電圧(7)、電圧印加後試料電圧が初期電圧の
半分になるまでの時間を電荷半減時間(see)とした
。表面抵抗値については、超絶縁抵抗計(タケダ理研製
TR−8601)を使用し、測定温度23℃、測定湿度
65チの条件で、印加電圧500vで1分後の表面抵抗
値(2)を測定した。洗浄は、30℃の温水中で超音波
洗浄を50分間行った。The charge half-life time was determined using a static honest meter (manufactured by Shishido Kuzukai), with an applied voltage of 1aaaav, a sample rotation speed of 1300 rpm, an application time of 30 seconds, and a measurement humidity of 23°C.
The sample voltage at the time of voltage application was defined as the initial voltage (7), and the time required for the sample voltage to become half of the initial voltage after voltage application was defined as the charge half-life time (see). Regarding the surface resistance value, use a super insulation resistance meter (TR-8601 manufactured by Takeda Riken), and measure the surface resistance value (2) after 1 minute at an applied voltage of 500 V at a measurement temperature of 23 degrees Celsius and a measurement humidity of 65 degrees Celsius. It was measured. For cleaning, ultrasonic cleaning was performed in warm water at 30° C. for 50 minutes.
耐熱性については試料をア二−μ後、ASTMD648
に準じてHD T (℃)を測定した。強度については
ASTM D638に準じて引張試験を行い、引張弾
性係数および引張破壊強度を測定した。透明性について
は、積分球式ヘーズメーター(日本精密光学製、5EP
−H−88)を使用して曇価を測定した。Regarding heat resistance, after testing the sample with ASTM D648
HD T (°C) was measured according to . As for the strength, a tensile test was conducted according to ASTM D638, and the tensile elastic modulus and tensile breaking strength were measured. Regarding transparency, an integrating sphere haze meter (manufactured by Nippon Seimitsu Kogaku, 5EP) was used.
-H-88) was used to measure the haze value.
実施例1
攪拌羽根付1!3tガフス製フラスコに、ジェニルアミ
ノエチルメタクリレート374重量部、ハイドロキノン
モノメチyエーテ/I/4重量部、メタノール450重
量部を入れ、攪拌しながらシメチμ硫酸252重量部、
メタノール80重量部の混合物を30℃以下になるよう
に滴下し、滴下終了後30分間攪拌を続けて四級アンモ
ニウム塩基を有する単量体(M−1)溶液を得た。Example 1 374 parts by weight of genylaminoethyl methacrylate, 4 parts by weight of hydroquinone monomethyate/I/4, and 450 parts by weight of methanol were placed in a 1!3 t gaff flask equipped with a stirring blade, and while stirring, 252 parts by weight of sulfuric acid was added. Department,
A mixture of 80 parts by weight of methanol was added dropwise to the mixture at a temperature of 30° C. or below, and stirring was continued for 30 minutes after the completion of the addition to obtain a monomer (M-1) solution having a quaternary ammonium base.
この溶液にアゾビヌイソプチロニトリ/I/6重量部、
n−オクチμメμカプタン4重量部、メタノ−/L/4
80重量部、ポリエチレングリコール(23)モノメタ
クリレートモノメチルエーテA/620重量部を加え、
60℃窒素雰囲気下で4時間重合させた。重合後、その
まま真空乾燥して共重合体(P−1)を得た。メチルメ
タクリレート100重量部に、上記共重合体(p−1)
を(L5重量部、化合物(III)として2−ヒドロキ
シエチ〜メタクリV−トを[1,5重量部、重合開始剤
として2.2′−アゾビスイソブチロニド!J/L’0
.05重址部を溶解させた後、減圧にして溶存空気を除
去し、ガスケット及び2枚の強化ガラスにより形成され
、あらかじめ厚さ3糟になるよう設定された七μ中に注
いだ。重合は、60℃において10時間、110℃にお
いて4時間行った。このキャスト板は、表面抵抗率が&
5 X 10’Ω、電荷半減時間2.4秒、曇価1.
0チであった。To this solution, 6 parts by weight of azobinuisoptilonitri/I,
n-octium μcaptan 4 parts by weight, methanol/L/4
Add 80 parts by weight of polyethylene glycol (23) monomethacrylate monomethyl ether A/620 parts by weight,
Polymerization was carried out at 60°C under a nitrogen atmosphere for 4 hours. After polymerization, the mixture was directly vacuum-dried to obtain a copolymer (P-1). The above copolymer (p-1) was added to 100 parts by weight of methyl methacrylate.
(L5 parts by weight, 2-hydroxyethyl-methacrylate as compound (III) [1.5 parts by weight, 2,2'-azobisisobutyronide as a polymerization initiator!J/L'0
.. After melting the 05 layer, the dissolved air was removed by reducing the pressure, and the mixture was poured into a 7-micrometer container made of a gasket and two sheets of tempered glass, and preset to have a thickness of 3 mm. Polymerization was carried out at 60°C for 10 hours and at 110°C for 4 hours. This cast board has a surface resistivity of &
5 x 10'Ω, charge half-life time 2.4 seconds, haze value 1.
It was 0chi.
又、得られた板に水洗処理を行い、ただちに帯電防止性
能を評価したところ、表面抵抗率&3X1010Ω、電
荷半減時間2.4秒であった。Further, when the obtained plate was washed with water and the antistatic performance was immediately evaluated, the surface resistivity was +3×10 10 Ω, and the charge half-life time was 2.4 seconds.
又、ASTM D648に準じてHDT試片を作成し
、アニール後I(DTを測定したところ100℃であシ
、ASTM D65Bに準じて引張試験を行ったとこ
ろ引張弾性係数3 X 10’(kg/an” )、引
張破壊強度750 (kli/cm” )であった。In addition, HDT specimens were prepared according to ASTM D648, and after annealing I (DT was measured at 100°C), and a tensile test was performed according to ASTM D65B, and the tensile elastic modulus was 3 × 10' (kg/ an"), and the tensile strength at break was 750 (kli/cm").
比較例1
メチルメタクリレート部分重合体(粘度100センチポ
イズ、重合率13%)100重量部に42′−アゾビス
イソブチロニトリ/L’105重量部を溶解させた後、
実施例1と同様な方法で重合させて板厚3+wのキャス
ト板を得た。この板の表面抵抗率は10160以上であ
シ、電荷半減時間120 sec以上、曇価1.0 %
であった。Comparative Example 1 After dissolving 105 parts by weight of 42'-azobisisobutyronitri/L' in 100 parts by weight of methyl methacrylate partial polymer (viscosity 100 centipoise, polymerization rate 13%),
Polymerization was performed in the same manner as in Example 1 to obtain a cast plate having a thickness of 3+w. The surface resistivity of this plate is 10160 or more, the charge half-life time is 120 seconds or more, and the haze value is 1.0%.
Met.
又HDTは100℃であ)、引張弾性係数は3 X 1
0’ (kg/m” )、引張破壊強度は760(kg
/菌2)であった。HDT is 100℃), and the tensile modulus is 3 x 1
0'(kg/m"), tensile breaking strength is 760 (kg/m")
/ Bacteria 2).
実施例2〜4
メチルメタクリレート部分重合体(粘度100センチポ
イズ、重合率8%)100重量部に実施例1で得られた
共重合体P−1to〜1゜Wit部、2−ヒドロキクエ
チルメタクリレート1.0〜4.0重量部を添加混合し
、実施例1と同様の手法によシ厚さ3■のメタクリ/I
/樹脂キャスト板を得た。23℃、65%相対湿度雰囲
気中で1日間調湿後の帯電防止性能及びその他の物性の
評価結果を表1に示す。Examples 2 to 4 To 100 parts by weight of methyl methacrylate partial polymer (viscosity 100 centipoise, polymerization rate 8%), 1 to 1° Wit part of copolymer P-1 obtained in Example 1, 2-hydroxyethyl methacrylate 1 .0 to 4.0 parts by weight were added and mixed, and the same method as in Example 1 was carried out to obtain a 3-inch thick methacrylate/I.
/Resin cast plate was obtained. Table 1 shows the evaluation results of antistatic performance and other physical properties after humidity conditioning for one day in an atmosphere of 23° C. and 65% relative humidity.
実施例5〜11
メチルメタクリレート部分重合体(粘度100センチポ
イズ、重合率8チ)I Do重量部K。Examples 5-11 Methyl methacrylate partial polymer (viscosity 100 centipoise, polymerization rate 8 cm) I Do parts by weight K.
共重合体P−1を2.0電蝕部と表1に示す種々の化合
物(III)を添加混合し、実施例1と同様の手法によ
り厚さ3鱈のメタクリ/I/樹脂キャスト板を得た。2
3℃、65%相対湿度雰囲気中で1日間調湿後の帯電防
止性能及びその他の物性の評価結果を表1に示す。Copolymer P-1 was mixed with 2.0% electrolytically eroded portion and various compounds (III) shown in Table 1, and a methacrylic/I/resin cast plate with a thickness of 3 was made by the same method as in Example 1. Obtained. 2
Table 1 shows the evaluation results of antistatic performance and other physical properties after humidity conditioning for one day in an atmosphere of 3° C. and 65% relative humidity.
実施例12〜19
実施例1で得た四級アンモニウム塩基を含む単量体M−
1溶液を用い、表2に示す組成の単量体混合物を加え、
実施例1と同様の手法で重合させて共重合体(P−2〜
7)を得た。これらの共重合体それぞれzoy量部を使
用して、実施例1と同様の手法により厚さ3瓢のメタク
リ/L’樹脂キャスト板を得た。25℃、65チ相対湿
度雰囲気で1日間調湿後の帯電防止性能及びその他の物
性の評価結果を表3に示す。Examples 12 to 19 Monomer M- containing quaternary ammonium base obtained in Example 1
1 solution, add a monomer mixture with the composition shown in Table 2,
Polymerization was performed in the same manner as in Example 1 to obtain a copolymer (P-2~
7) was obtained. Using zoy parts of each of these copolymers, a methacrylic/L' resin cast plate having a thickness of 3 gourds was obtained in the same manner as in Example 1. Table 3 shows the evaluation results of antistatic performance and other physical properties after humidity conditioning at 25° C. and 65° relative humidity for one day.
実施例20〜24
表4に示すアミノ基含有アクリレート又はメタクリレー
トと四級化剤の組み合せを用いた他は、実施例1と同様
の手法にょシ、四級アンモニウム塩基を有する共重合体
(P−8〜p−12)t−得た。これらをメチルメタク
リレート部分重合体(粘度100センチポイズ、重合率
8チ)100重量部に対して2−0重量部添加し、実施
例1と同様の手法により、厚さ3日のメタクリル樹脂板
を得た。23℃、65Is相対湿度雰囲気で1日間調湿
した後の帯電防止性能及びその他の物性の評価結果を表
5に示す。Examples 20 to 24 A copolymer having a quaternary ammonium base (P- 8-p-12) t-obtained. 2-0 parts by weight of these were added to 100 parts by weight of methyl methacrylate partial polymer (viscosity 100 centipoise, polymerization rate 8 cm), and a methacrylic resin plate with a thickness of 3 days was obtained by the same method as in Example 1. Ta. Table 5 shows the evaluation results of antistatic performance and other physical properties after humidity conditioning at 23° C. and 65Is relative humidity atmosphere for one day.
実施例25
実施例1で得た四級アンモニウム塩基を含む単量体(M
−1)溶液に、ポリエチレングリコ−7+/(23)モ
ノメタクリレートモノメチμエーテ、TI/620重量
及びスチレン310重量部を加え、実施例1と同様の手
法で重合させて共重合体(P−13)を得た。この共重
合体2.0重量部をメチルメタクリソート90重量部と
スチレン10重量部とからなる単量体混合物に加え、さ
らにプロピレングリコ−Iv五〇重量部を加えて、実施
例1と同様の手法によシ厚さ3flのメタクリル樹脂板
を得た。23℃、65チ相対湿度雰囲気で1日間調湿し
た後の帯電防止性能及びその他の物性の評価結果を表3
に示す。Example 25 Monomer containing quaternary ammonium base obtained in Example 1 (M
-1) To the solution, add polyethylene glyco-7+/(23) monomethacrylate monomethyl ether, TI/620 weight, and 310 parts by weight of styrene, and polymerize in the same manner as in Example 1 to obtain a copolymer (P- 13) was obtained. 2.0 parts by weight of this copolymer was added to a monomer mixture consisting of 90 parts by weight of methyl methacrysate and 10 parts by weight of styrene, and further 50 parts by weight of propylene glyco-Iv was added, and the same procedure as in Example 1 was carried out. A methacrylic resin plate with a thickness of 3 fl was obtained by this method. Table 3 shows the evaluation results of antistatic performance and other physical properties after one day of humidity control at 23°C and 65° relative humidity.
Shown below.
実施例26
メチルメタクリレート部分重合体(粘11000センチ
ポイズ、重合率20%)100重量部に、実施例1で得
た共重合体P−1を2.0重量部、化合ell (II
I)として2−ヒドロキシェチ〜メタクリレートzO重
量部、重合開始剤としてz 21 ++アゾビスイソブ
チロニトリ/vQ、05重量部、雌型剤としてジオクチ
pスμホサクシネート・ナトリウふ塩[1005重量部
を添加混合したものを、特公昭52−30985号に示
す如き連続製板装置で重合させて厚さ3簡のメタクリル
樹脂板を製造した。重合は70℃の温水雰囲気下で60
分、次いで130℃の空気雰囲気下で15分間滞在させ
て重合を完結させた。得られたメタクリル樹脂キャスト
板を実施例1と同様に評価したところ、表面抵抗率a
6 X 10’Ω、電荷半減時間Za秒、曇価1.5チ
であシ、水洗処理後の表面抵抗率は&3X10”Ωであ
った。Example 26 2.0 parts by weight of copolymer P-1 obtained in Example 1 was added to 100 parts by weight of methyl methacrylate partial polymer (viscosity 11000 centipoise, polymerization rate 20%), and compound ell (II
Parts by weight of 2-hydroxyethyl methacrylate zO as I), 05 parts by weight of z 21 ++ azobisisobutyronitrile/vQ as a polymerization initiator, and dioctips μ fosuccinate sodium salt [1005 parts by weight as a female agent] The added mixture was polymerized using a continuous plate making apparatus as disclosed in Japanese Patent Publication No. 52-30985 to produce a methacrylic resin plate having a thickness of 3 sheets. Polymerization was carried out at 60°C in a warm water atmosphere at 70°C.
The polymerization was completed by staying at 130° C. for 15 minutes under an air atmosphere. The obtained methacrylic resin cast plate was evaluated in the same manner as in Example 1, and the surface resistivity a
The resistivity was 6 x 10'Ω, the charge half-life time was Za seconds, the haze value was 1.5 cm, and the surface resistivity after washing with water was &3 x 10'Ω.
又、引張弾性係数は五OX 10’ kg/cM” 、
引張破壊強度は740 kg/crtt”、HDTは1
00℃であった。In addition, the tensile elastic modulus is 5OX 10'kg/cM",
Tensile breaking strength is 740 kg/crtt”, HDT is 1
It was 00℃.
実施例27
共重合体P−1の代夛にP−7を用いた他は実施例26
と同様にして、板厚3mのメタクリル樹脂キャスト板を
得た。表面抵抗率はtIX1010Ω、電荷半減時間は
2.0秒、曇価は1.5チであり、水洗処理後の表面抵
抗率は9.9X10’Ωであった。Example 27 Example 26 except that P-7 was used as a substitute for copolymer P-1.
In the same manner as above, a methacrylic resin cast plate having a thickness of 3 m was obtained. The surface resistivity was tIX1010Ω, the charge half-life time was 2.0 seconds, the haze value was 1.5H, and the surface resistivity after water washing was 9.9X10'Ω.
又、引張弾性係数は五OX 10 ’ kll/cs”
、引張破壊強度は740 kg7cm2であり、HD’
rは100℃でめった。Also, the tensile elastic modulus is 5OX 10'kll/cs"
, the tensile breaking strength is 740 kg7cm2, and HD'
r was reached at 100°C.
比較例2
メチルメタクリレート100重量部に対し実施例14で
得た共重合体P−4(L5重量部を加え、実施例1と同
様の手法によシ厚さ511IIのメタクリ/l/樹脂キ
ャスト板を得た。23℃、65Ls相対湿度雰囲気中で
1日間調湿した後の帯電防止性能及びその他の物性の評
価結果を表6に示す。Comparative Example 2 5 parts by weight of copolymer P-4 (L) obtained in Example 14 was added to 100 parts by weight of methyl methacrylate, and the same method as in Example 1 was carried out to produce a methacrylate/l/resin cast plate with a thickness of 511 II. Table 6 shows the evaluation results of antistatic performance and other physical properties after conditioning the humidity in an atmosphere of 23° C. and 65 Ls relative humidity for one day.
比較例3〜5
メチルメタクリレート部分重合体(粘度100センチボ
イズ、重合率8%)100重量部に化合物(m)として
2−ヒドロキシメチμメタクリV−ト、メタクリル酸、
プロピレングリコ−μをそれぞれ2.0重量部添加混合
し、実施例1と同様の手法によシ、厚さ3Mのメタクリ
ル樹脂キャスト板を得た。評価結果を表6に示す。Comparative Examples 3 to 5 100 parts by weight of methyl methacrylate partial polymer (viscosity 100 centiboise, polymerization rate 8%) was added as a compound (m) to 2-hydroxymethacrylate V-methacrylate, methacrylic acid,
2.0 parts by weight of each propylene glyco-μ was added and mixed, and the same method as in Example 1 was used to obtain a 3M thick methacrylic resin cast plate. The evaluation results are shown in Table 6.
比較例6
実施例1で得られた四級アンモニウム塩基を有する単量
体(M−1)溶液にポリエチレングリコ−/l/(23
)モノメタクリレートモノメチルニー・テμ5580重
量部を加えて実施例1と同様の手法によシ、共重合体P
−14を得た。Comparative Example 6 Polyethylene glycol/l/(23
) Copolymer P was prepared in the same manner as in Example 1 by adding 5,580 parts by weight of monomethacrylate monomethyl ni-teμ.
-14 was obtained.
メチμメタクリv−ト100重量部に上記共重合体P−
142,0重量部及び2−ヒドロキシエチルメタクリレ
ート1.0重量部添加混合し、実施例1と同様の手法に
よシ厚さ5tmのメタクリル樹脂キャスト板を得た。評
価結果を表6に示す。The above copolymer P- was added to 100 parts by weight of methacrylate.
142.0 parts by weight and 1.0 parts by weight of 2-hydroxyethyl methacrylate were added and mixed, and a methacrylic resin cast plate having a thickness of 5 tm was obtained in the same manner as in Example 1. The evaluation results are shown in Table 6.
比較例7
メチルメタクリレート部分重合体(粘度100センチボ
イズ、重合率8%)100重量部に、クリセリンモノメ
賃アレートを5重量部添加混合し、実施例1と同様の手
法により、板厚5■のメタクリル樹脂キャスト板を得た
。評価結果を表6に示す。Comparative Example 7 5 parts by weight of chrycerin monomer arate was added to 100 parts by weight of methyl methacrylate partial polymer (viscosity 100 centivoise, polymerization rate 8%) and mixed, and a methacrylic resin having a plate thickness of 5 cm was prepared by the same method as in Example 1. I got a cast board. The evaluation results are shown in Table 6.
比較例8
四級アンモニウム塩基を有する塗布型帯電防止剤(スタ
チサイド、Analytical ChemicalL
aboratories 社製)の1.5 ts水溶
液に板厚3■のメタクリル樹脂板(アクリフィト、三菱
レイヨン製)を1分間浸析し、風乾後、実施例1と同様
に評価した。結果を表6に示す。Comparative Example 8 Coating type antistatic agent having quaternary ammonium base (Staticide, Analytical Chemical L
A 3-inch thick methacrylic resin plate (Acryphyte, manufactured by Mitsubishi Rayon) was soaked in a 1.5 ts aqueous solution of Aboratories Co., Ltd. for 1 minute, and after air-drying, it was evaluated in the same manner as in Example 1. The results are shown in Table 6.
本発明によれば、良好且つ恒久的な帯電防止性能を有し
、メタクリμ樹脂本来の物性を低下させることのないメ
タクリル樹脂キャスト板を提供することができる。この
メタクリル樹脂板は静電気によるトラプμがないのでエ
レクトロニクス関連分野等の高信頼性を必要とする産業
にも使用できる。According to the present invention, it is possible to provide a methacrylic resin cast plate that has good and permanent antistatic performance and does not deteriorate the inherent physical properties of methacrylic μ resin. This methacrylic resin plate has no trap μ caused by static electricity, so it can be used in industries that require high reliability such as electronics-related fields.
表 ま
ただし PEG(23):ポリエチレングリコー/I/
(2!S)モノメタクリV−トモノメチμエーテμ
MMA :メチルメタクリレート表 4
ただし DEMA :ジメチμアミノエチルメタクリ
レートDMMA :ジメチルアミノメチμメタクリレ
ートDEA :ジエチルアミノエチルアクリ、レー
トDE8 ニジエチル硫酸
DMS ニジメチ/%/#Table Matadashi PEG (23): Polyethylene glycol/I/
(2!S) Monomethacrylic V-monomethi ether μ MMA: Methyl methacrylate Table 4 However, DEMA: Dimethyl μ aminoethyl methacrylate DMMA: Dimethylaminomethy μ methacrylate DEA: Diethylaminoethyl acrylate, rate DE8 Nidiethyl sulfate DMS Nizimethy/%/#
Claims (1)
0重量%以上とこれと共重合可能な少なくとも一種の単
量体50重量%以下とからなる単量体混合物或いはそれ
らの部分重合体( I )100重量部に対し、 一般式 ▲数式、化学式、表等があります▼ (R_1は水素原子又はメチル基、R_2〜R_4は水
素原子又は炭素数1〜9の置換基を含んでいてもよいア
ルキル基、mは1〜10、X^−は四級化剤のアニオン
) で表される四級アンモニウム塩基を有する単量体30〜
100重量%及びこれと共重合可能な少なくとも一種の
単量体0〜70重量%からなる単量体又は単量体混合物
を重合させて得られた(共)重合体(II)0.1〜20
重量部、及び一般式 ▲数式、化学式、表等があります▼(a) (R_5は水素原子又は炭素数1〜22の脂肪族炭化水
素残基)で表される脂肪酸、 一般式 ▲数式、化学式、表等があります▼(b) (R_6は水素原子又は炭素数1〜4の脂肪族炭化水素
残基、A_1は炭素数2〜6のアルキレン基、nは0又
は1以上の整数)で表されるアクリル酸又はその誘導体
及び 一般式 ▲数式、化学式、表等があります▼(c) (A_2は炭素数2〜4のアルキレン基、pは1以上の
整数)で表されるアルキレングリコール の中から選ばれる化合物(III)0.1〜20重量部を
混合して重合させることを特徴とする帯 電防止性に優れたメタクリル樹脂キャスト板の製造方法
。 2、四級アンモニウム塩基を有する単量体と共重合可能
な単量体として、 一般式 ▲数式、化学式、表等があります▼ (R_7は水素原子又はメチル基、R_8は水素原子又
は炭素数1〜18のアルキル基、アリル基、アリール基
、アラルキル基、A_3は炭素数2〜4のアルキレン基
、qは0〜500の整数)で表される化合物を使用する
特許請求の範囲第1項記載の帯電防止性に優れたメタク
リル樹脂キャスト板の製造方法。 3、四級アンモニウム塩基のカウンターアニオンが 一般式 R_9SO_3^−又はR_9OSO_3^−(R_9
は水素原子又は炭素数1〜20のフエニル基を含んでい
てもよいアルキル基) で表される特許請求の範囲第1項記載の帯電防止性に優
れたメタクリル樹脂キャスト板の製造方法。 4、キャスト板を製造する際の重合を2枚の無機ガラス
板又は金属板とガスケットで構成された鋳型内で行なう
特許請求の範囲第1項記載の帯電防止性に優れたメタク
リル樹脂キャスト板の製造方法。 5、キャスト板を製造する際の重合を、同一方向に同一
速度で進行する片面鏡面研摩された2枚のステンレス鋼
製エンドレスベルトとガスケットで構成された鋳型内で
連続的に行なう特許請求の範囲第1項記載の帯電防止性
に優れたメタクリル樹脂キャスト板の製造方法。[Claims] 1. Methyl methacrylate or methyl methacrylate 5
For 100 parts by weight of a monomer mixture or a partial polymer thereof (I) consisting of 0% by weight or more and 50% by weight or less of at least one monomer copolymerizable with the monomer mixture, the general formula ▲ mathematical formula, chemical formula, There are tables, etc. ▼ (R_1 is a hydrogen atom or a methyl group, R_2 to R_4 are hydrogen atoms or an alkyl group that may contain a substituent having 1 to 9 carbon atoms, m is 1 to 10, and X^- is a quaternary monomer 30-having a quaternary ammonium base represented by
(Co)polymer (II) obtained by polymerizing a monomer or a monomer mixture consisting of 100% by weight and 0 to 70% by weight of at least one monomer copolymerizable with this (co)polymer (II) 0.1 to 20
Parts by weight, and general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (a) Fatty acid represented by (R_5 is a hydrogen atom or an aliphatic hydrocarbon residue having 1 to 22 carbon atoms) General formula ▲ Numerical formula, chemical formula , tables, etc.▼(b) (R_6 is a hydrogen atom or an aliphatic hydrocarbon residue having 1 to 4 carbon atoms, A_1 is an alkylene group having 2 to 6 carbon atoms, and n is an integer of 0 or 1 or more) Among the alkylene glycols represented by acrylic acid or its derivatives and general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (c) (A_2 is an alkylene group having 2 to 4 carbon atoms, p is an integer of 1 or more) A method for producing a methacrylic resin cast plate with excellent antistatic properties, comprising mixing and polymerizing 0.1 to 20 parts by weight of a compound (III) selected from the following. 2. As monomers that can be copolymerized with monomers having a quaternary ammonium base, there are general formulas, mathematical formulas, chemical formulas, tables, etc. (R_7 is a hydrogen atom or a methyl group, R_8 is a hydrogen atom or a carbon number of 1 -18 alkyl group, allyl group, aryl group, aralkyl group, A_3 is an alkylene group having 2 to 4 carbon atoms, and q is an integer of 0 to 500) is used, according to claim 1. A method for manufacturing a methacrylic resin cast plate with excellent antistatic properties. 3. The counter anion of the quaternary ammonium base has the general formula R_9SO_3^- or R_9OSO_3^-(R_9
is a hydrogen atom or an alkyl group which may contain a phenyl group having 1 to 20 carbon atoms) The method for producing a methacrylic resin cast plate with excellent antistatic properties according to claim 1. 4. A methacrylic resin cast plate with excellent antistatic properties as claimed in claim 1, in which polymerization during production of the cast plate is carried out in a mold composed of two inorganic glass plates or metal plates and a gasket. Production method. 5. The claim that the polymerization during production of the cast plate is carried out continuously in a mold consisting of two single-sided mirror-polished stainless steel endless belts and gaskets that proceed in the same direction and at the same speed. 2. The method for producing a methacrylic resin cast plate with excellent antistatic properties as described in item 1.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21189086A JPH075683B2 (en) | 1986-09-09 | 1986-09-09 | Method for producing methacrylic resin cast plate excellent in antistatic property |
EP87112988A EP0259802B1 (en) | 1986-09-08 | 1987-09-04 | Methacrylic resin cast plate having excellent antistatic property and process for preparation thereof |
CA000546195A CA1318064C (en) | 1986-09-08 | 1987-09-04 | Methacrylic resin cast plate having excellent antistatic property and process for preparation thereof |
DE8787112988T DE3784202T2 (en) | 1986-09-08 | 1987-09-04 | MOLDED METHACRYL RESIN PLATE WITH GOOD ANTISTATIC PROPERTIES AND METHOD FOR THE PRODUCTION THEREOF. |
KR1019870009857A KR910003737B1 (en) | 1986-09-08 | 1987-09-07 | Methacrylic resin cast plate having excellent antistatic property and process for preparation thereof |
US07/423,596 US5086106A (en) | 1986-09-08 | 1989-10-17 | Methacrylic resin cast plate having excellent antistatic property |
US07/498,547 US5118744A (en) | 1986-09-08 | 1990-03-26 | Process for the preparation of a methacrylic resin cast plate having excellent antistatic property |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21189086A JPH075683B2 (en) | 1986-09-09 | 1986-09-09 | Method for producing methacrylic resin cast plate excellent in antistatic property |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6368614A true JPS6368614A (en) | 1988-03-28 |
JPH075683B2 JPH075683B2 (en) | 1995-01-25 |
Family
ID=16613332
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21189086A Expired - Lifetime JPH075683B2 (en) | 1986-09-08 | 1986-09-09 | Method for producing methacrylic resin cast plate excellent in antistatic property |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH075683B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02212505A (en) * | 1988-12-13 | 1990-08-23 | Smith Kline Ltd | Anion exchange polymer |
JP2011506370A (en) * | 2007-12-13 | 2011-03-03 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Quaternization of the additive aminoalkyl methacrylate copolymer E to improve the permeability and solubility of pharmaceutical substances |
CN115260382A (en) * | 2022-08-23 | 2022-11-01 | 浙江工业大学 | Transparent antistatic PMMA material and preparation method thereof |
-
1986
- 1986-09-09 JP JP21189086A patent/JPH075683B2/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02212505A (en) * | 1988-12-13 | 1990-08-23 | Smith Kline Ltd | Anion exchange polymer |
JP2011506370A (en) * | 2007-12-13 | 2011-03-03 | エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング | Quaternization of the additive aminoalkyl methacrylate copolymer E to improve the permeability and solubility of pharmaceutical substances |
CN115260382A (en) * | 2022-08-23 | 2022-11-01 | 浙江工业大学 | Transparent antistatic PMMA material and preparation method thereof |
CN115260382B (en) * | 2022-08-23 | 2024-02-13 | 浙江工业大学 | Transparent antistatic PMMA material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH075683B2 (en) | 1995-01-25 |
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