JP2006124608A - Methacrylic resin composition for extruded sheet and method for producing its extruded sheet - Google Patents
Methacrylic resin composition for extruded sheet and method for producing its extruded sheet Download PDFInfo
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- JP2006124608A JP2006124608A JP2004318163A JP2004318163A JP2006124608A JP 2006124608 A JP2006124608 A JP 2006124608A JP 2004318163 A JP2004318163 A JP 2004318163A JP 2004318163 A JP2004318163 A JP 2004318163A JP 2006124608 A JP2006124608 A JP 2006124608A
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- 239000000113 methacrylic resin Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 87
- 238000011282 treatment Methods 0.000 claims abstract description 36
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001125 extrusion Methods 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 239000011347 resin Substances 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 48
- 238000005498 polishing Methods 0.000 claims description 23
- 238000006073 displacement reaction Methods 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 3
- 125000005641 methacryl group Chemical group 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 11
- -1 alkyl methacrylates Chemical class 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 8
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920000800 acrylic rubber Polymers 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 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 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 229910000394 calcium triphosphate Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- RFWLACFDYFIVMC-UHFFFAOYSA-D pentacalcium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O RFWLACFDYFIVMC-UHFFFAOYSA-D 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
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000570 polyether Chemical class 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- OWHSTLLOZWTNTQ-UHFFFAOYSA-N 2-ethylhexyl 2-sulfanylacetate Chemical compound CCCCC(CC)COC(=O)CS OWHSTLLOZWTNTQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical class 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- RNOOHTVUSNIPCJ-UHFFFAOYSA-N butan-2-yl prop-2-enoate Chemical compound CCC(C)OC(=O)C=C RNOOHTVUSNIPCJ-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 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
- 238000005457 optimization Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
Abstract
Description
本発明は、薄肉のシート押出時のバンクの安定性に優れ、シート成形性を向上させ、ハードコート処理や反射防止処理、帯電防止処理での外観不良を防止した優れた押出しシート用メタクリル樹脂に関する。 The present invention relates to an excellent methacrylic resin for an extruded sheet that has excellent bank stability during extrusion of a thin sheet, improved sheet formability, and prevented appearance defects in hard coat treatment, antireflection treatment, and antistatic treatment. .
メタクリル樹脂は、透明樹脂として他のプラスチック透明樹脂よりその高い光透過率、耐候性、高い剛性に特徴があり、車両用部品、照明器具、建築用材料、看板、絵画や、表示装置の窓や銘板等広い用途で用いられている。中でも、携帯電話の表示窓は、内部の液晶表示を見やすくすることと同時に、外からの衝撃や圧力から内部の液晶を守ることや平滑性が必要なことから、メタクリル樹脂シートが広く用いられている。この携帯電話は、近年の小型化、薄肉化に従い、この表示窓のメタクリル樹脂シートも厚み精度の高い薄肉化が進んでいる。 Methacrylic resin is characterized by its high light transmittance, weather resistance, and high rigidity compared to other plastic transparent resins as a transparent resin, such as vehicle parts, lighting equipment, building materials, signboards, paintings, display windows, It is used in a wide range of applications such as nameplates. In particular, methacrylic resin sheets are widely used for the display windows of mobile phones because the internal liquid crystal display is easy to see and at the same time it is necessary to protect the internal liquid crystal from external impact and pressure and smoothness. Yes. With the recent reduction in size and thickness of the mobile phone, the methacrylic resin sheet of the display window is also being thinned with high thickness accuracy.
一般的にメタクリル樹脂シートの製造方法としては、平滑性と厚み精度と量産性から、Ｔダイ及びロールを用いた押出機によるシート押出し法が広く用いられている。しかし、シートが薄肉になると、ポリッシングロール引き取り中に樹脂が冷却されて、引取りが難しくなるため、引き取りの線速を上げて製造が行われる。このときに、板厚とロールの鏡面の転写性を上げるために、ポリッシングロールのところにバンクと呼ばれる溶融した樹脂の溜りを設けて製造するが、このバンクが、引き取りの線速を上げるに従い、シート幅方向でのバンクの大きさが不均一になる。バンクが小さくなると、ポリッシングロール面の転写が不十分となったり、厚みが薄くなったりする。バンクが大きくなると、厚みが厚くなったり、バンクがきれいにつぶれずにシート表面にバンク模様が生じる不具合が生じる。 In general, as a method for producing a methacrylic resin sheet, a sheet extrusion method using an extruder using a T die and a roll is widely used because of smoothness, thickness accuracy, and mass productivity. However, when the sheet becomes thin, the resin is cooled during the taking-up of the polishing roll, and the take-up becomes difficult. Therefore, the production is performed by increasing the drawing speed. At this time, in order to increase the transferability of the plate thickness and the mirror surface of the roll, it is manufactured by providing a pool of molten resin called a bank at the polishing roll, but as this bank increases the linear speed of take-up, The bank size in the sheet width direction becomes non-uniform. When the bank becomes small, the transfer on the polishing roll surface becomes insufficient or the thickness becomes thin. When the bank becomes larger, the thickness becomes thicker, or the bank does not collapse cleanly and a bank pattern is generated on the sheet surface.
また、表示窓として用いられるシートは、携帯電話使用中の耐擦傷性のためのハードコート処理や表示を見やすくするための反射防止処理や、ゴミ、ほこり付着防止のための帯電防止処理が望まれる。この処理の際に、シートのみでは見られなかった表面凹凸の不良がさらに大きく見える現象が発生し、処理後のシートの外観がより悪くなる不具合が生じる。また、一部溶剤や未反応のモノマー等が処理液に存在するため、これら溶剤によるクラックが発生しやすくなる。
これまで、一般的にメタクリル樹脂シート加工時の不具合を改善する公知の方法として、高分子量のメタクリル樹脂を添加する技術が報告されている。しかし、薄肉シートの場合、高分子量のメタクリル樹脂の分子量が不適正に高いことから、未溶融の高分子量のメタクリル樹脂がシート表面に発生するため、シート表面に凹凸形状やシート表面のゆがみが発生し好ましくない。また、バンク形状が大きくなりすぎるため、バンク模様が発生しやすくなる（例えば、特許文献１参照）。
In addition, a sheet used as a display window is required to have a hard coat treatment for scratch resistance during use of a mobile phone, an antireflection treatment for making the display easy to see, and an antistatic treatment for preventing dust and dust from adhering. . During this process, a phenomenon in which the surface irregularities that were not seen with the sheet alone appear to be larger occurs, and the appearance of the sheet after the process becomes worse. In addition, since a part of the solvent, unreacted monomer, and the like are present in the treatment liquid, cracks due to these solvents are likely to occur.
So far, a technique of adding a high molecular weight methacrylic resin has been reported as a publicly known method for improving a defect during processing of a methacrylic resin sheet. However, in the case of thin-walled sheets, the molecular weight of the high molecular weight methacrylic resin is inappropriately high, so unmelted high molecular weight methacrylic resin is generated on the sheet surface, resulting in uneven shape and distortion of the sheet surface. It is not preferable. Further, since the bank shape becomes too large, a bank pattern is likely to occur (see, for example, Patent Document 1).
さらには、多段重合で得られるアクリルゴムを添加したり、アクリルゴムと高分子量のメタクリル樹脂を併用して添加する技術がある。しかし、アクリルゴムは架橋体であることから樹脂と相溶しないため、薄肉シートの表面に小さな凹凸形状が発生し外観不良となる。シートにハードコート処理や反射防止処理、帯電防止処理をした後、処理後のシートの外観がより悪くなる不具合が生じる。また、アクリルゴムを添加により流動性が低下するため、流動性向上のため押出し温度を高くする必要があり、その結果樹脂の分解が発生しシートが部分的に発泡する不具合が生じる（例えば、特許文献２、３、４参照）。
また、分岐構造をもつメタクリル樹脂を用いる技術がある。しかし、この場合は得られたポリマーの剛直性が高すぎるため、薄肉シートを成形したとき歪が残りやすい。このメタクリル樹脂組成物で成形した薄肉シートは、エタノール等の溶剤を主成分とするハードコート処理や反射防止処理、帯電防止処理の処理を行った際に、ストレスクラックが発生しやすくなる。また、分岐構造は、多官能モノマーを使用して得られるが、分岐構造が多い場合可塑化することが出来ない。導入する分岐構造が少ないと、ロットによるメタクリル樹脂のバラツキが生じやすく、シートの押出し条件の最適化が得られない（特許文献５）。
Furthermore, there is a technique of adding acrylic rubber obtained by multistage polymerization, or adding acrylic rubber and a high molecular weight methacrylic resin in combination. However, since acrylic rubber is a cross-linked product and is not compatible with resin, a small uneven shape is generated on the surface of the thin sheet, resulting in poor appearance. After the sheet is subjected to a hard coat treatment, an antireflection treatment, or an antistatic treatment, there arises a problem that the appearance of the sheet after the treatment becomes worse. Moreover, since the fluidity is reduced by adding acrylic rubber, it is necessary to increase the extrusion temperature to improve the fluidity. As a result, the resin decomposes and the sheet partially foams (for example, patents). References 2, 3, and 4).
There is also a technique using a methacrylic resin having a branched structure. However, in this case, since the obtained polymer is too rigid, distortion tends to remain when a thin sheet is formed. A thin-walled sheet molded from this methacrylic resin composition is prone to stress cracking when it is subjected to a hard coat treatment mainly composed of a solvent such as ethanol, an antireflection treatment, or an antistatic treatment. Moreover, although a branched structure is obtained using a polyfunctional monomer, when there are many branched structures, it cannot plasticize. If the branched structure to be introduced is small, variations in methacrylic resin due to lots are likely to occur, and optimization of sheet extrusion conditions cannot be obtained (Patent Document 5).
このように、薄肉のシート押出時のバンクの安定性に優れ、シート成形性を向上し、外観不良の無い、ハードコート処理や反射防止処理、帯電防止処理での外観不良を防止した優れた押出しシート用メタクリル系樹脂組成物を提供することである。 In this way, excellent bank stability during extrusion of thin sheets, improved sheet formability, no appearance defects, and excellent extrusion that prevents appearance defects in hard coat treatment, antireflection treatment, and antistatic treatment It is to provide a methacrylic resin composition for a sheet.
これらの問題を解決するために鋭意研究を重ねた結果、分子量がある範囲にある２種類のメタクリル系樹脂を適正な割合で用いることにより薄肉シート押出時のバンク安定性に優れ、外観不良の無い押出しシート用メタクリル樹脂組成物を見出した。
すなわち、本発明は、
［１］ メタクリル酸メチル単量体７０〜９９．５ｗｔ％及びメタクリル酸メチルに共重合可能な他のビニル単量体の少なくとも１種で構成される単量体０．５〜３０ｗｔ％からなる共重合体であって、ゲルパーミエーションクロマトグラフィーで測定した重量平均分子量が５万〜１８万である共重合体（１）を９７〜５０ｗｔ％および重量平均分子量が２０万〜５０万である共重合体（２）を３〜５０ｗｔ％含んでなる押出しシート用メタクリル樹脂組成物、
［２］ 該メタクリル樹脂組成物のダイスウェルが１．１５〜１．４０であることを特徴とする上記１に記載の押出しシート用メタクリル樹脂組成物、
［３］ 該共重合体（１）を１００ｗｔ％としたときの該共重合体（１）を構成するメタクリル酸メチル単体量の重量百分率および該共重合体（２）を１００ｗｔ％としたときの該共重合体（２）を構成するメタクリル酸メチル単量体の重量百分率の差が１５ｗｔ％以内であることを特徴とする上記１または２に記載の押出しシート用メタクリル樹脂組成物、
［４］ 上記１〜３のいずれかに記載の押出しシート用メタクリル樹脂組成物を用いて製造したシートの厚みが０．６〜１．５ｍｍであることを特徴とする押出しシート、
［５］ 該シートに片面もしくは両面にハードコート処理、反射防止処理、帯電防止処理のいずれかまたは２種以上の処理を施すことを特徴とする上記４に記載の押出しシート、
［６］ Ｔダイ、押出し機、２本以上のポリッシングロール及び引き取りロールからなる、シート成形機を用いて、上記１〜３のいずれかに記載の押出しシート用メタクリル樹脂組成物を押出し機で溶融混練し、Ｔダイより出た樹脂を２本のポリッシングロール間に供給し、さらに並んだ各ポリッシングロール間に連続的に供給し、引き取りロールで引っ張る押出しシートの製造方法において、最初に樹脂を供給する２本のポリッシングロールの供給側にバンクを形成させ、シート成形時の幅方向のバンクの平均高さが３ｍｍ以下であり高さの変位量が６ｍｍ以下で押出しシート成形することを特徴とするシートの製造方法、
である。
As a result of diligent research to solve these problems, the use of two kinds of methacrylic resins having a molecular weight within a certain range at an appropriate ratio provides excellent bank stability when extruding thin sheets, and there is no appearance defect. The methacrylic resin composition for extrusion sheets was discovered.
That is, the present invention
[1] Copolymer comprising 70 to 99.5 wt% of methyl methacrylate monomer and 0.5 to 30 wt% of monomer composed of at least one other vinyl monomer copolymerizable with methyl methacrylate. Copolymer with a polymer (1) having a weight average molecular weight of 50,000 to 180,000 measured by gel permeation chromatography and 97 to 50 wt% and a weight average molecular weight of 200,000 to 500,000. A methacrylic resin composition for an extruded sheet comprising 3 to 50 wt% of the combined body (2),
[2] The methacrylic resin composition for extruded sheets as described in 1 above, wherein the swell of the methacrylic resin composition is 1.15 to 1.40,
[3] When the copolymer (1) is 100 wt%, the weight percentage of the amount of methyl methacrylate alone constituting the copolymer (1) and the copolymer (2) is 100 wt% 3. The methacrylic resin composition for extruded sheets according to 1 or 2 above, wherein the difference in weight percentage of methyl methacrylate monomers constituting the copolymer (2) is within 15 wt%,
[4] An extruded sheet, wherein the sheet manufactured using the methacrylic resin composition for extruded sheet according to any one of 1 to 3 above has a thickness of 0.6 to 1.5 mm,
[5] The extruded sheet as described in 4 above, wherein the sheet is subjected to any one of hard coating treatment, antireflection treatment, antistatic treatment or two or more treatments on one side or both sides.
[6] Melting the methacrylic resin composition for an extruded sheet according to any one of the above 1 to 3 with an extruder using a sheet molding machine comprising a T die, an extruder, two or more polishing rolls and a take-up roll. In the manufacturing method of the extruded sheet that is kneaded and supplied from the T-die between the two polishing rolls, continuously supplied between the polishing rolls arranged side by side, and pulled by the take-up roll, the resin is supplied first. A bank is formed on the supply side of the two polishing rolls, and the extruded sheet is formed with an average height of the bank in the width direction of the sheet forming of 3 mm or less and a displacement of the height of 6 mm or less. Sheet manufacturing method,
It is.
本発明の組成物及びシートは、薄肉のシート押出時のバンクの安定性に優れ、シート成形性を向上し、そしてシートのハードコート処理や反射防止処理、帯電防止処理での外観不良を防止する効果を有する。 The composition and sheet of the present invention are excellent in bank stability when extruding a thin sheet, improve sheet formability, and prevent appearance defects in the hard coat treatment, antireflection treatment and antistatic treatment of the sheet. Has an effect.
以下本発明をさらに詳細に説明する。本発明における共重合体（１）及び共重合体（２）の組成は、メタクリル酸メチル単量体が７０〜９９．５ｗｔ％含まれる。７０ｗｔ％以上では耐熱性や光学性能が充分であり、９９．５ｗｔ％以下では熱安定性が充分となり好ましい。特に好ましくは、８５〜９９ｗｔ％である。また、共重合体（１）を１００ｗｔ％としたときの共重合体（１）を構成するメタクリル酸メチル単体量の重量百分率と共重合体（２）を１００ｗｔ％としたときの共重合体（２）を構成するメタクリル酸メチル単量体の重量百分率の差が１５ｗｔ％以内が好ましい。１５ｗｔ％以内とすることにより、共重合体（１）と共重合体（２）の屈折率が近くなり得られたメタクリル樹脂組成物の光学特性が維持できて好ましい。より好ましくは、１０ｗｔ％以内である。 The present invention is described in further detail below. The composition of the copolymer (1) and the copolymer (2) in the present invention contains 70 to 99.5 wt% of methyl methacrylate monomer. When it is 70 wt% or more, heat resistance and optical performance are sufficient, and when it is 99.5 wt% or less, thermal stability is sufficient, which is preferable. Most preferably, it is 85-99 wt%. Further, the weight percentage of the amount of methyl methacrylate alone constituting the copolymer (1) when the copolymer (1) is 100 wt% and the copolymer (100) when the copolymer (2) is 100 wt% ( The difference in weight percentage of the methyl methacrylate monomer constituting 2) is preferably within 15 wt%. Within 15 wt%, the optical properties of the methacrylic resin composition obtained by making the refractive indexes of the copolymer (1) and the copolymer (2) close are preferable. More preferably, it is within 10 wt%.
本発明における共重合体（１）及び共重合体（２）に用いられるメタクリル酸メチルと共重合可能な他のビニル単量体としては、アルキル基の数が２〜１８のアルキルメタクリレート、アルキル基の炭素数が２〜１８のアルキルアクリレートの他、アクリル酸やメタクリル酸等のα，β−不飽和酸、マレイン酸、フマル酸、イタコン酸等の不飽和基含有二価カルボン酸及びそれらのアルキルエステル、スチレン、α−メチルスチレン、核置換スチレン等の芳香族ビニル化合物、アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物、無水マレイン酸、マレイミド、Ｎ−置換マレイミド等が挙げられ、これらは、単独或いは２種類以上を併用して用いることが出来る。これらの中でも、耐光性、熱安定性、耐熱性、流動性の観点から、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、ｎ−ブチルアクリレート、ｓ−ブチルアクリレート、２−エチルヘキシルアクリレート等が好ましく用いられ、メチルアクリレート、エチルアクリレート、ｎ−ブチルアクリレートが特に好ましい。 Other vinyl monomers copolymerizable with methyl methacrylate used in the copolymer (1) and copolymer (2) in the present invention include alkyl methacrylates having 2 to 18 alkyl groups, alkyl groups In addition to alkyl acrylates having 2 to 18 carbon atoms, α, β-unsaturated acids such as acrylic acid and methacrylic acid, unsaturated group-containing divalent carboxylic acids such as maleic acid, fumaric acid and itaconic acid, and alkyls thereof. Examples thereof include aromatic vinyl compounds such as esters, styrene, α-methylstyrene, and nucleus-substituted styrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, maleic anhydride, maleimide, N-substituted maleimide, and the like. Alternatively, two or more types can be used in combination. Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferably used from the viewpoints of light resistance, heat stability, heat resistance, and fluidity. , Methyl acrylate, ethyl acrylate, and n-butyl acrylate are particularly preferable.
共重合体（１）の重量平均分子量は、５万〜１８万が良く、共重合体（２）の重量平均分子量は２０万〜５０万が良い。共重合体（１）の重量平均分子量が５万以上では樹脂の機械強度が低下はおこらず好ましい。共重合体（１）の重量平均分子量が１８万以下では、共重合体（２）の分子量差が充分にあるために、押出シート成形したときのバンク安定性が改良される。共重合体（２）の重量平均分子量が２０万以上の場合、やはり共重合体（１）との分子量差が充分となるためにシートを押出したときのバンク安定性が改良される。共重合体（２）の重量平均分子量が５０万以下では、シートを押出したときシート内に未溶融樹脂が発生してシート表面に小さな凹凸形状が発生することもなく好ましい。より好ましくは、共重合体（１）の重量平均分子量が８万〜１４万であり、共重合体２の重量平均分子量が２５万〜５０万である。 The weight average molecular weight of the copolymer (1) is preferably 50,000 to 180,000, and the weight average molecular weight of the copolymer (2) is preferably 200,000 to 500,000. When the weight average molecular weight of the copolymer (1) is 50,000 or more, the mechanical strength of the resin does not decrease, which is preferable. When the weight average molecular weight of the copolymer (1) is 180,000 or less, the difference in molecular weight of the copolymer (2) is sufficient, so that the bank stability is improved when the extruded sheet is formed. When the weight average molecular weight of the copolymer (2) is 200,000 or more, the difference in molecular weight from the copolymer (1) is sufficient, so that the bank stability when the sheet is extruded is improved. When the weight average molecular weight of the copolymer (2) is 500,000 or less, it is preferable that when the sheet is extruded, an unmelted resin is generated in the sheet and a small uneven shape is not generated on the sheet surface. More preferably, the weight average molecular weight of the copolymer (1) is 80,000 to 140,000, and the weight average molecular weight of the copolymer 2 is 250,000 to 500,000.
本発明で測定される重量平均分子量は、ゲルパーミエーションクロマトグラフィーで測定される。あらかじめ、分子量分布が狭く、分子量が既知で試薬として入手可能な標準メタクリル樹脂を用いて、溶出時間と分子量から検量線を作成し、その検量線から各試料の分子量を測定することが出来る。
共重合体（１）の単量体の組成及び重量平均分子量範囲内及び共重合体２の単量体の組成及び重量平均分子量範囲内にある共重合体は、それぞれ１つであっても複数であっても良い。複数の場合例えば、共重合体（１）の組成及び重量平均分子量範囲にある共重合体が２つ以上存在する場合、組成は、平均した単量体組成が共重合体（１）の組成であり、平均した重量平均分子量が共重合体（１）の重量平均分子量である。共重合体（２）の場合も同様である。
The weight average molecular weight measured in the present invention is measured by gel permeation chromatography. Using a standard methacrylic resin having a narrow molecular weight distribution, known molecular weight, and available as a reagent in advance, a calibration curve can be created from the elution time and molecular weight, and the molecular weight of each sample can be measured from the calibration curve.
The copolymer (1) has a monomer composition and a weight average molecular weight range and a copolymer 2 monomer composition and a weight average molecular weight range. It may be. In the case where there are a plurality of copolymers in the range of the weight average molecular weight and the composition of the copolymer (1), for example, the composition is such that the average monomer composition is the composition of the copolymer (1). Yes, the average weight average molecular weight is the weight average molecular weight of the copolymer (1). The same applies to the copolymer (2).
本発明における、共重合体（１）の比率は、９７〜６０ｗｔ％であり、共重合体（２）の比率は３〜４０ｗｔ％である。共重合体（２）の比率が３ｗｔ％以上で効果を発揮し、共重合体（２）の比率が４０ｗｔ％以下では全体の樹脂の流動性が適度なものとなり好ましい。好ましくは共重合体（２）の比率が５〜３５ｗｔ％である。
本発明における共重合体（１）と共重合体（２）で得られるメタクリル樹脂組成物のダイスウェルは、１．１５〜１．４０が好ましい。１．１５以上ではバンクが安定して均一となるが１．４０以下ではバンクが大きくなることによるバンク模様が出ることはない。好ましくは１．１５〜１．３７である。
In the present invention, the ratio of the copolymer (1) is 97 to 60 wt%, and the ratio of the copolymer (2) is 3 to 40 wt%. When the ratio of the copolymer (2) is 3 wt% or more, the effect is exhibited, and when the ratio of the copolymer (2) is 40 wt% or less, the fluidity of the entire resin becomes appropriate. The ratio of the copolymer (2) is preferably 5 to 35 wt%.
The die swell of the methacrylic resin composition obtained by the copolymer (1) and the copolymer (2) in the present invention is preferably from 1.15 to 1.40. At 1.15 or higher, the bank is stable and uniform, but at 1.40 or lower, there is no bank pattern due to the large bank. Preferably it is 1.15 to 1.37.
本発明における共重合体（１）ならびに共重合体（２）の製造方法としては、特に制限は無く懸濁重合、乳化重合、塊状重合、溶液重合等の公知の方法のいずれも可能である。また、共重合体（１）と共重合体（２）は別々に重合し、混合して、シート押出し機で溶融、混練して用いる。もしくは、混合して、押出し機で溶融、混練して、ペレット化し、シート押出し機に用いることも可能である。また、共重合体（１）ならびに共重合体（２）を連続して重合しても良い。例えば、
１．複数の反応器を用いて重合反応を並列して行う段階と、各々の反応器で生成した重合体を溶液状態または溶融状態で均一に混合して、それぞれの比率と分子量を制御して、製造する方法、
２．複数の直列した反応器を用いて重合反応を連続して行い、各々の反応器で生成する比率及び分子量を制御して製造する方法、
３．あらかじめどちらかの共重合体を重合しておき、残りの共重合体を重合するための規定の量の単量体にすでに得られた規定量の共重合体を溶解し、その後重合反応を行うことによって、それぞれの比率、分子量を制御して、製造する方法、
４．あらかじめどちらかの共重合体を重合する途中で、連鎖移動剤及び／又は単量体を後添加することによって最終的に比率及び分子量を制御して、製造する方法、
が挙げられる。
The method for producing the copolymer (1) and the copolymer (2) in the present invention is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, and solution polymerization can be used. The copolymer (1) and the copolymer (2) are separately polymerized, mixed, melted and kneaded with a sheet extruder. Alternatively, they can be mixed, melted and kneaded with an extruder, pelletized, and used in a sheet extruder. Moreover, you may superpose | polymerize a copolymer (1) and a copolymer (2) continuously. For example,
1. A stage where the polymerization reaction is performed in parallel using multiple reactors, and the polymer produced in each reactor is uniformly mixed in a solution state or a molten state, and the ratio and molecular weight of each are controlled to produce how to,
2. A method of continuously performing a polymerization reaction using a plurality of series reactors, and controlling the ratio and molecular weight produced in each reactor,
3. Leave polymerizing either copolymer beforehand, dissolving prescribed amounts of the monomers already obtained the provisions of the copolymer for polymerizing the remainder of the copolymer, performs subsequent polymerization reaction By controlling the ratio and molecular weight of each,
4). In the course of pre-polymerizing either a copolymer, ultimately control the ratio and molecular weight by post-adding a chain transfer agent and / or monomer, a method of manufacturing,
Is mentioned.
本発明における共重合体（１）及び共重合体（２）を製造するための重合開始剤としては、フリーラジカル重合を用いる場合は、ジ−ｔ−ブチルパーオキサイド、ジラウロイルパーオキサイド、ｔ−ブチルパーオキシ２−エチルヘキサノエート、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサンなどのパーオキサイド系や、アゾビスイソブチロニトリル、アゾビスイソバレロニトリル、１，１−アゾビス（１−シクロヘキサンカルボニトリル）などのアゾ系の一般的なラジカル重合開始剤を用いることができ、これらは単独でもあるいは２種類以上を併用しても良い。これらのラジカル開始剤と適当な還元剤とを組み合わせてレドックス系開始剤として実施しても良い。その他にアルキルリチウムなどを用いたアニオン重合法、有機金属錯体を用いた配位重合法、基転移重合法などを用いて製造しても良い。これらの開始剤は、単量体混合物に対して、０．００１〜１ｗｔ％の範囲で用いるのが一般的である。 As a polymerization initiator for producing the copolymer (1) and the copolymer (2) in the present invention, when using free radical polymerization, di-t-butyl peroxide, dilauroyl peroxide, t- Peroxides such as butyl peroxy 2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane And general azo-based radical polymerization initiators such as azobisisobutyronitrile, azobisisovaleronitrile, 1,1-azobis (1-cyclohexanecarbonitrile) can be used, either alone or Two or more types may be used in combination. A combination of these radical initiators and a suitable reducing agent may be used as a redox initiator. In addition, an anionic polymerization method using alkyllithium or the like, a coordination polymerization method using an organometallic complex, a group transfer polymerization method, or the like may be used. These initiators are generally used in the range of 0.001 to 1 wt% with respect to the monomer mixture.
本発明における共重合体（１）及び共重合体（２）の分子量を調整するために、ラジカル重合法で製造する場合には一般的に用いられている連鎖移動剤を使用できる。連鎖移動剤としては、例えばｎ−ブチルメルカプタン、ｎ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、２−エチルヘキシルチオグリコレート、エチレングリコールジチオグリコレート、トリメチロールプロパントリス（チオグリコート）、ペンタエリスリトールテトラキス（チオグリコレート）などのメルカプタン類が好ましく用いられる。一般的に単量体混合物に対して、０．００１〜１ｗｔ％の範囲で用いるのが一般的である。
本発明におけるシートの厚みは、０．６〜１．５ｍｍが好ましい。より好ましくは０．６５〜１．２ｍｍである。
In order to adjust the molecular weight of the copolymer (1) and the copolymer (2) in the present invention, a chain transfer agent that is generally used can be used in the case of producing by radical polymerization. Examples of the chain transfer agent include n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, 2-ethylhexyl thioglycolate, ethylene glycol dithioglycolate, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate). Etc.) are preferably used. Generally, it is generally used in the range of 0.001 to 1 wt% with respect to the monomer mixture.
The thickness of the sheet in the present invention is preferably 0.6 to 1.5 mm. More preferably, it is 0.65-1.2 mm.
本発明におけるメタクリル樹脂組成物は、薄肉シート押出し成形中もしくは押出シート成形後に片面もしくは両面にハードコート処理、反射防止処理、もしくは、帯電防止処理のいずれかもしくは２種以上の処理を施すことが好適である。これらは、一般的に用いられている公知の方法が用いられる。例えばハードコート処理としては、エタノール、トルエン等の溶媒やアクリル系硬化樹脂にシリカや酸化チタン等を添加した液を塗布もしくは液にシートを浸漬する方法や熱硬化性アクリル樹脂や熱硬化性シリコン樹脂を塗布し、硬化する方法や、半硬化性アクリル樹脂シートやシリコン樹脂シートをシートに張り合わせて、硬化する方法等が挙げられる。これらの方法は、シート押出しの工程中もしくは、シート成形後に処理を行うことが出来る。 The methacrylic resin composition in the present invention is preferably subjected to one or more of hard coating treatment, antireflection treatment, or antistatic treatment on one side or both sides during or after the extrusion of the thin sheet. It is. For these, known methods that are generally used are used. For example, as a hard coat treatment, a solvent such as ethanol or toluene, a method in which silica or titanium oxide is added to an acrylic curable resin, or a sheet is immersed in the solution, a thermosetting acrylic resin, or a thermosetting silicon resin The method of apply | coating and hardening | curing, the method of sticking a semi-curable acrylic resin sheet or a silicon resin sheet on a sheet | seat, and hardening are mentioned. These methods can be performed during the sheet extrusion step or after the sheet is formed.
本発明における押出しシート用メタクリル樹脂を製造する際もしくは、押出し機で使用する際に、必要に応じて染料、顔料、ヒンダードフェノール系やリン酸塩等の熱安定剤、ベンゾトリアゾール系、２−ヒドロキシベンゾフェノン系、サリチル酸フェニルエステル系などの紫外線吸収剤、フタル酸エステル系、脂肪酸エステル系、トリメリット酸エステル系、リン酸エステル系、ポリエステル系などの可塑剤、高級脂肪酸、高級脂肪酸エステル、高級脂肪酸のモノ、ジ、またはトリグリセリド系などの離型剤、高級脂肪酸エステル、ポリオレフィン系などの滑剤、ポリエーテル系、ポリエーテルエステル系、ポリエーテルエステルアミド系、アルキルスルフォン酸塩、アルキルベンゼンスルフォン酸塩などの帯電防止剤、リン系、リン／塩素系、リン／臭素系などの難燃剤、反射光のぎらつきを防止するためにメタクリル酸メチル／スチレン共重合体ビーズなどの有機系光拡散剤、硫酸バリウム、酸化チタン、炭酸カルシウム、タルクなどの無機系光拡散剤、補強剤として多段重合で得られるアクリル系ゴム等を使用しても良い。これらの添加剤を配合するときには、公知の方法で実施しうる。例えば、単量体混合物にあらかじめ添加剤を溶解しておき重合する方法や、溶融状態、ビーズ状あるいはペレット状の樹脂に添加剤をミキサー等でドライブレンドし、押出し機を用いて混練、造粒する方法などが挙げられる。 When producing a methacrylic resin for an extruded sheet in the present invention or when using it in an extruder, a heat stabilizer such as a dye, pigment, hindered phenol or phosphate, benzotriazole, 2- UV absorbers such as hydroxybenzophenone and salicylic acid phenyl ester, plasticizers such as phthalate ester, fatty acid ester, trimellitic acid ester, phosphate ester and polyester, higher fatty acid, higher fatty acid ester, higher fatty acid Release agents such as mono-, di-, or triglycerides, lubricants such as higher fatty acid esters and polyolefins, polyethers, polyether esters, polyether ester amides, alkyl sulfonates, alkyl benzene sulfonates, etc. Antistatic agent, phosphorus, phosphorus / salt , Flame retardants such as phosphorus / bromine, organic light diffusing agents such as methyl methacrylate / styrene copolymer beads to prevent glare from reflected light, barium sulfate, titanium oxide, calcium carbonate, talc, etc. Acrylic rubber obtained by multistage polymerization may be used as the inorganic light diffusing agent and reinforcing agent. When these additives are blended, it can be carried out by a known method. For example, a method in which an additive is dissolved in a monomer mixture in advance and polymerized, or an additive is dry-blended with a mixer or the like in a molten state, bead-like or pellet-like resin, and kneaded and granulated using an extruder The method of doing is mentioned.
本発明におけるシートの製造方法は、押出し機を用いた押出し法で製造される。製造する装置としては、Ｔダイ、押出し機、２本以上のポリッシングロール及び引き取りロールを用いることが好ましい。押出し機は単軸でも良いし２軸であっても良い。そのスクリューは混練性を良くするためにフルフライト形状やダルメージがついたものであっても良い。
押出し機で溶融混練した樹脂を安定量供給するために公知のギアポンプを押出し機とＴダイとの間に用いても良い。ポリッシングロールは表裏の表面状態をコントロールするため、３本もしくは４本用いることが好ましい。また、その並び方は、直線でも良いし、シートの引き取りに合わせて曲線状に並べても良い。Ｔダイより出た樹脂を２本のポリッシングロール間に供給し、さらに並んだ各ポリッシングロール間に連続的に供給し、引き取りロールで引っ張る方法が好ましい。このポリッシングロールは鏡面であっても良いし、微細な凹凸模様のついた表面形状を持っていても良い。引き取りロールは２本の鏡面もしくはゴムロールで、シート製造時に、シートの表面温度が用いる樹脂の軟化温度以下のところで、２本の間で引っ張るように回転してシートを引き取る。引き取りロールは、シートに抵抗をかけて引っ張ることが出来るよう表面がゴム状であることがより好ましい。
The sheet manufacturing method in the present invention is manufactured by an extrusion method using an extruder. As an apparatus to manufacture, it is preferable to use a T die, an extruder, two or more polishing rolls, and a take-up roll. The extruder may be uniaxial or biaxial. The screw may have a full flight shape or a dull image to improve kneadability.
A known gear pump may be used between the extruder and the T die in order to supply a stable amount of the resin melt-kneaded by the extruder. It is preferable to use three or four polishing rolls in order to control the surface state of the front and back surfaces. Further, the arrangement may be a straight line, or may be arranged in a curved shape in accordance with the take-up of the sheet. A method of supplying the resin from the T die between two polishing rolls, continuously supplying the resin between the polishing rolls arranged side by side, and pulling with a take-up roll is preferable. The polishing roll may be a mirror surface or may have a surface shape with a fine concavo-convex pattern. The take-up rolls are two mirror surfaces or rubber rolls, and at the time of manufacturing the sheet, the sheet is pulled by rotating to pull between the two when the surface temperature of the sheet is equal to or lower than the softening temperature of the resin used. It is more preferable that the surface of the take-up roll is rubbery so that the sheet can be pulled with resistance.
本発明における押出しシートの製造方法としては、Ｔダイから出た樹脂を、最初に樹脂を供給する２本のポリッシングロールの供給側にバンクを形成させることが好ましい。バンクのシート成形時の幅方向のバンクの平均高さは３ｍｍ以下が好ましい。バンクの平均高さが３ｍｍ以下ではシートを製造したときにバンクの跡が縞状に残るバンク模様が形成されてることもなく好ましい。バンクが形成されないと、ポリッシングロール表面がシート表面に反映されない表面ムラが発生し、板厚もムラが生じるため好ましくない。より好ましくは２．５ｍｍ以下である。
本発明におけるバンクの高さの変位量は６ｍｍ以下が好ましい。バンクの高さの変位量とは、バンクを形成したときの各時間トータルでの高さの最大値と高さの最小値の差である。６ｍｍ以下ではバンク模様と表面不良の両方が交互に出ることもなく好ましい。好ましくは５ｍｍ以下であり、より好ましくは４ｍｍ以下である。バンクの平均高さは、シート製造中にポリッシングロール間隔を大きくあけて、形成していたバンクの高さを幅方向で調べ、さらに３０分ごともしくは一定時間ごとのそれを実施し、バンク高さの平均値として求めることが出来る。また高さの変位量は、バンクの幅方向に測定したときのトータルの高さの最大値と最小値の差として求めることが出来る。
As a method for producing an extruded sheet in the present invention, it is preferable to form a bank on the supply side of the two polishing rolls that first supply the resin from the T-die. The average height of the bank in the width direction when forming the bank sheet is preferably 3 mm or less. When the average height of the banks is 3 mm or less, it is preferable that the bank pattern in which the traces of the banks remain in a striped pattern is not formed when the sheet is manufactured. If the bank is not formed, surface unevenness that does not reflect the surface of the polishing roll on the sheet surface occurs, and the plate thickness also becomes uneven, which is not preferable. More preferably, it is 2.5 mm or less.
The amount of displacement of the bank height in the present invention is preferably 6 mm or less. The amount of bank height displacement is the difference between the maximum height value and the minimum height value for each time when the bank is formed. If it is 6 mm or less, both bank patterns and surface defects do not appear alternately, which is preferable. Preferably it is 5 mm or less, More preferably, it is 4 mm or less. The average height of the bank is determined by widening the polishing roll interval during sheet manufacture, checking the height of the formed bank in the width direction, and performing it every 30 minutes or every fixed time. It can be obtained as an average value of. The amount of displacement of the height can be obtained as a difference between the maximum value and the minimum value of the total height when measured in the bank width direction.
以下に実施例、比較例を用いて本発明をさらに具体的に説明する。単位について部で表示しているところは、重量部を表す。
１．メタクリル樹脂の重量平均分子量の測定
トーソー株式会社製ゲルパーミエーションクロマトグラフィー（ＨＬＣ−８１２０＋８０２０）を用い、カラムに東ソー製ＴＳＫスーパーＨＨ−Ｍ（２本）＋スーパーＨ２５００（１本）を直列に並べ検出器にＲＩを用いた。測定試料は、０．０２ｇのメタクリル樹脂を２０ｃｃのＴＨＦ溶媒に溶解し、注入量１０ｍｌ、展開流量０．３ｍｌ／ｍｉｎで溶出時間と、強度を測定した。ジーエルサイエンス製の単分散の重量平均分子量が既知なメタクリル樹脂を標準試料とした検量線を元に重量平均分子量を求めた。混合物の重量平均分子量の測定は、どれか単体の重量平均分子量を元に混合物の重量平均分子量から引くことで、混合物の残りの単体の重量平均分子量及び比率を求めることにした。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The unit displayed in parts represents parts by weight.
1. Measurement of weight average molecular weight of methacrylic resin Using Tosoh Corporation gel permeation chromatography (HLC-8120 + 8020), Tosoh's TSK Super HH-M (2) + Super H2500 (1) are aligned and detected in series. RI was used for the vessel. As a measurement sample, 0.02 g of methacrylic resin was dissolved in 20 cc of a THF solvent, and the elution time and strength were measured at an injection amount of 10 ml and a development flow rate of 0.3 ml / min. The weight average molecular weight was determined based on a calibration curve using a monodispersed methacrylic resin with a known monodispersed weight average molecular weight as a standard sample. The weight average molecular weight of the mixture was determined by subtracting the weight average molecular weight of any single substance from the weight average molecular weight of the mixture to obtain the weight average molecular weight and the ratio of the remaining simple substance of the mixture.
２．ダイスウェルの測定
東洋精機製メルトインデクサＦ−Ｂ０１を用いて、ＩＳＯ １１３３ ｃｏｎｄ１３の条件に従って、２３０℃、荷重３．８ｋｇの条件下で出てきたストランド径の最大値をノギスもしくはマイクロメーターで測定し、オリフィスの径２．０９ｍｍで割った値をダイスウェル値とする。
2. Measurement of die swell Using a Toyo Seiki melt indexer F-B01, according to the conditions of ISO 1133 cond13, the maximum value of the strand diameter that came out under the conditions of 230 ° C. and a load of 3.8 kg was measured with a caliper or a micrometer. The value divided by the orifice diameter of 2.09 mm is taken as the die swell value.
３．シート押出し成形性の評価
５０ｍｍφの押出し機にギアポンプとＴダイのついた押出し機と３本の縦に並んだポリッシングロールとその先に引き取りロールを組み合わせたシート押出し機を用い、押出し機温度２５０℃Ｔダイ温度２５５℃で、Ｔダイより溶融した樹脂を下から１本目と２本目のポリッシングロール間に入れて、２本目に沿わすようにシートを持っていき、２本目と３本目の間に供給し、３本目のポリッシングロールに沿わすようにシートを供給し、５ｍ先に設置した引き取りロールに供給、シート引き取りを行い、０．９ｍｍ厚のシートを作成した。シートの幅は３０ｃｍである。シート長６０ｃｍごとにシートを切り出した。
シートを２時間連続で成形し、３０分ごとに３本のポリッシングロールの間隔を空け、１本目と２本目に生成するバンクの大きさとシート幅３０ｍｍのうちシート幅の中心をセンターとする２０ｍｍにおける幅内でのバンクの高さを測定し、各サンプル間を含めバンク平均高さと、バンク高さの最大値と最小値の差から幅方向の変位量とを得た。また、４つのバンクサンプルの形状を見比べ、経時変化の有無を評価した。
3. Evaluation of sheet extrudability Using a 50 mmφ extruder, a sheet extruder in which an extruder with a gear pump and a T-die, three vertically aligned polishing rolls and a take-off roll are combined, and an extruder temperature of 250 ° C. At the T die temperature of 255 ° C., the resin melted from the T die is placed between the first and second polishing rolls from below, and the sheet is held along the second, and between the second and third Then, the sheet was supplied along the third polishing roll, supplied to the take-up roll installed 5 m ahead, and the sheet was taken out to prepare a 0.9 mm thick sheet. The width of the sheet is 30 cm. Sheets were cut out every 60 cm sheet length.
The sheet is formed continuously for 2 hours, and three polishing rolls are spaced every 30 minutes, and the size of the bank generated in the first and second sheets and the sheet width of 30 mm is 20 mm centered on the center of the sheet width. The height of the bank within the width was measured, and the average bank height including between samples and the displacement in the width direction were obtained from the difference between the maximum value and the minimum value of the bank height. Moreover, the shape of four bank samples was compared and the presence or absence of a change with time was evaluated.
４．シート外観の評価
蛍光灯がついている部屋で、蛍光灯がシートに写りこむ（反射する）ようにし、シートを斜めから見て蛍光灯の像がゆがむ個所で凹凸の有無を評価する。
次にシートの下から、蛍光灯で照らして蛍光灯の光散乱する部分がないかどうかを評価した。シートを５０枚評価し、蛍光灯がはっきり写って蛍光灯の光が散乱しないシートが５０枚中４５枚以上の場合を良とし、４５枚より少ない場合の場合を悪とした。
4). Evaluation of sheet appearance In a room with a fluorescent lamp, the fluorescent lamp is reflected (reflected) on the sheet, and the presence or absence of unevenness is evaluated at a position where the fluorescent lamp image is distorted when the sheet is viewed from an oblique direction.
Next, it was evaluated from the bottom of the sheet whether there was any portion of the fluorescent light that was scattered by illuminating with a fluorescent light. Fifty sheets were evaluated, and the case where 45 or more sheets out of 50 sheets in which the fluorescent lamp was clearly visible and the light from the fluorescent lamp was not scattered was considered good, and the case where the number was less than 45 was regarded as bad.
５．ハードコート処理評価シートの外観評価
得られたシートのうちシート外観で問題なかったシートについて、市販のＪＰＣ製ハードコート液ＴＫＨ−３６Ａに得られたシートを浸漬し、引き上げて紫外線を照射し、ハードコート層をシート表面に形成した。その後４．と同等の外観の評価を行い、シートに凹凸がないか、蛍光灯がはっきり写り、蛍光灯の光が散乱しないかどうか、蛍光灯でシートが光って見える処理によるクラックが発生していないかを評価する。シート外観と同じく、シート５０枚を評価し、シート外観が良好であるものが５０枚中４５枚以上の場合を良とし、４５枚より少ない場合を悪とした。
5. Appearance evaluation of hard coat treatment evaluation sheet Of the obtained sheets, there was no problem in the sheet appearance, the sheet obtained in a commercially available JPC hard coat liquid TKH-36A was immersed, pulled up and irradiated with ultraviolet rays, hard A coating layer was formed on the sheet surface. 4. Evaluate the appearance equivalent to that of the sheet, check whether the sheet is uneven, whether the fluorescent light is clearly visible, the light from the fluorescent light is not scattered, and whether there is a crack due to the process in which the sheet appears to shine with the fluorescent light. evaluate. As with the sheet appearance, 50 sheets were evaluated, and the case where the sheet appearance was good was 45 or more out of 50 sheets, and the case where there were less than 45 sheets was regarded as bad.
［実施例１］
６０Ｌの反応器にメタクリル酸メチル９４ｗｔ％及びアクリル酸メチル６ｗｔ％の比率でこれらの合計を７０部と、ラウリルパーオキサイド０．１７５部、ｎ−オクチルメルカプタン０．１９３部（以上が共重合体（１）の原料）、脱イオン水２００部、三リン酸カルシウム０．５部、炭酸カルシウム０．３部、ラウリル硫酸ナトリウム０．００３部を投入し攪拌混合し、反応器の反応温度を８０℃で１５０分懸濁重合し、重合物を少量を抜き取った。ゲルパーミエーションクロマトグラフィーで測定し、重量平均分子量１０万の共重合体（１）であることを確認した。その１０分後に共重合体（２）の原料であるメタクリル酸メチル９４ｗｔ％及びアクリル酸メチル６ｗｔ％の比率でこれらの合計を３０部と、ラウリルパ−オキサイド０．００６部、ｎ−オクチルメルカプタン０．０１２部を反応器に投入し、引き続き８０℃で９０分懸濁重合し、続いて９２℃で６０分熟成し、重合反応を実質終了し、次に５０℃まで冷却して鉱酸を投入し、洗浄脱水乾燥処理し、ビーズ状メタクリル樹脂（共重合体１と共重合体２の混合物）を得た。このビーズ状ポリマーをゲルパーミエーションクロマトグラフィーで測定し、表１の結果の通り、先の共重合体（１）の重量平均分子量の結果を用いて計算し、重量平均分子量が１０万で比率が７２ｗｔ％の共重合体（１）と重量平均分子量が４６万で比率が２８ｗｔ％の共重合体（２）の混合物であることを確認した。このビーズ状メタクリル樹脂を２軸ベント付押出機に供給し、温度２４５〜２５０℃、ベント圧力６５０〜７５０ｍｍＨｇで押出してペレタイズ化し、表１の樹脂１を得た。この樹脂１を用いて、シート押出し成形を行い評価した。その結果を表２に示す。
[Example 1]
In a 60 L reactor, 70 parts of these in a ratio of 94 wt% methyl methacrylate and 6 wt% methyl acrylate, 0.175 parts lauryl peroxide, 0.193 parts n-octyl mercaptan (the above is a copolymer ( 1) raw material), 200 parts of deionized water, 0.5 part of calcium triphosphate, 0.3 part of calcium carbonate and 0.003 part of sodium lauryl sulfate are added and mixed by stirring. The reaction temperature of the reactor is 150 ° C. at 150 ° C. Suspension polymerization was carried out, and a small amount of the polymer was taken out. It was measured by gel permeation chromatography and confirmed to be a copolymer (1) having a weight average molecular weight of 100,000. Ten minutes later, 30 parts of these were in a ratio of 94 wt% of methyl methacrylate and 6 wt% of methyl acrylate as raw materials for the copolymer (2), 0.006 parts of lauryl peroxide, 0. 0 parts of n-octyl mercaptan. 012 parts are charged into the reactor, followed by suspension polymerization at 80 ° C. for 90 minutes, followed by aging at 92 ° C. for 60 minutes to substantially complete the polymerization reaction, then cooled to 50 ° C. and charged with mineral acid. Then, it was washed and dehydrated and dried to obtain a bead-like methacrylic resin (mixture of copolymer 1 and copolymer 2). This bead-shaped polymer was measured by gel permeation chromatography, and as shown in Table 1, calculated using the result of the weight average molecular weight of the previous copolymer (1), the weight average molecular weight was 100,000 and the ratio was It was confirmed that this was a mixture of 72 wt% copolymer (1) and copolymer (2) having a weight average molecular weight of 460,000 and a ratio of 28 wt%. This bead-like methacrylic resin was supplied to an extruder equipped with a biaxial vent and extruded at a temperature of 245 to 250 ° C. and a vent pressure of 650 to 750 mmHg to be pelletized to obtain a resin 1 shown in Table 1. Using this resin 1, sheet extrusion molding was performed and evaluated. The results are shown in Table 2.
［実施例２、３］
共重合体（２）の原料のｎ−オクチルメルカプタンの量を樹脂２では０．０２２部、樹脂３では０．０１６５部とする以外は樹脂１と同様にして、メタクリル樹脂を得た。共重合体（１、２）の単量体組成ならびに各重量平均分子量の結果を表１に示す。それぞれの樹脂を用いて、シート押出し成形を行い評価した。その結果を表２に示す。
[Examples 2 and 3]
A methacrylic resin was obtained in the same manner as in the resin 1 except that the amount of n-octyl mercaptan as a raw material for the copolymer (2) was 0.022 part for the resin 2 and 0.0165 part for the resin 3. Table 1 shows the monomer composition of the copolymer (1, 2) and the results of the respective weight average molecular weights. Using each resin, sheet extrusion molding was performed and evaluated. The results are shown in Table 2.
［比較例１］
６０Ｌの反応器にメタクリル酸メチル９８ｗｔ％及びアクリル酸メチル２ｗｔ％の比率でこれらの合計を１００部と、ラウリルパ−オキサイド０．２５部、ｎ−オクチルメルカプタン０．２７５部、脱イオン水２００部、三リン酸カルシウム０．５部、炭酸カルシウム０．３部、ラウリル硫酸ナトリウム０．００３部を投入し攪拌混合し、反応器の反応温度を８０℃で１５０分懸濁重合し、続いて９２℃で６０分熟成し、重合反応を実質終了し、次に５０℃まで冷却して鉱酸を投入し、洗浄脱水乾燥処理し、ビーズ状メタクリル樹脂を得た。このビーズ状ポリマーをゲルパーミエーションクロマトグラフィーで測定し、樹脂１と同様にペレタイズ化し、表１にある組成の樹脂４を得た。
この樹脂４を用いてシート押出し成形を行い評価した。その結果を表２に示す。
[Comparative Example 1]
In a 60 L reactor, 100 parts of these in a ratio of 98 wt% methyl methacrylate and 2 wt% methyl acrylate, 0.25 parts lauryl peroxide, 0.275 parts n-octyl mercaptan, 200 parts deionized water, 0.5 parts of calcium triphosphate, 0.3 part of calcium carbonate and 0.003 part of sodium lauryl sulfate are added and mixed by stirring. Suspension polymerization is carried out at 80 ° C. for 150 minutes, followed by 60 ° C. at 92 ° C. for 60 minutes. After completion of the polymerization reaction, the polymerization reaction was substantially completed, and then cooled to 50 ° C., a mineral acid was added, washed, dehydrated and dried to obtain a bead-like methacrylic resin. This bead polymer was measured by gel permeation chromatography and pelletized in the same manner as in Resin 1 to obtain Resin 4 having the composition shown in Table 1.
The resin 4 was used for sheet extrusion molding and evaluated. The results are shown in Table 2.
［実施例４］
共重合体１である樹脂４と、さらに共重合体１と共重合体２の混合物である樹脂１とを、樹脂１を１，樹脂４を２の割合で混合し、２軸ベント付押出機に供給して実施例１と同様にペレタイズ化した。表1に示す平均の単量体の組成と重量平均分子量を持つ共重合体１および共重合体２の混合物である樹脂５を得た。この樹脂５を用いてシート押出し成形を行い評価した。その結果を表２に示す。
[Example 4]
Resin 4 which is copolymer 1 and resin 1 which is a mixture of copolymer 1 and copolymer 2 are mixed with resin 1 and resin 4 at a ratio of 2, and an extruder with a twin screw vent And pelletized as in Example 1. Resin 5 which is a mixture of copolymer 1 and copolymer 2 having the average monomer composition and weight average molecular weight shown in Table 1 was obtained. Using this resin 5, sheet extrusion molding was performed and evaluated. The results are shown in Table 2.
［実施例５］
共重合体（１）の原料であるメタクリル酸メチルを９８ｗｔ％及びアクリル酸メチル２ｗｔ％の比率でこれらの合計を１００部と、ラウリルパ−オキサイド０．２５部、ｎ−オクチルメルカプタン０．２７５部とした以外は樹脂４と同様にして重合を行い、重量平均分子量１０万の共重合体（１）を得た。得られたビーズ状ポリマーはゲルパーミエーションクロマトグラフィーで測定したところ重量平均分子量１０万であった。
共重合体（２）の原料であるメタクリル酸メチルを８７ｗｔ％及びアクリル酸メチル１３ｗｔ％の比率でこれらの合計を１００部と、ラウリルパ−オキサイド０．１０部、ｎ−オクチルメルカプタン０．０４部とした以外は樹脂４と同様にして得られたビーズ状ポリマーをゲルパーミエーションクロマトグラフィーで測定し、重量平均分子量５０万の共重合体（２）を得た。共重合体（１）を９０ｗｔ％、共重合体（２）を１０ｗｔ％の割合で混合し、樹脂１と同様に２軸ベント付押出機を用いて押出し表１にある樹脂６を得た。この樹脂６を用いてシート押出し成形を行い評価した。その結果を表２に示す。
[Example 5]
100 parts by weight of methyl methacrylate as a raw material of the copolymer (1) at a ratio of 98 wt% and methyl acrylate 2 wt%, 0.25 parts of lauryl peroxide, 0.275 parts of n-octyl mercaptan, Except for the above, polymerization was carried out in the same manner as in Resin 4 to obtain a copolymer (1) having a weight average molecular weight of 100,000. The obtained bead polymer had a weight average molecular weight of 100,000 as measured by gel permeation chromatography.
100 parts of methyl methacrylate as a raw material of the copolymer (2) at a ratio of 87 wt% and methyl acrylate 13 wt%, 0.10 parts of lauryl peroxide, 0.04 parts of n-octyl mercaptan, Except that, the bead polymer obtained in the same manner as in Resin 4 was measured by gel permeation chromatography to obtain a copolymer (2) having a weight average molecular weight of 500,000. 90 wt% of copolymer (1) and 10 wt% of copolymer (2) were mixed and extruded using a biaxial vented extruder in the same manner as resin 1 to obtain resin 6 in Table 1. Using this resin 6, sheet extrusion molding was performed and evaluated. The results are shown in Table 2.
［比較例２］
共重合体（２）の原料であるメタクリル酸メチルを６０ｗｔ％、アクリル酸ブチル４０ｗｔ％の比率でこれらの合計を１００部と、ラウリルパーオキサイド０．１０部、ｎ−オクチルメルカプタン０．００３５部とする以外は樹脂４と同様に重合した。得られたビーズ状ポリマーを７ｗｔ％そして樹脂５を９３ｗｔ％の割合で混合し、ベント付押出し機で押出し表１にある樹脂７を得た。この樹脂７を用いてシート押出し成形を行い評価した。その結果を表２に示す。
実施例１〜５ともシート押出し成形時中のバンク形状はフラットに近い形状をして、その時間における変化もなく好ましい。比較例１では、バンク形状がフラットなものもあればシート中央付近のバンクが小さいものもあり経時変化が非常に大きく、結果として、平均高さ、変位量がともに大きく良くない。比較例２では、シート中央のバンクが大きい状態で経時的には安定して好ましいが、バンクはフラットではなく、平均高さと変位量が大きくシート成形時のバンク形状としては良くない。これらのバンク形状により、シート外観を評価したときには、実施例１〜５は、外観不良が無く良いシートが得られているが、比較例１では、バンクが小さかった中央付近で、ロールの鏡面が転写されずに蛍光灯が散乱して見える鏡面性の低いシートが５０枚中１２枚発生する不具合が生じた。比較例２は、シート中央部に蛍光灯がきちんと写る部分と散乱して見える部分とが見え、これは鏡面と鏡面でない部分が繰り返し発生するバンク模様によるもので、不良が５０枚中１７枚発生した。ハードコート処理したシートの外観も実施例１〜５では良好な結果となったが、比較例２では、ハードコート処理した後に共重合体２の未溶融樹脂が原因である微細な凹凸の不良による蛍光灯のゆがみが発生し、また、全体に蛍光灯が散乱して見える不良のシートが５０枚中２１枚見られて、良くなかった。
[Comparative Example 2]
100 parts of these in a ratio of 60% by weight of methyl methacrylate as a raw material of the copolymer (2) and 40% by weight of butyl acrylate, 0.10 parts of lauryl peroxide, 0.0035 parts of n-octyl mercaptan Polymerization was conducted in the same manner as Resin 4 except that. The obtained bead polymer was mixed at a ratio of 7 wt% and resin 5 at a ratio of 93 wt%, and extruded with a vented extruder to obtain resin 7 in Table 1. Using this resin 7, sheet extrusion molding was performed and evaluated. The results are shown in Table 2.
In all of Examples 1 to 5, the bank shape during sheet extrusion molding is almost flat, and there is no change in the time. In Comparative Example 1, the bank shape is flat and the bank near the center of the sheet is small, and the change over time is very large. As a result, both the average height and the displacement amount are not large and good. In Comparative Example 2, it is preferable that the bank at the center of the sheet is large and stable over time. However, the bank is not flat, and the average height and displacement are large, so that the bank shape during sheet molding is not good. When the sheet appearance was evaluated by these bank shapes, Examples 1 to 5 were good sheets with no appearance defects. In Comparative Example 1, the mirror surface of the roll was near the center where the bank was small. There was a problem that 12 sheets of low specularity in which the fluorescent lamp was scattered without being transferred were generated out of 50 sheets. In Comparative Example 2, a portion where the fluorescent lamp is properly reflected and a portion that appears to be scattered can be seen in the center of the sheet. This is due to a bank pattern in which a mirror surface and a portion that is not a mirror surface are repeatedly generated. did. The appearance of the hard-coated sheet was also good in Examples 1 to 5, but in Comparative Example 2, it was due to the fine irregularities caused by the unmelted resin of the copolymer 2 after the hard-coating process. The fluorescent lamps were distorted, and 21 of the 50 defective sheets that the fluorescent lamps scattered throughout were seen, which was not good.
本発明の押出しシート用メタクリル樹脂組成物を用いることにより、外観品質が非常に重要な、携帯電話、液晶モニター、液晶テレビ等の表示（装置）窓や、表示装置の前面板や絵画等の額や、外光を取り入れる窓、表示用看板、カーポートの屋根等のエクステリア、展示品の棚、車両用光学部品等において生産性を向上しながら、外観品質のよい薄肉シートを提供することが可能となる。 By using the methacrylic resin composition for extruded sheets of the present invention, appearance quality is very important. Display (device) windows of mobile phones, liquid crystal monitors, liquid crystal televisions, etc. It is possible to provide thin sheets with good appearance quality while improving productivity in exterior windows, display signs, carport roofs, exhibition shelves, vehicle optical components, etc. It becomes.
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