CN104520377B - Resin combination, the manufacture method of resin combination and formed body - Google Patents
Resin combination, the manufacture method of resin combination and formed body Download PDFInfo
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- CN104520377B CN104520377B CN201380041443.9A CN201380041443A CN104520377B CN 104520377 B CN104520377 B CN 104520377B CN 201380041443 A CN201380041443 A CN 201380041443A CN 104520377 B CN104520377 B CN 104520377B
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- 239000011347 resin Substances 0.000 title claims abstract description 131
- 229920005989 resin Polymers 0.000 title claims abstract description 130
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000004417 polycarbonate Substances 0.000 claims abstract description 53
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 49
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 45
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 39
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 21
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 230000000379 polymerizing Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 29
- -1 bicyclo-pentyl ester Chemical class 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 22
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 4
- 238000011068 load Methods 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 69
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000002194 synthesizing Effects 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000001294 propane Substances 0.000 description 6
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical group CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 description 4
- 229940106691 bisphenol A Drugs 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-Dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N O-Cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 **[N+]([N+]([N-])N*)O Chemical compound **[N+]([N+]([N-])N*)O 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N 2-cyanopropene-1 Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N 4,4'-Biphenol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N 4,4'-cyclohexane-1,1-diyldiphenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- ASURBSPIYIISGI-UHFFFAOYSA-N 4-(3,3,5-trimethylcyclohexyl)phenol Chemical class C1C(C)(C)CC(C)CC1C1=CC=C(O)C=C1 ASURBSPIYIISGI-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- AWPROQFCCQOROZ-UHFFFAOYSA-N 4-(4-methylpentyl)phenol Chemical compound CC(C)CCCC1=CC=C(O)C=C1 AWPROQFCCQOROZ-UHFFFAOYSA-N 0.000 description 1
- TZEASLWZHZAIQO-UHFFFAOYSA-N 4-(4-propan-2-ylcyclohexyl)phenol Chemical compound C1CC(C(C)C)CCC1C1=CC=C(O)C=C1 TZEASLWZHZAIQO-UHFFFAOYSA-N 0.000 description 1
- GIXNHONPKYUROG-UHFFFAOYSA-N 4-(9H-fluoren-1-yl)phenol Chemical class C1=CC(O)=CC=C1C1=CC=CC2=C1CC1=CC=CC=C12 GIXNHONPKYUROG-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-Ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DUJMVKJJUANUMQ-UHFFFAOYSA-N 4-methylpentanenitrile Chemical compound CC(C)CCC#N DUJMVKJJUANUMQ-UHFFFAOYSA-N 0.000 description 1
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- 206010055000 Bromhidrosis Diseases 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N Butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N Diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M Sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N Tert-Butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010192 crystallographic characterization Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003014 reinforcing Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The resin combination of the present invention contains acrylic resin with the ratio of 50～95 weight %, and contain polycarbonate-based resin with the ratio of 5～50 weight %, described acrylic resin is for containing making to comprise methyl methacrylate 50～95 weight %, (methyl) acrylate 5～50 weight % shown in formula (I), the copolymer obtained with the polymerizing monomer components of monofunctional monomer 0.1～20 weight % beyond these, and there is the resin of the viscosity-average molecular weight of 80000～300000, described polycarbonate-based resin has the viscosity-average molecular weight of 16000～25000, and in temperature 240 DEG C and shear rate 60sec‑1Under the conditions of the melt viscosity (η of acrylic resinA) and in temperature 240 DEG C and shear rate 60sec‑1Under the conditions of the melt viscosity (η of MerlonB) ratio (ηA/ηB) it is 0.40～3.00, meet formula (a).
Description
Technical field
The present invention relates to resin combination and the manufacture method thereof with the transparency of excellence.It is additionally related to this resin group
The formed body that compound shapes and obtains.
Background technology
Generally, polycarbonate-based resin has the high-temperature stability of excellence, dimensional stability, resistance to impact, rigidity, transparent
Property etc..But, scratch resistance and long-term UV patience are insufficient, it may have the shortcoming that stress birfringence occurs.On the other hand it is known that
The acrylic resins such as polymethyl methacrylate have excellence the transparency, case hardness, UV patience, weatherability, chemistry resistance to
Property etc..But, the dimensional stability of acrylic resin, resistance to impact, Heat pretreatment etc. are insufficient.
Therefore, for the mixture of polycarbonate-based resin Yu acrylic resin, expect to make up mutually resin each institute
Have the disadvantage that there is the character that can be used in various uses.But, generally, polycarbonate-based resin and acrylic resin
Mixture opaque, there is the problem of purposes being not used to require the transparency.Therefore, in order to obtain polycarbonate-based resin
Transparent mixture with acrylic resin, it is proposed that various methods.
For example, Patent Document 1 discloses following method: by aromatic copolycarbonate and whole methyl methacrylate
At least the 50% of ester units belongs to the syndiotaxy polymethyl methacrylate mixing of syndiotaxy configuration.But, pass through the party
The transparency of the mixture that method obtains may not be abundant.
It addition, Patent Document 2 discloses following melting mixing method: will comprise Merlon 97～60 weight % and
The resin trace type high shear forming maker of polymethyl methacrylate 3～40 weight % carries out melting mixing.But, logical
The transparency crossing the melting mixing thing that the method obtains also may not be abundant.
It addition, Patent Document 3 discloses following copolymer mixture: comprise aromatic copolycarbonate and by methyl
Acrylic acid methyl ester. and cyclohexyl methacrylate copolymerization and the methacrylate copolymer that obtains.But, this copolymer mixes
The transparency of thing also may not be abundant.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 6-128475 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2009-196196 publication
Patent documentation 3: Japanese Unexamined Patent Publication 1-1749 publication
Summary of the invention
Invent problem to be solved
The problem of the present invention is to provide the resin combination of the transparency with excellence.
Solve the means of problem
The present invention relates to following (1)～(6).
(1) a kind of resin combination, it is to contain acrylic resin and with 5～50 with the ratio of 50～95 weight %
The ratio of weight % contains the resin combination of polycarbonate-based resin, wherein,
Described acrylic resin contains to be made to comprise (the first shown in methyl methacrylate 50～95 weight %, lower formula (I)
Base) acrylate 5～50 weight % and the polymerizing monomer components of the monofunctional monomer beyond these 0.1～20 weight % and obtain
The copolymer arrived, and be the resin of the viscosity-average molecular weight with 80000～300000,
(in formula (I), R1Represent hydrogen atom or methyl, R2Represent alkyl, cycloalkyl or the alkyl-cycloalk being substituted by cycloalkyl
Base.)
Described polycarbonate-based resin has the viscosity-average molecular weight of 16000～25000, and in temperature 240 DEG C and shearing speed
Degree 60sec-1Under the conditions of the melt viscosity (η of acrylic resinA) and in temperature 240 DEG C and shear rate 60sec-1Under the conditions of
The melt viscosity (η of MerlonB) ratio (ηA/ηB) it is 0.40～3.00,
Meet following formula (a),
2≤(MVRPC×Wa×Wa)/(Wb×Wb)≤50 (a)
(in formula (a), MVRPCThe melt volume-flow rate of the polycarbonate-based resin at representing 300 DEG C, WaRepresent described
Weight % of (methyl) acrylate shown in formula (I) in monomer component, WbRepresent in resin combination is polycarbonate-based
Weight % of resin.).
(2) resin combination as described in (1), wherein, (methyl) acrylate shown in described formula (I) is selected from methyl
At least one ester in cyclohexyl acrylate, cyclohexyl acrylate, methacrylic acid bicyclo-pentyl ester and acrylic acid bicyclo-pentyl ester.
(3) resin combination as described in (1), wherein, described monofunctional monomer is selected from acrylic acid methyl ester., acrylic acid second
At least one monomer in ester and butyl acrylate.
(4) a kind of method of resin combination manufactured according to any one of above-mentioned (1)～(3), comprising: to comprising third
The resin compound of olefin(e) acid system resin and polycarbonate-based resin carries out the operation of melting mixing.
(5) method as described in (4), wherein, described melting mixing is the temperature and 10～500sec of 180～320 DEG C-1
Shear rate under carry out.
(6) a kind of formed body, it obtains by above-mentioned (1) being shaped to the resin combination according to any one of (3).
Invention effect
According to the present invention, the resin combination with the transparency of excellence can be obtained, by this resin combination is shaped,
Thus can obtain the formed body with the transparency of excellence.It addition, the formed body of the resin combination of the present invention and the present invention is also
There is the mechanical strength of excellence.Therefore, the resin combination of the present invention and the formed body of the present invention are suitable for electron-optical material
Material, covering material, resin finish (ゲ レ mono-ジ Application ゲ) material etc..
Detailed description of the invention
The resin combination of the present invention contains specific acrylic resin and specific polycarbonate-based resin.
<acrylic resin>
The acrylic resin used in the present invention is for containing making to comprise methyl methacrylate 50～95 weight %, following formula
(I) (methyl) acrylate 5～50 weight % shown in and the monomer of the monofunctional monomer beyond these 0.1～20 weight %
The copolymer that composition is polymerized and obtains, and there is the resin of the viscosity-average molecular weight of 80000～300000,
(in formula (I), R1Represent hydrogen atom or methyl, R2Represent alkyl, cycloalkyl or the alkyl-cycloalk being substituted by cycloalkyl
Base).
It should be noted that in this manual, term " (methyl) acrylic acid " expression " acrylic acid " or " metering system
Acid ".
The R of formula (I)2Represent alkyl, cycloalkyl, alkyl-cycloalkyl or the bicyclopentyl being substituted by cycloalkyl.Wherein, preferably
Cycloalkyl or bicyclopentyl.
As cycloalkyl, the preferably cycloalkyl of carbon number 5～12.As the cycloalkyl of carbon number 5～12, can enumerate
Such as: cyclopenta, cyclohexyl, suberyl, ring octyl group, cyclo-dodecyl etc..Wherein, preferred cyclohexyl.
As alkyl, the preferably alkyl of carbon number 1～4.As the alkyl of carbon number 1～4, can enumerate such as: first
Base, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group etc..
As the alkyl being substituted by cycloalkyl, can enumerate such as: at least 1 H (hydrogen atom) is by above-mentioned carbon number 5～12
The methyl of cycloalkyl substituted, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group etc..
As alkyl-cycloalkyl, can enumerate such as: the ring penta that at least 1 H is replaced by the alkyl of above-mentioned carbon number 1～4
Base, cyclohexyl, suberyl, ring octyl group, cyclo-dodecyl etc..
As (methyl) acrylate shown in formula (I), it is preferably selected from cyclohexyl methacrylate, acrylate
Ester, methacrylic acid bicyclo-pentyl ester (methacrylic acid dicyclopentanyl) and acrylic acid bicyclo-pentyl ester
At least one ester in (acrylic acid dicyclopentanyl), more preferably cyclohexyl methacrylate.
As the monofunctional monomer beyond (methyl) acrylate shown in methyl methacrylate and formula (I), can enumerate
Such as: (methyl) alkyl acrylate beyond (methyl) acrylate shown in methyl methacrylate and formula (I), thiazolinyl cyanogen
Compound (such as, acrylonitrile, methacrylonitrile etc.), acrylic acid, methacrylic acid, maleic anhydride etc..Wherein, preferred metering system
Acid alkyl ester or alkyl acrylate.
As alkyl methacrylate, can enumerate such as: ethyl methacrylate, n propyl methacrylate, methyl
The secondary butyl ester of isopropyl acrylate, n-BMA, Tert-butyl Methacrylate, methacrylic acid, methacrylic acid are different
Butyl ester, 2-Ethylhexyl Methacrylate etc..Wherein, preferably there is the methacrylate of the alkyl of carbon number 2～4
Ester.As alkyl acrylate, can enumerate such as: acrylic acid methyl ester., ethyl acrylate, n-propyl, acrylic acid isopropyl
Ester, butyl acrylate (n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate, Isobutyl 2-propenoate), acrylic acid 2-second
The own ester of base etc..Wherein, preferably there is the alkyl acrylate of the alkyl of carbon number 1～4, more preferably acrylic acid methyl ester..
It should be noted that monofunctional monomer may be used singly or in combination of two or more.
From the viewpoint of the weatherability and the transparency of acrylic resin, at the monomer component constituting acrylic resin
In, contain methyl methacrylate with the ratio of 50～95 weight %, preferably contain methyl-prop with the ratio of 60～90 weight %
E pioic acid methyl ester.
In the monomer component constituting acrylic resin, contain (the first shown in formula (I) with the ratio of 5～50 weight %
Base) acrylate, preferably contains (methyl) acrylate shown in formula (I) with the ratio of 10～40 weight %.Shown in formula (I)
When the content of (methyl) acrylate is less than 5 weight %, obtained acrylic resin is compatible to polycarbonate-based resin
Property reduce, resin combination the transparency reduction.On the other hand, the content of (methyl) acrylate shown in formula (I) is more than 50
During weight %, the compatibility (transparent) reduces, and the weatherability of resin combination also reduces.It should be noted that for inciting somebody to action
For the formed body lacking the transparent and resin combination shaping of weatherability and obtain, its transparency and weatherability also reduce.
In the monomer component constituting acrylic resin, contain monofunctional monomer with the ratio of 0.1～20 weight %, excellent
Choosing contains monofunctional monomer with the ratio of 0.2～10 weight %, more preferably contains simple function list with the ratio of 0.3～5 weight %
Body.When the content of monofunctional monomer is less than 0.1 weight %, easily cause the thermal decomposition of acrylic resin.On the other hand, single official
When the content of energy monomer is more than 20 weight %, the transparency and thermostability reduce.
The polymerization of monomer component is not particularly limited, such as, can pass through emulsion polymerization, suspension polymerization, polymerisation in bulk
The known polymerization such as method, solution polymerization process (curtain coating polymerization) is carried out.Polymerization uses light to irradiate, polymerization initiator enters
OK, be preferably used azo series initiators (such as, 2,2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile)
Deng), peroxide series initiators (lauroyl peroxide, 1,1-bis-(tert-butyl peroxide) hexamethylene, benzoyl peroxide etc.),
The polymerization initiators such as the oxidoreduction series initiators that organic peroxide and amine combine.
The usage amount of polymerization initiator suitably can determine according to the ratio etc. of the kind of monomer, monomer, but relative to monomer
Composition 100 weight portion, generally with 0.01～1 weight portion, preferably 0.01～0.5 weight portion ratio use.
It should be noted that polymerization initiator can be used alone, it is also possible to and use two or more.
It addition, in order to control molecular weight, can add chain-transferring agent (methyl mercaptan, butyl mercaptan, tert-butyl mercaptan,
The thio-alcohols etc. such as n octylmercaptan, n-dodecyl mercaptan, 2-ethylhexyl thioglycolic hydrochlorate), cross-linking agent etc..Making of they
Consumption suitably can determine according to the ratio etc. of the kind of monomer, monomer.
It should be noted that chain-transferring agent and cross-linking agent can individually use, it is also possible to be respectively combined use 2 kinds with
On.
The polymerization temperature of monomer component, polymerization time etc. are not particularly limited, can be according to the kind of monomer, the ratio of monomer
Deng suitably determining.
The acrylic resin used in the present invention comprises the copolymer making above-mentioned polymerizing monomer components and obtain, and has
There is the viscosity-average molecular weight of 80000～300000.When the viscosity-average molecular weight of acrylic resin is less than 80000, resistance to impact and resistance to
Hot reduction.On the other hand, when the viscosity-average molecular weight of acrylic resin is more than 300000, becomes to be difficult to melting mixing, become
It is difficult to form processing.Acrylic resin preferably has the viscosity-average molecular weight of 90000～250000.
The viscosity-average molecular weight (Mv) of acrylic resin is obtained by using following formula (1).
LnMv={ln [η]-ln (4.8 × 10-5)}/0.8 (1)
In formula (1), [η] characterization viscosity, by the viscosity number V measured according to ISO 1628-6NFollowing formula (2) is used to ask
Go out.
VN=[η]+0.4 × [η]2 (2)
The mobility of acrylic resin is by the melt mass flow rate at 230 DEG C with 3.8kg load mensuration
(MFR) evaluate.The mobility (MFR) of acrylic resin is not particularly limited, but preferably 0.1～50g/10 minute, more excellent
Elect 0.2～30g/10 minute as.When acrylic resin has the MFR of this scope, mobility is excellent, and therefore processability improves,
It is prone to carry out melting mixing when manufacturing resin combination.It addition, obtained resin combination and the transparency of formed body and
Intensity also improves.
<polycarbonate-based resin>
As long as the polycarbonate-based resin used in the present invention has the viscosity-average molecular weight of 16000～25000, then there is no spy
Do not limit.About polycarbonate-based resin, such as, can enumerate: by making dihydric phenol and carbonyl agent utilize interface polycondensation, melt
The resin melting the reactions such as ester-interchange method and obtain；Obtain by making polycarbonate prepolymer thing utilize solid phase ester-interchange method etc. to carry out being polymerized
The resin arrived；The resin etc. obtained by making cyclic carbonate compound utilize ring-opening polymerisation method to carry out being polymerized.
When the viscosity-average molecular weight of polycarbonate-based resin is less than 16000, resistance to impact and thermostability reduce.On the other hand,
When the viscosity-average molecular weight of polycarbonate-based resin is more than 25000, need to improve temperature during melting mixing, and and acrylic acid series
The compatibility poor of resin.Polycarbonate-based resin preferably has the viscosity-average molecular weight of 16000～24000.
The viscosity-average molecular weight (Mv) of polycarbonate-based resin can be by using Schnell formula [η]=1.23 × 10- 4Mv0.83Calculated by the intrinsic viscosity [η] of 20 DEG C of dichloromethane solutions.
The mobility of the polycarbonate-based resin used in the present invention is by with melting at 300 DEG C of 1.2kg load mensuration
Body rate of volume flow (MVR) is evaluated.The mobility (MVR) of polycarbonate-based resin is not particularly limited, but preferably 8～
50g/10 minute, more preferably 10～45g/10 minute.When polycarbonate-based resin has the MVR of this scope, mobility is excellent,
Therefore processability improves, and is prone to carry out melting mixing when manufacturing resin combination.It addition, obtained resin combination and one-tenth
The transparency and the mechanical strength of body also improve.
As dihydric phenol, can enumerate such as: hydroquinone, resorcinol, 4,4 '-dihydroxybiphenyl, double (4-hydroxy benzenes
Base) methane, double { (4-hydroxyl-3,5-dimethyl) phenyl } methane, 1, double (4-hydroxy phenyl) ethane of 1-, 1, double (the 4-hydroxyl of 1-
Phenyl)-1-diphenylphosphino ethane, 2, double (4-hydroxy phenyl) propane (common name bisphenol-A) of 2-, 2, double { (4-hydroxy-3-methyl) benzene of 2-
Base } propane, 2, double { (4-hydroxyl-3,5-dimethyl) phenyl } propane of 2-, 2, double { (4-hydroxyl-3, the 5-dibromo) phenyl } third of 2-
Alkane, 2, double { (3-isopropyl-4-hydroxyl) phenyl } propane of 2-, 2, double { (4-hydroxyl-3-phenyl) phenyl } propane of 2-, 2,2-is double
(4-hydroxy phenyl) butane, 2, double (4-hydroxy phenyl)-3-methybutane of 2-, 2, double (the 4-hydroxy phenyl)-3 of 2-, 3-dimethyl
Butane, 2, double (4-hydroxy phenyl)-2-methybutane of 4-, 2, double (4-hydroxy phenyl) pentane of 2-, 2,2-double (4-hydroxy phenyl)-
4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1, double (4-hydroxy phenyl)-4-isopropyl cyclohexane of 1-, 1,1-is double
(4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexanes, 9, double (4-hydroxy phenyl) fluorenes of 9-, 9, double { (4-hydroxy-3-methyl) benzene of 9-
Base } fluorenes, α, α '-bis-(4-hydroxy phenyls) adjacent diisopropyl benzene, α, diisopropyl benzene, α between α '-bis-(4-hydroxy phenyl), α '-bis-
(4-hydroxy phenyl) to diisopropyl benzene, 1, double (the 4-hydroxy phenyl)-5 of 3-, 7-dimethyladamantane, 4,4 '-dihydroxy hexichol
Base sulfone, 4,4 '-dihydroxydiphenyl sulfoxide, 4,4 '-dihydroxydiphenyl thioether, 4,4 '-dihydroxydiphenyl ketone, 4,4 '-two
Hydroxy diphenyl ether, 4,4 '-dihydroxydiphenyl ester etc..They can be used alone, it is also possible to and use two or more.
In these dihydric phenols, preferably bisphenol-A, 2, double { (4-hydroxy-3-methyl) phenyl } propane of 2-, 2, double (the 4-hydroxyl of 2-
Phenyl) butane, 2, double (4-hydroxy phenyl)-3-methybutane of 2-, 2, double (the 4-hydroxy phenyl)-3 of 2-, 3-dimethylbutane, 2,
Double (4-the hydroxy phenyl)-4-methylpentane of 2-, 1, double (the 4-hydroxy phenyl)-3 of 1-, 3,5-trimethyl-cyclohexanes and α, α '-bis-(4-
Hydroxy phenyl) between diisopropyl benzene.Spy is the most preferably used alone bisphenol-A, or and with bisphenol-A and selected from 1, double (the 4-hydroxyl of 1-
Phenyl)-3,3,5-trimethyl-cyclohexanes, 2, double { (4-hydroxy-3-methyl) phenyl } propane of 2-and α, α '-bis-(4-hydroxy phenyls)
Between at least one in diisopropyl benzene.
As carbonyl agent, can enumerate such as: carbonyl carboxylic acid halides (phosgene etc.), carbonic ester (diphenyl carbonate etc.), halo
Formic acid esters (bishaloformate etc. of dihydric phenol) etc..They can be used alone, it is also possible to and use two or more.
<resin combination>
The resin combination of the present invention contains acrylic resin and with 5～50 weights with the ratio of 50～95 weight %
The ratio of amount % contains polycarbonate-based resin.Such as, when the content of polycarbonate-based resin is less than 5 weight %, engineering properties
Become insufficient.On the other hand, when the content of polycarbonate-based resin is more than 50 weight %, resin combination and shaping and obtain
Formed body the transparency reduction.
Preferably contain acrylic resin with the ratio of 50～80 weight %, preferably contain with the ratio of 20～50 weight %
Polycarbonate-based resin.
In addition to above-mentioned specific acrylic resin and above-mentioned specific polycarbonate-based resin, do not damaging the present invention
Purpose in the range of, the resin combination of the present invention can also coordinate: compatibility agent, stabilizer, antioxidant, light are stable
Agent, coloring agent, foaming agent, lubricant, releasing agent, antistatic agent, fire retardant, flame retardant, UV absorbent, dyestuff, face
The usual additive such as material, polymerization inhibitor, reinforcing agent, a small amount of other thermoplastic resins etc..These additives can incited somebody to action
Resin compound containing acrylic resin and polycarbonate-based resin carries out interpolation during melting mixing, it is also possible to melted mixed
Add before or after refining.When adding additive, its content is left relative to resin combination preferably 0.005～30 weight %
Right.
In the resin combination of the present invention, the melt viscosity (η of acrylic resinA) and the melt viscosity of Merlon
(ηB) ratio (ηA/ηB) it is 0.40～3.00.It should be noted that melt viscosity is in temperature 240 DEG C and shear rate 60sec-1
Under conditions of melt viscosity.This is than (ηA/ηB) less than 0.40 or during more than 3.00, the differences in viscosity between resin is away from excessive, melted
It is difficult to time mixing mix equably, the transparency reduction of obtained resin combination.This is than (ηA/ηB) it is preferably 0.42
～2.90.
It addition, the resin combination of the present invention meets following formula (a).
2≤(MVRPC×Wa×Wa)/(Wb×Wb)≤50 (a)
(in formula (a), MVRPCThe melt volume-flow rate of the polycarbonate-based resin at representing 300 DEG C, Wa represents described
Weight % of (methyl) acrylate shown in formula (I) in monomer component, it is polycarbonate-based that Wb represents in resin combination
Weight % of resin.)
By meeting formula (a), the resin combination with the transparency of excellence can be obtained.When being unsatisfactory for formula (a), acrylic acid
It is the affinity reduction of resin and polycarbonate-based resin, it is impossible to obtain transparent resin combination.
The resin combination of the present invention particularly preferably meets following formula (a) '.
2.4≤(MVRPC×Wa×Wa)/(Wb×Wb)≤40 (a)’
<manufacture method of resin combination>
The resin combination of the present invention passes through will be containing above-mentioned specific acrylic resin and above-mentioned specific poly-carbonic acid
The resin compound melting mixing of ester system resin and obtain.
In order to these resins being carried out equably melting mixing, melting mixing generally at 180～320 DEG C, preferably 200～
Under the temperature conditions of 300 DEG C, generally with 10～500sec-1Shear rate, preferably 20～300sec-1, more preferably 30～
200sec-1Shear rate carry out.
As the equipment used in melting mixing, it is possible to use common mixer, mixing roll etc..Specifically, can lift
Go out single shaft mixing extruder, two axle mixing extruders, ribbon stirrer, Henschel mixer, banbury mixers, drum type rolling
Cylinder machine etc..Wherein, preferably two axle mixing extruder.Melting mixing can be as required at torpescence gas such as nitrogen, argon, helium
Carry out under bromhidrosis atmosphere.
So can be obtained by the transparency and the resin combination of mechanical strength with excellence.
(formed body)
The resin combination of the present invention is processed into desired shape, is processed into the transparency (the optics spy with excellence
Property) and the formed body of intensity.This formed body such as electron-optical material, cover material, resin finish material etc. useful.
Form in the equipment that obtained resin combination can directly use in above-mentioned melting mixing.It addition,
After obtained resin combination can also be configured to graininess etc., use the forming machine such as injection machine, hydraulic press, becoming
Melt-shaping is carried out in shape machine.
Forming temperature is usually about 150～350 DEG C, preferably about 180～320 DEG C, more preferably 180～300 DEG C left sides
Right.
Embodiment
Hereinafter enumerate embodiment and comparative example illustrates the present invention, but the present invention is not limited to these embodiments.
It should be noted that acrylic resin, polycarbonate-based resin, obtained resin combination and formed body
Various physical property are measured by following method and evaluate.
<melt mass flow rate (MFR)>
It is measured with the condition of 230 DEG C and 3.8kg loads according to JIS K7210.
<melt volume-flow rate (MVR)>
It is measured with 300 DEG C and 1.2kg loads according to ISO 1133.
<outward appearance of resin combination>
Visualization particulate resins compositions, evaluates whether transparent (nebulousurine).
(synthesis example 1: the synthesis of acrylic resin)
As shown in table 1, the methyl methacrylate (MMA) of 89.7 weight %, the methacrylic acid ring of 10 weight % are mixed
The acrylic acid methyl ester. (MA) of own ester (CHMA) and 0.3 weight % and obtain monomer component.This monomer component adds as poly-
Close lauryl peroxide 0.2 weight % of initiator, be then added as n octylmercaptan 0.2 weight % of chain-transferring agent,
Make them be dissolved in monomer component and obtain monomer mixture.
This monomer mixture 100 weight portion, ion exchange water 285 weight portion and as suspended is added in reaction vessel
Aqueous sodium polyacrylate 0.18 weight portion of 1.2 weight % of stabilizer, carries out the suspension polymerisation of 3 hours at 80 DEG C.Will
After obtained pulp-like reactant liquor dewaterer carries out dehydration washing, it is dried, obtains pearl acrylic resin.
This pearl acrylic resin is joined in two axle mixing rolls ((strain) JSW system, TEX-30), with 250
DEG C and the condition of 200rpm rotating speed carry out melting mixing.Then, fused mass is extruded as wire, after cooling, uses cutting machine
(strand cutter) cuts off, and obtains graininess acrylic resin.The viscosity-average molecular weight of obtained acrylic resin
And MFR is as shown in table 1 (Mv).
(synthesis example 2～8 and compare synthesis example 1～3: the preparation of acrylic resin)
The ratio recorded with table 1 uses the composition that table 1 is recorded, and obtains with the order as synthesis example 1 in addition
Particulate acrylic acid system resin.Viscosity-average molecular weight (Mv) and the MFR of obtained acrylic resin are as shown in table 1.
[table 1]
MMA: methyl methacrylate
CHMA: cyclohexyl methacrylate
MA: acrylic acid methyl ester.
The viscosity-average molecular weight (Mv) of the Merlon (PC) used shown in table 2 and MVR.These all Sumika
The Merlon that Styron Polycarbonate (strain) makes.Below as described in table 2, if カ is リ バ mono-301-40, then have
Time image PC-40 records the most briefly.
[table 2]
| Mv | MVR (g/10 minute) | |
| カリバ-301-40(PC-40) | 16500 | 40 |
| カリバ-301-30(PC-30) | 17000 | 30 |
| カリバ-301-10(PC-10) | 23000 | 10 |
| カリバ-200-3(PC-3)* | 28000 | 3 |
*: there is the Mv bigger than the polycarbonate-based resin used in the present invention.
(embodiment 1: the preparation of resin combination)
As shown in table 3, the PC-40 of the acrylic resin obtained in the synthesis example 1 of 70 weight % and 30 weight % is used
((strain) JSW system, TEX-30SS, the length (L) of screw rod with the ratio (L/D) of screw rod footpath (D) are two axle mixing extruders
41) with barrel temperature 250 DEG C and rotating speed 100rpm (shear rate 81sec-1) condition carry out melting mixing.To just mixing from two axles
The temperature of the fused mass after the die head discharge of refining extruder is measured, and result is 250～255 DEG C.It should be noted that propylene
Acid is the melt viscosity ratio (η of resin and polycarbonate-based resinA/ηB) as shown in table 3.
Fused mass is extruded as wire, cuts off with cutting machine after cooling, obtain granular resin combination.Visualization
The outward appearance of obtained resin combination, result is as shown in table 3.
Then, by obtained resin combination injection machine (" IS130FII " that toshiba machine (strain) is made) with
The barrel temperature injection moulding of 250 DEG C, to being set as the mould of 60 DEG C, obtains the tabular formed body of 50mm × 50mm × 3.4mm.
For obtained tabular formed body, calculate " (MVRPC×Wa×Wa)/(Wb×Wb) " value.Result is as shown in table 3.
(embodiment 2～8 and comparative example 1～7: the preparation of resin combination)
The ratio recorded with table 3 uses the composition that table 3 is recorded, and obtains respectively with order similarly to Example 1 in addition
To resin combination.The outward appearance of the resin combination obtained by visualization, result is as shown in table 3.
Then, obtained resin combination is configured to tabular formed body with order similarly to Example 1, calculates
“(MVRPC×Wa×Wa)/(Wb×Wb) " value.Result is as shown in table 3.
[table 3]
*: result of calculation is served as reasons (MVRPC×Wa×Wa)/(Wb×Wb) " value that calculates
As known from Table 3, the resin combination (embodiment 1～8) of the present invention is water white transparency, has the transparency of excellence.
On the other hand understanding, the resin combination of comparative example 1～7 all produces nebulousurine, opaque.
<mensuration of various physical property>
Then, the tabular formed body obtained in embodiment 1～8, comparative example 1～3 and 5 is measured total light transmittance
(Tt), vicat softening temperature (VST) and impact strength.
It should be noted that to suitable with similarly to Example 1 of the acrylic resin that will obtain in synthesis example 1,3 and 5
The tabular formed body that sequence shapes also measures total light transmittance (Tt), vicat softening temperature (VST) and impact strength (reference example 1
～3).
(total light transmittance (Tt))
Use absorbance meter (color technical research institute system in HR-100, (strain) village), measure total light according to JIS K7361-1
Line absorbance (Tt).Its numerical value is the biggest, represents the easiest transmission of light, thus the transparency is the highest.Result is as shown in table 4.
(vicat softening temperature (VST))
Obtained formed body is cut into the size of 20mm × 20mm, makes test film.For obtained test film,
According to JIS K7206 B50 method with load 50N and programming rate 50 DEG C/time condition measure vicat softening temperature (VST).Should
Temperature is the highest, represents have the most excellent thermostability.Result is as shown in table 4.
(impact strength)
Carry out charpy impact test according to JIS K7111-2, measure impact strength.
The formed body measured all does not has breach (ノ Star チ) (entry).The value of impact strength is the biggest, and expression has the most excellent
Different thermostability.Result is as shown in table 4.
[table 4]
As shown in Table 4, the formed body shaped by the resin combination (embodiment 1～8) of the present invention and obtain has
With will have excellence the transparency acrylic resin (synthesis example 1,3 and 5) shape and obtain formed body (reference example 1～
3) transparency the most in no way inferior is compared.In addition we know, the formed body of the present invention has thermostability and the resistance to impact of excellence.
On the other hand, although the formed body resin combination of comparative example 1～3 and 5 being shaped and obtaining at thermostability and
Resistance to impact aspect is the poorest, but Tt is the lowest, opaque.
Claims (6)
1. a resin combination, it is to contain acrylic resin and with 5～50 weight % with the ratio of 50～95 weight %
Ratio contain the resin combination of polycarbonate-based resin, wherein,
Described acrylic resin contains to be made to comprise (methyl) shown in methyl methacrylate 50～95 weight %, lower formula (I)
Acrylate 5～50 weight % and the polymerizing monomer components of the monofunctional monomer beyond these 0.1～20 weight % and obtain
Copolymer, above-mentioned three kinds of component content sums are less than 100 weight %, and for having the viscous equal molecule of 80000～300000
The resin of amount,
In formula (I), R1Represent hydrogen atom or methyl, R2Represent alkyl, cycloalkyl or the alkyl-cycloalkyl being substituted by cycloalkyl,
Described polycarbonate-based resin is by making a kind of dihydric phenol react, with carbonyl agent, the resin obtained, its have 16000～
The viscosity-average molecular weight of 25000,
And in temperature 240 DEG C and shear rate 60sec-1Under the conditions of the melt viscosity (η of acrylic resinA) and in temperature
240 DEG C and shear rate 60sec-1Under the conditions of the melt viscosity (η of MerlonB) ratio (ηA/ηB) it is 0.40～3.00,
Meet following formula (a),
2≤(MVRPC×Wa×Wa)/(Wb×Wb)≤50 (a)
In formula (a), MVRPCRepresent according to ISO 1133, polycarbonate-based resin that measure with 1.2kg load, at 300 DEG C
Melt volume-flow rate, WaRepresent weight % of (methyl) acrylate shown in formula (I) in described monomer component, WbTable
Show weight % of polycarbonate-based resin in resin combination.
2. resin combination as claimed in claim 1, wherein,
(methyl) acrylate shown in described formula (I) is selected from cyclohexyl methacrylate, cyclohexyl acrylate, metering system
At least one ester in acid bicyclo-pentyl ester and acrylic acid bicyclo-pentyl ester.
3. resin combination as claimed in claim 1, wherein,
Described monofunctional monomer is at least one monomer in acrylic acid methyl ester., ethyl acrylate and butyl acrylate.
4. a method for the resin combination described in manufacturing claims 1, comprising:
The resin compound comprising acrylic resin and polycarbonate-based resin is carried out the operation of melting mixing.
5. method as claimed in claim 4, wherein,
Described melting mixing is the temperature and 10～500sec of 180～320 DEG C-1Shear rate under carry out.
6. a formed body, it obtains by being shaped by the resin combination described in claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-173634 | 2012-08-06 | ||
| JP2012173634A JP5959102B2 (en) | 2012-08-06 | 2012-08-06 | Resin composition, method for producing resin composition, and molded article |
| PCT/JP2013/071444 WO2014024949A1 (en) | 2012-08-06 | 2013-08-01 | Resin composition, method for producing resin composition, and molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104520377A CN104520377A (en) | 2015-04-15 |
| CN104520377B true CN104520377B (en) | 2016-11-30 |
Family
ID=
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906696A (en) * | 1987-06-06 | 1990-03-06 | Rohm Gmbh Chemische Fabrik | Transparent, thermoplastically processable polymer blends made of an aromatic polycarbonate and a methyacrylate polymer |
| CN101747610A (en) * | 2008-12-17 | 2010-06-23 | 第一毛织株式会社 | Polycarbonate resin composition with improved transparency and scratch-resistance |
| CN102227293A (en) * | 2008-11-26 | 2011-10-26 | 独立行政法人产业技术综合研究所 | Method of melt kneading, extrudate, and transparent resin material |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4906696A (en) * | 1987-06-06 | 1990-03-06 | Rohm Gmbh Chemische Fabrik | Transparent, thermoplastically processable polymer blends made of an aromatic polycarbonate and a methyacrylate polymer |
| CN102227293A (en) * | 2008-11-26 | 2011-10-26 | 独立行政法人产业技术综合研究所 | Method of melt kneading, extrudate, and transparent resin material |
| CN101747610A (en) * | 2008-12-17 | 2010-06-23 | 第一毛织株式会社 | Polycarbonate resin composition with improved transparency and scratch-resistance |
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