JP2016030817A - Styrene-based resin sheet and molded article using the same - Google Patents
Styrene-based resin sheet and molded article using the same Download PDFInfo
- Publication number
- JP2016030817A JP2016030817A JP2014154904A JP2014154904A JP2016030817A JP 2016030817 A JP2016030817 A JP 2016030817A JP 2014154904 A JP2014154904 A JP 2014154904A JP 2014154904 A JP2014154904 A JP 2014154904A JP 2016030817 A JP2016030817 A JP 2016030817A
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- branched
- macromonomer
- resin composition
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229920005989 resin Polymers 0.000 title claims abstract description 36
- 239000011347 resin Substances 0.000 title claims abstract description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011342 resin composition Substances 0.000 claims abstract description 40
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 229920005605 branched copolymer Polymers 0.000 claims abstract description 3
- 238000000569 multi-angle light scattering Methods 0.000 claims description 15
- 229920001890 Novodur Polymers 0.000 claims description 9
- 239000005022 packaging material Substances 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 27
- 239000004721 Polyphenylene oxide Substances 0.000 description 24
- 229920000570 polyether Polymers 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 21
- -1 acrylic compound Chemical class 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 229920005862 polyol Polymers 0.000 description 16
- 150000003077 polyols Chemical class 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 9
- 229920005906 polyester polyol Polymers 0.000 description 9
- 229920002223 polystyrene Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 125000005504 styryl group Chemical group 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229920000962 poly(amidoamine) Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- BWXAUWJMUAOSLG-UHFFFAOYSA-N 5-(bromomethyl)benzene-1,3-diol Chemical compound OC1=CC(O)=CC(CBr)=C1 BWXAUWJMUAOSLG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 2
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- UTDREDDDGVJRGG-UHFFFAOYSA-N 3-[4-(3-hydroxypropyl)phenyl]propan-1-ol Chemical compound OCCCC1=CC=C(CCCO)C=C1 UTDREDDDGVJRGG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 229920006150 hyperbranched polyester Polymers 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- QQHZNUPEBVRUFO-UHFFFAOYSA-N (3-methyloxiran-2-yl)methanol Chemical compound CC1OC1CO QQHZNUPEBVRUFO-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- FJEKUEUBQQWPBY-UHFFFAOYSA-N 1$l^{2}-stanninane Chemical compound C1CC[Sn]CC1 FJEKUEUBQQWPBY-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
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VWVZFHRDLPHBEG-UHFFFAOYSA-N 1-(chloromethyl)-4-methylsulfanylbenzene Chemical group CSC1=CC=C(CCl)C=C1 VWVZFHRDLPHBEG-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N 2,2-dimethylhexane Chemical compound CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- MMHHBAUIJVTLFZ-UHFFFAOYSA-N 2-(bromomethyl)-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CBr MMHHBAUIJVTLFZ-UHFFFAOYSA-N 0.000 description 1
- GDMBPPMGWKQBAE-UHFFFAOYSA-N 2-(bromomethyl)-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)CBr GDMBPPMGWKQBAE-UHFFFAOYSA-N 0.000 description 1
- CRXGGNZLPTXQHB-UHFFFAOYSA-N 2-(bromomethyl)-2-methylpropane-1,3-diol Chemical compound OCC(C)(CO)CBr CRXGGNZLPTXQHB-UHFFFAOYSA-N 0.000 description 1
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 description 1
- HPVOTSMEHLZBJY-UHFFFAOYSA-N 2-(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)C(O)=O HPVOTSMEHLZBJY-UHFFFAOYSA-N 0.000 description 1
- AVSUMWIDHQEMPD-UHFFFAOYSA-N 2-(oxiran-2-yl)ethanol Chemical compound OCCC1CO1 AVSUMWIDHQEMPD-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- QPIAAQDLOJNQMP-UHFFFAOYSA-N 2-ethyl-2-propylpropane-1,3-diol Chemical compound CCCC(CC)(CO)CO QPIAAQDLOJNQMP-UHFFFAOYSA-N 0.000 description 1
- DDBYLRWHHCWVID-UHFFFAOYSA-N 2-ethylbut-1-enylbenzene Chemical compound CCC(CC)=CC1=CC=CC=C1 DDBYLRWHHCWVID-UHFFFAOYSA-N 0.000 description 1
- ZMZQVAUJTDKQGE-UHFFFAOYSA-N 2-ethylhydracrylic acid Chemical compound CCC(CO)C(O)=O ZMZQVAUJTDKQGE-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、分岐末端に二重結合を有する特定の多分岐マクロモノマーとスチレン系モノマー及びメタクリル酸との共重合体を含有する樹脂組成物を用いてなるシートに関し、詳しくは、従来のスチレン−メタクリル酸共重合体よりも成形性に優れたシートに関するものである。 The present invention relates to a sheet comprising a resin composition containing a copolymer of a specific multi-branched macromonomer having a double bond at a branched end, a styrene monomer, and methacrylic acid. The present invention relates to a sheet having better moldability than a methacrylic acid copolymer.
ポリスチレンシートは、透明性や剛性が優れているため、主に食品包装用容器として使用されている。しかし、このポリスチレンシート製の容器は一般的な食品包装容器としては適しているものの、耐熱性が不十分であるため、電子レンジで加熱するような用途には不向きである。このため、これらの分野にも利用できるように、シートの透明性、剛性、成形性を損なうことなく、耐熱性を向上させる技術が求められている。 Polystyrene sheets are mainly used as food packaging containers because of their excellent transparency and rigidity. However, although this polystyrene sheet container is suitable as a general food packaging container, its heat resistance is insufficient, so that it is not suitable for use in heating in a microwave oven. For this reason, a technique for improving heat resistance without impairing the transparency, rigidity, and formability of the sheet is required so that it can be used in these fields.
ポリスチレンシートの耐熱性を向上させる手法としては、例えば、ポリスチレンとスチレン／マレイン酸共重合体との混合物からなる二軸延伸シート（例えば、特許文献１参照。）、スチレンとアクリル酸、メタクリル酸又は無水マレイン酸との共重合体からなるシートが提案されている（例えば、特許文献２参照）。しかし、これらのシートは、二軸延伸における適正な加工条件が狭いため、均一な物理的性質を有するものが得にくく、これらのシートから得られる成形品の実用強度も満足できるものではない。 As a method for improving the heat resistance of the polystyrene sheet, for example, a biaxially stretched sheet made of a mixture of polystyrene and a styrene / maleic acid copolymer (see, for example, Patent Document 1), styrene and acrylic acid, methacrylic acid or A sheet made of a copolymer with maleic anhydride has been proposed (see, for example, Patent Document 2). However, these sheets are difficult to obtain those having uniform physical properties because the proper processing conditions in biaxial stretching are narrow, and the practical strength of molded products obtained from these sheets is not satisfactory.
また、スチレン／マレイミド共重合体からなる二軸延伸シートが提案されている（例えば、特許文献３参照）。しかし、このシートは着色が激しく、成形品の実用強度も不足している。 In addition, a biaxially stretched sheet made of a styrene / maleimide copolymer has been proposed (see, for example, Patent Document 3). However, this sheet is intensely colored, and the practical strength of the molded product is insufficient.
ポリスチレンの耐熱性を向上させるため、ポリスチレンにポリカーボネートを配合する試みがなされているが、ポリスチレンとポリカーボネートとは相溶性が悪いために、溶融混合操作の制御が困難である。そこで、従来はスチレンと、アクリロニトリル、メチルメタクリレート、アクリル酸、メタクリル酸又は不飽和ジカルボン酸とを共重合させたスチレン系樹脂とポリカーボネートとの混合物が用いられてきたが、このようなスチレン系樹脂とポリカーボネートは屈折率が異なるため、透明性の点で実用上満足できるものではなく、さらなる改良が求められている。 In order to improve the heat resistance of polystyrene, attempts have been made to blend polycarbonate with polystyrene. However, since polystyrene and polycarbonate are poorly compatible, it is difficult to control the melt mixing operation. Therefore, conventionally, a mixture of styrene resin and polycarbonate obtained by copolymerizing styrene and acrylonitrile, methyl methacrylate, acrylic acid, methacrylic acid or unsaturated dicarboxylic acid has been used. Since polycarbonate has a different refractive index, it is not practically satisfactory in terms of transparency, and further improvements are required.
これらの事情に鑑み、本発明が解決しようとする課題は、耐熱性を有し、成形性も兼ね備えた外観が良好であるスチレン系樹脂シートを提供することにある。 In view of these circumstances, the problem to be solved by the present invention is to provide a styrenic resin sheet that has heat resistance and good appearance that also has moldability.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、多分岐状マクロモノマーとスチレン系モノマーとメタクリル酸とを共重合させることにより得られる多分岐状スチレン−メタクリル酸樹脂と線状スチレン−メタクリル酸樹脂とを含むスチレン系樹脂組成物を用いてなるシートが上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have obtained a multibranched styrene-methacrylic acid resin and a wire obtained by copolymerizing a multibranched macromonomer, a styrene monomer, and methacrylic acid. It discovered that the sheet | seat formed using the styrene-type resin composition containing a glassy styrene-methacrylic acid resin can solve the said subject, and came to complete this invention.
即ち、本発明は、複数の分岐を有し、且つ複数の重合性二重結合を有する多分岐状マクロモノマー（ａ１）と、スチレン系モノマー（ａ２）と、メタクリル酸（ａ３）とを共重合してなる多分岐状共重合体（Ａ１）、及びスチレン系モノマー（ａ２）とメタクリル酸（ａ３）とを共重合してなる共重合体（Ａ２）を含有するスチレン系樹脂組成物からなることを特徴とするスチレン系樹脂シートを提供するものである。 That is, the present invention is a copolymer of a multi-branched macromonomer (a1) having a plurality of branches and a plurality of polymerizable double bonds, a styrene monomer (a2), and methacrylic acid (a3). And a styrene resin composition containing a copolymer (A2) obtained by copolymerizing a styrene monomer (a2) and methacrylic acid (a3). A styrene-based resin sheet characterized by the above is provided.
本発明のスチレン系樹脂シートはスチレン−メタクリル酸共重合体に多分岐構造を導入したことで、スチレン−メタクリル酸共重合体からなるシートの弱点である脆性を改善でき、耐熱性を保持しながら、成形性及び物性強度の向上を図ることができ、電子レンジ等での加熱を行う食品用途等にも好適に用いることができる。 The styrene-based resin sheet of the present invention has introduced a multi-branched structure into a styrene-methacrylic acid copolymer, thereby improving the brittleness, which is a weak point of a sheet made of a styrene-methacrylic acid copolymer, while maintaining heat resistance. In addition, the moldability and physical property strength can be improved, and it can also be suitably used for food applications such as heating in a microwave oven.
以下に本発明の樹脂シートに用いる組成物について詳細に説明する。
〔スチレン系樹脂組成物〕
本発明で用いるスチレン系樹脂組成物は、複数の分岐を有し、且つ複数の重合性二重結合を有する多分岐状マクロモノマー（ａ１）とスチレン系モノマー（ａ２）とメタクリル酸（ａ３）とを共重合させることにより得られる多分岐状共重合体（Ａ１）を必須とし、共重合時に同時に生成するスチレン系モノマー（ａ２）とメタクリル酸（ａ３）とを共重合してなる線状樹脂である共重合体（Ａ２）を含有し、更に、スチレン系モノマー（ａ２）の単独重合体や、メタクリル酸（ａ３）の単独重合体を含有していても良い。
Below, the composition used for the resin sheet of this invention is demonstrated in detail.
[Styrene resin composition]
The styrenic resin composition used in the present invention has a multi-branched macromonomer (a1), a styrenic monomer (a2), and methacrylic acid (a3) having a plurality of branches and a plurality of polymerizable double bonds. It is a linear resin obtained by copolymerizing a styrene monomer (a2) and methacrylic acid (a3), which are produced at the same time as the copolymer, with the hyperbranched copolymer (A1) obtained by copolymerizing It contains a certain copolymer (A2), and may further contain a homopolymer of a styrene monomer (a2) or a homopolymer of methacrylic acid (a3).
更に、予め製造したスチレン系モノマー（ａ２）とメタクリル酸（ａ３）とを共重合してなる線状樹脂である共重合体（Ａ２）、スチレン系モノマー（ａ２）の単独重合体、メタクリル酸（ａ３）の単独重合体を、多分岐状マクロモノマー（ａ１）とスチレン系モノマー（ａ２）とメタクリル酸モノマーを共重合させた樹脂に混合して用いても良い。 Furthermore, a copolymer (A2) which is a linear resin obtained by copolymerizing a styrene monomer (a2) and methacrylic acid (a3) produced in advance, a homopolymer of styrene monomer (a2), methacrylic acid ( The homopolymer of a3) may be mixed with a resin obtained by copolymerizing a hyperbranched macromonomer (a1), a styrene monomer (a2), and a methacrylic acid monomer.
また、本発明に使用するスチレン系樹脂組成物は、スチレン系モノマー（ａ２）由来構造部分とメタクリル酸（ａ３）由来構造部分との存在割合が、（ａ２）／（ａ３）で表される質量比として９７／３〜９９．９／０．１の範囲であると、これを用いて得られるシートの耐熱性と成形性とのバランスに優れる点で好ましい。 In the styrene resin composition used in the present invention, the mass ratio of the styrene monomer (a2) -derived structure portion and the methacrylic acid (a3) -derived structure portion is represented by (a2) / (a3). When the ratio is in the range of 97/3 to 99.9 / 0.1, it is preferable in terms of excellent balance between heat resistance and formability of a sheet obtained using the ratio.
本発明に使用されるスチレン系樹脂組成物は、ＧＰＣ−ＭＡＬＬＳ法により求められる重量平均分子量が１５万〜７５万であることが好ましく、更に、生産性、加工性の観点から、２０万〜６０万の範囲であることがより好ましい。また、前記多分岐状共重合体（Ａ１）のＧＰＣ−ＭＡＬＬＳで求められる重量平均分子量が１００万〜１０００万の範囲であり、前記共重合体（Ａ２）のＧＰＣ−ＭＡＬＬＳで求められる重量平均分子量が１０万〜４５万の範囲であることが好ましい。 The styrene resin composition used in the present invention preferably has a weight average molecular weight of 150,000 to 750,000 determined by the GPC-MALLS method. Furthermore, from the viewpoint of productivity and workability, 200,000 to 60 More preferably, it is in the range of 10,000. Moreover, the weight average molecular weight calculated | required by GPC-MALLS of the said multibranched copolymer (A1) is the range of 1 million-10 million, The weight average molecular weight calculated | required by GPC-MALLS of the said copolymer (A2) Is preferably in the range of 100,000 to 450,000.
〔ＧＰＣ−ＭＡＬＬＳ〕
本発明に使用されるスチレン系樹脂組成物をＧＰＣ−ＭＡＬＬＳにより分子量を測定すると、例えば、図１に示すクロマトグラフが得られる。図１中、低分子量側のピークがＰ１であり、高分子量側のピークがＰ２である。ピークＰ１には、線状の樹脂と、低分岐度の樹脂が含まれていると推測される。そして、ピークＰ２には主として多分岐状の高分岐度の樹脂が含まれていると推測される。なお、ピークＰ２の領域は、ピークＰ２の最高点からベースライン（図１中、ｖｏｌｕｍｅ軸にほぼ平行に引かれた点線）に降ろした垂線と、ベースラインと、該最高点から左側の分子量カーブとで囲まれた領域（１）と、該領域（１）を、前記垂線を対称軸として右側に折り返したときに形成される分子量カーブ（図１中、垂線の右側に点線で示した仮想の分子量カーブ）と、垂線と、ベースラインとで囲まれた領域（２）とにより形成される領域である。そして、ピークＰ１の領域は、分子量カーブと、ベースラインとで囲まれた領域から前記領域（１）と領域（２）からなるピークＰ１の領域を差し引いた部分である。
[GPC-MALLS]
When the molecular weight of the styrene resin composition used in the present invention is measured by GPC-MALLS, for example, the chromatograph shown in FIG. 1 is obtained. In FIG. 1, the peak on the low molecular weight side is P1, and the peak on the high molecular weight side is P2. The peak P1 is presumed to contain a linear resin and a resin with a low degree of branching. The peak P2 is presumed to contain mainly a multi-branched resin having a high degree of branching. The region of peak P2 includes a perpendicular line drawn from the highest point of peak P2 to the baseline (a dotted line drawn substantially parallel to the volume axis in FIG. 1), a baseline, and a molecular weight curve on the left side from the highest point. And a molecular weight curve formed when the region (1) is folded to the right side with the perpendicular as the axis of symmetry (in FIG. 1, a virtual line indicated by a dotted line on the right side of the perpendicular). This is a region formed by a region (2) surrounded by a molecular weight curve), a perpendicular, and a base line. The region of peak P1 is a portion obtained by subtracting the region of peak P1 composed of the region (1) and region (2) from the region surrounded by the molecular weight curve and the baseline.
〔ピークＰ１の領域中の樹脂とピークＰ２の領域中の樹脂の配合比〕
本発明に使用されるスチレン系樹脂組成物のピークＰ１の領域中の樹脂とピークＰ２の領域中の樹脂の質量比は、得られるシートの強度と加工性とのバランスに優れる点で（ピークＰ２の領域中の樹脂）／（ピークＰ１の領域中の樹脂）＝３０／７０〜７０／３０が好ましく、より好ましくは、４０／６０〜６０／４０である。この比率は、多分岐状マクロモノマー（ａ１）とスチレン系モノマー（ａ２）、メタクリル酸（ａ３）との使用割合の調整や、連鎖移動剤の種類及びその使用量によって、容易に制御可能である。
[Blend ratio of resin in peak P1 region and resin in peak P2 region]
The mass ratio of the resin in the peak P1 region and the resin in the peak P2 region of the styrenic resin composition used in the present invention is excellent in the balance between the strength and workability of the obtained sheet (peak P2 Resin in the region) / (resin in the region of peak P1) = 30/70 to 70/30, more preferably 40/60 to 60/40. This ratio can be easily controlled by adjusting the use ratio of the hyperbranched macromonomer (a1), the styrene monomer (a2), and the methacrylic acid (a3), the type of chain transfer agent, and the amount used. .
〔スチレン系樹脂組成物の両対数グラフの傾き〕
また、本発明に使用されるスチレン系樹脂組成物のＧＰＣ−ＭＡＬＬＳから求められる分子量を横軸、慣性半径を縦軸とした両対数グラフにおける分子量２５万〜１０００万の領域での傾きは、強度と成形加工性とを優れたバランスで発現させる点で、０．２５〜０．５５であることが最も好ましい。傾きが０．５５よりも大きくなると、線状樹脂により近い物性となり、逆に０．２５よりも小さくなると、分岐度増加に伴う分子量増大により流動性が低下することがある。
[Slope of logarithmic graph of styrene resin composition]
Further, the gradient in the region of molecular weight 250,000 to 10 million in the logarithmic graph with the horizontal axis representing the molecular weight obtained from GPC-MALLS of the styrene resin composition used in the present invention and the vertical axis representing the inertial radius is the strength. And 0.25 to 0.55 are most preferable in terms of exhibiting an excellent balance between moldability and moldability. When the slope is larger than 0.55, the physical properties are closer to those of the linear resin. Conversely, when the slope is smaller than 0.25, the fluidity may be lowered due to an increase in molecular weight accompanying an increase in the degree of branching.
〔多分岐状マクロモノマー（ａ１）〕
本発明で使用する複数の分岐を有し、且つ複数の重合性二重結合を有する多分岐状マクロモノマー（ａ１）としては、上記諸特性に優れたスチレン系樹脂組成物を容易に得られる点、特に多分岐状共重合体（Ａ１）の重量平均分子量を１０００万以下に制御してゲル物発生を抑制し、流動性を確保する観点から、多分岐状マクロモノマー（ａ１）の重量平均分子量（Ｍｗ）が、好ましくは１，０００〜１５，０００、より好ましくは３，０００〜８，０００の範囲のものを用いる。
[Multi-branched macromonomer (a1)]
As the multi-branched macromonomer (a1) having a plurality of branches and a plurality of polymerizable double bonds used in the present invention, a styrenic resin composition excellent in the above properties can be easily obtained. In particular, from the viewpoint of controlling gel weight generation by controlling the weight average molecular weight of the multibranched copolymer (A1) to 10 million or less and ensuring fluidity, the weight average molecular weight of the multibranched macromonomer (a1) (Mw) is preferably 1,000 to 15,000, more preferably 3,000 to 8,000.
多分岐状マクロモノマー（ａ１）における分岐構造としては、特に制限はないが、電子吸引基と、該電子吸引基に結合する結合手以外の３つの結合手すべてが炭素原子に結合している４級炭素原子によって枝分かれしているもの、及びエーテル結合、エステル結合又はアミド結合を有する構造単位の繰り返しによって分岐構造を形成するものが好ましい。 The branched structure in the multi-branched macromonomer (a1) is not particularly limited, but all three bonds other than the electron-withdrawing group and the bond that is bonded to the electron-withdrawing group are bonded to the carbon atom. Those that are branched by secondary carbon atoms and those that form a branched structure by repeating structural units having an ether bond, an ester bond or an amide bond are preferred.
前記多分岐状マクロモノマー（ａ１）が前述の４級炭素によって分岐構造を形成するものである場合、前記電子吸引基含有量としては、多分岐状マクロモノマー（ａ１）１ｇ当たり２．５×１０−４ｍｍｏｌ〜５．０×１０−１ｍｍｏｌの範囲であることが好ましく、更に好ましくは５．０×１０−４ｍｍｏｌ〜５．０×１０−２ｍｍｏｌの範囲である。 When the hyperbranched macromonomer (a1) forms a branched structure with the quaternary carbon, the electron withdrawing group content is 2.5 × 10 5 per g of the hyperbranched macromonomer (a1). It is preferably in the range of −4 mmol to 5.0 × 10 −1 mmol, more preferably in the range of 5.0 × 10 −4 mmol to 5.0 × 10 −2 mmol.
前記多分岐状マクロモノマー（ａ１）には１分子あたり２個以上の重合性二重結合を有していることを必須とする。前記重合性二重結合の含有量としては、該マクロモノマー（ａ１）１ｇ当たり０．１〜５．５ｍｍｏｌの範囲であることが好ましく、より好ましくは０．５〜３．５ｍｍｏｌの範囲である。０．１ｍｍｏｌより少ない場合は、高分子量の多分岐状共重合体（Ａ１）が得られにくくなり、５．５ｍｍｏｌを超える場合は、多分岐状共重合体（Ａ１）の分子量が過度に増大する傾向がある。また、前記重合性二重結合は多分岐状マクロモノマー（ａ１）の先端部に存在することが好ましい。 It is essential that the multi-branched macromonomer (a1) has two or more polymerizable double bonds per molecule. The content of the polymerizable double bond is preferably in the range of 0.1 to 5.5 mmol, and more preferably in the range of 0.5 to 3.5 mmol, per 1 g of the macromonomer (a1). When the amount is less than 0.1 mmol, it is difficult to obtain a high molecular weight multibranched copolymer (A1). When the amount exceeds 5.5 mmol, the molecular weight of the multibranched copolymer (A1) increases excessively. Tend. The polymerizable double bond is preferably present at the tip of the multi-branched macromonomer (a1).
本発明において使用できる多分岐状マクロモノマー（ａ１）としては、エステル結合、エーテル結合又はアミド結合を有する構造単位を繰り返すことによって形成する分岐構造と、分岐末端に１分子中２個以上の重合性二重結合とを有する多分岐状マクロモノマー（ａ１−ｉ）を挙げることができる。 The multibranched macromonomer (a1) that can be used in the present invention includes a branched structure formed by repeating a structural unit having an ester bond, an ether bond or an amide bond, and two or more polymerizable groups in one molecule at the branch end. A multi-branched macromonomer (a1-i) having a double bond can be mentioned.
エステル結合を有する構造単位を繰り返して分岐構造を形成した多分岐状マクロモノマー（ａ１−ｉ−１）は、分子鎖を形成するエステル結合のカルボニル基に隣接する炭素原子が４級の炭素原子である多分岐状ポリエステルポリオールに、ビニル基またはイソプロペニル基などの重合性二重結合を導入したものを好ましい態様として挙げることができる。多分岐状ポリエステルポリオールに重合性二重結合を導入するには、エステル化反応や付加反応によって行なうことができる。 In the multibranched macromonomer (a1-i-1) in which a structural unit having an ester bond is repeatedly formed to form a branched structure, the carbon atom adjacent to the carbonyl group of the ester bond forming the molecular chain is a quaternary carbon atom. A preferred embodiment is one in which a polymerizable double bond such as a vinyl group or an isopropenyl group is introduced into a multi-branched polyester polyol. Introducing a polymerizable double bond into a multi-branched polyester polyol can be carried out by an esterification reaction or an addition reaction.
前記多分岐状ポリエステルポリオールは、そのヒドロキシ基の一部にあらかじめエーテル結合やその他の結合によって置換基が導入されていてもよいし、また、そのヒドロキシ基の一部が酸化反応やその他の反応で変性されていてもよい。また、多分岐状ポリエステルポリオールは、そのヒドロキシ基の一部が、あらかじめエステル化されていてもよい。 In the multi-branched polyester polyol, a substituent may be introduced into a part of the hydroxy group in advance by an ether bond or other bond, and a part of the hydroxy group may be oxidized or other reaction. It may be denatured. Further, in the hyperbranched polyester polyol, a part of the hydroxy group may be esterified in advance.
前記多分岐状マクロモノマー（ａ１−ｉ−１）としては、例えばヒドロキシ基を１個以上有する化合物に、カルボキシ基に隣接する炭素原子が４級の炭素原子であり、且つヒドロキシ基を２個以上有するモノカルボン酸を反応させて多分岐状のポリマーとし、次いで該ポリマーの末端基であるヒドロキシ基にアクリル酸やメタクリル酸などの不飽和酸、イソシアネート基含有アクリル系化合物などを反応させて得られるものが挙げられる。尚、エステル結合を有する構造単位を繰り返して分岐構造を形成した多分岐状ポリマーについては、タマリア（Ｔａｍａｌｉａ）氏等による「Ａｎｇｅｗ．Ｃｈｅｍ．Ｉｎｔ．Ｅｄ．Ｅｎｇｌ．２９」ｐ１３８〜１７７（１９９０）に記載されている。 Examples of the multi-branched macromonomer (a1-i-1) include a compound having one or more hydroxy groups, a carbon atom adjacent to the carboxy group being a quaternary carbon atom, and two or more hydroxy groups. It is obtained by reacting a monocarboxylic acid having a multi-branched polymer, and then reacting the hydroxyl group, which is a terminal group of the polymer, with an unsaturated acid such as acrylic acid or methacrylic acid or an acrylic compound containing an isocyanate group. Things. In addition, about the multibranched polymer which formed the branched structure by repeating the structural unit which has an ester bond, "Angew.Chem.Int.Ed.Engl.29" p138-177 (1990) by Mr. Tamalia etc. Have been described.
前記ヒドロキシ基を１個以上有する化合物としては、ａ）脂肪族ジオール、脂環式ジオール、又は芳香族ジオール、ｂ）トリオール、ｃ）テトラオール、ｄ）ソルビトール及びマンニトール等の糖アルコール、ｅ）アンヒドロエンネア−ヘプチトール又はジペンタエリトリトール、ｆ）α−メチルグリコシド等のα−アルキルグルコシド、ｇ）エタノール、ヘキサノールなどの一官能性アルコール、ｈ）重量平均分子量が多くとも８，０００であるアルキレンオキシド或いはその誘導体と、上記ａ）〜ｇ）のいずれかから選択された１種以上の化合物中のヒドロキシ基とを反応させることにより生成されたヒドロキシ基含有ポリマーなどを挙げることができる。 Examples of the compound having at least one hydroxy group include a) aliphatic diol, alicyclic diol, or aromatic diol, b) triol, c) tetraol, d) sugar alcohols such as sorbitol and mannitol, e) anne Hydroenenea-heptitol or dipentaerythritol, f) α-alkyl glucoside such as α-methyl glycoside, g) monofunctional alcohol such as ethanol, hexanol, h) alkylene oxide having a weight average molecular weight of at most 8,000, or The hydroxy group containing polymer etc. which were produced | generated by making the derivative and the hydroxyl group in 1 or more types of compounds selected from any of said a) -g) react can be mentioned.
前記ａ）肪族ジオール、脂環式ジオール及び芳香族ジオールとしては、例えば、１，２−エタンジオール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ポリテトラヒドロフラン、ジメチロールプロパン、ネオペンチルプロパン、２−プロピル−２−エチル−１，３−プロパンジオール、１，２−プロパンジオール、１，３−ブタンジオール、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール；シクロヘキサンジメタノール、１，３−ジオキサン−５，５−ジメタノール；１，４−キシリレンジメタノール、１−フェニル−１，２−エタンジオールなどが挙げられる。前記ｂ）トリオールとしては、例えば、トリメチロールプロパン、トリメチロールエタン、トリメチロールブタン、グリセロール、１，２，５−ヘキサントリオール、１，３，５−トリヒドロキシベンゼンなどが挙げられる。前記ｃ）テトラオールとしては、ペンタエリスリトール、ジトリメチロールプロパン、ジグリセロール、ジトリメチロールエタンなどを挙げることができる。 Examples of the a) aliphatic diol, alicyclic diol and aromatic diol include, for example, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, polytetrahydrofuran, dimethylolpropane, neopentylpropane, 2-propyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 1,3-butanediol, diethylene glycol, triethylene glycol , Polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol; cyclohexanedimethanol, 1,3-dioxane-5,5-dimethanol; 1,4-xylylenediethanol, 1-phenyl-1,2-ethanediol Etc. . Examples of the b) triol include trimethylolpropane, trimethylolethane, trimethylolbutane, glycerol, 1,2,5-hexanetriol, 1,3,5-trihydroxybenzene, and the like. Examples of c) tetraol include pentaerythritol, ditrimethylolpropane, diglycerol, and ditrimethylolethane.
前記カルボキシル基に隣接する炭素原子が４級の炭素原子であり、且つヒドロキシ基を２個以上有するモノカルボン酸としては、例えば、ジメチロールプロピオン酸、α，α−ビス（ヒドロキシメチル）酪酸、α，α，α−トリス（ヒドロキシメチル）酢酸、α，α−ビス（ヒドロキシメチル）吉草酸、α，α−ビス（ヒドロキシメチル）プロピオン酸などがあげられる。前記モノカルボン酸を使用することにより、エステル分解反応が抑制され、多分岐状ポリエステルポリオールを形成することができる。 Examples of the monocarboxylic acid in which the carbon atom adjacent to the carboxyl group is a quaternary carbon atom and having two or more hydroxy groups include, for example, dimethylolpropionic acid, α, α-bis (hydroxymethyl) butyric acid, α , Α, α-tris (hydroxymethyl) acetic acid, α, α-bis (hydroxymethyl) valeric acid, α, α-bis (hydroxymethyl) propionic acid, and the like. By using the monocarboxylic acid, the ester decomposition reaction is suppressed and a multibranched polyester polyol can be formed.
また、前記多分岐状ポリエステルポリオールを製造する際に、触媒を使用するのが好ましく、前記触媒としては、例えば、ジアルキルスズオキシド、ハロゲン化ジアルキルスズ、ジアルキルスズビスカルボキシレート、あるいはスタノキサンなどの有機錫化合物、テトラブチルチタネートなどのチタネート、ルイス酸、パラトルエンスルホン酸などの有機スルホン酸などが挙げられる。 Further, it is preferable to use a catalyst when producing the multi-branched polyester polyol. Examples of the catalyst include organic tins such as dialkyltin oxide, halogenated dialkyltin, dialkyltin biscarboxylate, and stannoxane. Examples thereof include compounds, titanates such as tetrabutyl titanate, organic sulfonic acids such as Lewis acid and p-toluenesulfonic acid.
エーテル結合を有する構造単位を繰り返して分岐構造を形成した多分岐状マクロモノマー（ａ１−ｉ−２）としては、例えば、ヒドロキシ基や環状エーテル化合物が１個以上有する化合物に、ヒドロキシ基を１個以上有する環状エーテル化合物を反応させることにより多分岐状のポリマーとし、次いで該ポリマーの末端基であるヒドロキシ基にアクリル酸やメタクリル酸などの不飽和酸、イソシアネート基含有アクリル系化合物、４−クロロメチルスチレンなどのハロゲン化メチルスチレンを反応させて得られるものが挙げられる。また、該多分岐状ポリマーの製法としては、Ｗｉｌｌｉａｍｓｏｎのエーテル合成法に基づいて、ヒドロキシ基を１個以上有する化合物と、２個以上のヒドロキシ基とハロゲン原子、−ＯＳＯ２ＯＣＨ３又は−ＯＳＯ２ＣＨ３を含有する化合物とを反応する方法も有用である。 Examples of the hyperbranched macromonomer (a1-i-2) in which a structural unit having an ether bond is repeated to form a branched structure include, for example, one hydroxy group in a compound having one or more hydroxy groups or cyclic ether compounds. By reacting the cyclic ether compound having the above, a multi-branched polymer is obtained, and then an unsaturated acid such as acrylic acid or methacrylic acid, an isocyanate group-containing acrylic compound, 4-chloromethyl is added to the hydroxy group which is a terminal group of the polymer. Examples thereof include those obtained by reacting halogenated methylstyrene such as styrene. Further, as a method for producing the multi-branched polymer, a compound containing one or more hydroxy groups and two or more hydroxy groups and a halogen atom, -OSO2OCH3 or -OSO2CH3, based on Williamson's ether synthesis method A method of reacting with is also useful.
ヒドロキシ基を１個以上有する化合物としては、前記で挙げたものを何れも使用することができ、ヒドロキシ基を１個以上有する環状エーテル化合物としては、例えば、３−エチル−３−（ヒドロキシメチル）オキセタン、２，３−エポキシ−１−プロパノール、２，３−エポキシ−１−ブタノール、３，４−エポキシ−１−ブタノールなどが挙げられる。Ｗｉｌｌｉａｍｓｏｎのエーテル合成法に於いて使用されるヒドロキシ基を１個以上有する化合物としても、前記したものでよいが、芳香環に結合したヒドロキシ基を２個以上有する芳香族化合物が好ましい。前記化合物としては、例えば、１，３，５−トリヒドロキシベンゼン、１，４−キシリレンジメタノール、１−フェニル−１，２−エタンジオールなどが挙げられる。また、２個以上のヒドロキシ基とハロゲン原子、−ＯＳＯ２ＯＣＨ３又は−ＯＳＯ２ＣＨ３を含有する化合物としては、例えば、５−（ブロモメチル）−１，３−ジヒドロキシベンゼン、２−エチル−２−（ブロモメチル）−１，３−プロパンジオール、２−メチル−２−（ブロモメチル）−１，３−プロパンジオール、２−（ブロモメチル）−２−（ヒドロキシメチル）−１，３−プロパンジオールなどが挙げられる。なお、上記多分岐状のポリマーを製造する際には、通常触媒を使用することが好ましく、前記触媒としては、例えば、ＢＦ３ジエチルエーテル、ＦＳＯ３Ｈ、ＣｌＳＯ３Ｈ、ＨＣｌＯ４などを挙げることができる。 As the compound having one or more hydroxy groups, any of those mentioned above can be used, and as the cyclic ether compound having one or more hydroxy groups, for example, 3-ethyl-3- (hydroxymethyl) Examples include oxetane, 2,3-epoxy-1-propanol, 2,3-epoxy-1-butanol, and 3,4-epoxy-1-butanol. The compounds having one or more hydroxy groups used in the Williamson ether synthesis method may be those described above, but aromatic compounds having two or more hydroxy groups bonded to an aromatic ring are preferred. Examples of the compound include 1,3,5-trihydroxybenzene, 1,4-xylylenediethanol, 1-phenyl-1,2-ethanediol and the like. Examples of the compound containing two or more hydroxy groups and a halogen atom, —OSO 2 OCH 3 or —OSO 2 CH 3 include 5- (bromomethyl) -1,3-dihydroxybenzene, 2-ethyl-2- (bromomethyl) -1 , 3-propanediol, 2-methyl-2- (bromomethyl) -1,3-propanediol, 2- (bromomethyl) -2- (hydroxymethyl) -1,3-propanediol, and the like. In addition, when manufacturing the said multi-branched polymer, it is preferable to use a catalyst normally, and examples of the catalyst include BF3 diethyl ether, FSO3H, ClSO3H, and HClO4.
また、アミド結合を有する構造単位を繰り返して分岐構造を形成した多分岐状マクロモノマー（ａ１−ｉ−３）としては、例えば、分子中に窒素原子を介してアミド結合を繰り返し構造に有するものがあり、Ｄｅｎｔｏｒｉｔｅｃｈ社製のゼネレーション２．０（ＰＡＭＡＭデントリマー）が代表的なものである。 In addition, examples of the multi-branched macromonomer (a1-i-3) in which a structural unit having an amide bond is repeated to form a branched structure include those having an amide bond in a repeating structure via a nitrogen atom in the molecule. A typical example is the generation 2.0 (PAMAM dentrimer) manufactured by Dentorite.
本発明で用いることのできるスチレン系モノマー（ａ２）としては、例えば以下の物が挙げられる。スチレン及びその誘導体；例えばスチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、トリエチルスチレン、プロピルスチレン、ブチルスチレン、ヘキシルスチレン、ヘプチルスチレン、オクチルスチレンの如きアルキルスチレン、フロロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨードスチレンの如きハロゲン化スチレン、更にニトロスチレン、アセチルスチレン、メトキシスチレン等がある。 Examples of the styrene monomer (a2) that can be used in the present invention include the following. Styrene and its derivatives; for example, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, alkyl styrene such as octyl styrene, fluorostyrene, chlorostyrene , Halogenated styrene such as bromostyrene, dibromostyrene and iodostyrene, nitrostyrene, acetylstyrene, methoxystyrene and the like.
〔多分岐状マクロモノマー（ａ１）とスチレン系モノマー（ａ２）とメタクリル酸（ａ３）の重合方法〕
前記多分岐状マクロモノマー（ａ１）とスチレン系モノマー（ａ２）とメタクリル酸（ａ３）を、必要に応じて併用されるその他のモノマーとを共重合させることにより、多分岐状の樹脂と、重合条件により同時に生成する線状の樹脂及び低分岐樹脂との混合物である樹脂混合物が得られる。この時、前述の多分岐状マクロモノマー（ａ１）をスチレン系モノマー（ａ２）とメタクリル酸（ａ３）との総量に対して好ましくは５０ｐｐｍ〜１％、より好ましくは１００ｐｐｍ〜３０００ｐｐｍ（質量基準）の比率で用いることにより、多分岐状の樹脂の生成が容易であり、本発明に使用されるスチレン系樹脂シート用の樹脂組成物の作製を安易にする。
[Polymerization method of hyperbranched macromonomer (a1), styrene monomer (a2) and methacrylic acid (a3)]
By polymerizing the multi-branched macromonomer (a1), the styrene-based monomer (a2) and methacrylic acid (a3) with other monomers used in combination as necessary, polymerization is performed with a multi-branched resin. Depending on conditions, a resin mixture which is a mixture of a linear resin and a low-branched resin that are simultaneously generated is obtained. At this time, the above-mentioned multibranched macromonomer (a1) is preferably 50 ppm to 1%, more preferably 100 ppm to 3000 ppm (mass basis) with respect to the total amount of the styrene monomer (a2) and methacrylic acid (a3). By using the ratio, it is easy to produce a multi-branched resin, and the production of the resin composition for the styrene resin sheet used in the present invention is facilitated.
また、スチレン系モノマー（ａ２）とメタクリル酸（ａ３）との使用割合が、（ａ２）／（ａ３）で表される質量比として９９．９／０．１〜９７．０／３．０の範囲であると、得られる組成物を用いたシートの耐熱性により優れると共に、二次成形時の成形性も良好となる点から、好ましい。 Moreover, the use ratio of a styrene-type monomer (a2) and methacrylic acid (a3) is 99.9 / 0.1-97.0 / 3.0 as mass ratio represented by (a2) / (a3). When it is in the range, it is preferable from the viewpoint that the sheet using the composition obtained is more excellent in heat resistance and also has good moldability during secondary molding.
重合反応には種々の汎用されているスチレン系モノマーの重合方法を応用することができる。重合方式には特に限定はないが、塊状重合、懸濁重合、あるいは溶液重合が好ましい。中でも生産効率の点で特に連続塊状重合が好ましく、例えば一個以上の攪拌式反応器と可動部分の無い複数のミキシングエレメントが内部に固定されている管状反応器を組み込んだ連続塊状重合を行うことにより、優れた樹脂を得ることができる。重合開始剤を使用せずに熱重合させることもできるが、種々のラジカル重合開始剤を使用することが好ましい。また、重合に必要な懸濁剤や乳化剤などのような重合助剤は、通常のポリスチレンの製造に使用されるものを使用できる。 Various commonly used polymerization methods of styrene monomers can be applied to the polymerization reaction. The polymerization method is not particularly limited, but bulk polymerization, suspension polymerization, or solution polymerization is preferable. Among them, continuous bulk polymerization is particularly preferable from the viewpoint of production efficiency.For example, by performing continuous bulk polymerization incorporating one or more stirred reactors and a tubular reactor in which a plurality of mixing elements having no moving parts are fixed. An excellent resin can be obtained. Although thermal polymerization can be performed without using a polymerization initiator, it is preferable to use various radical polymerization initiators. Moreover, what is used for manufacture of a normal polystyrene can be used for polymerization adjuvants, such as a suspending agent and an emulsifier required for superposition | polymerization.
重合反応での反応物の粘性を低下させるために、反応系に有機溶剤を添加してもよく、その有機溶剤としては、例えば、トルエン、エチルベンゼン、キシレン、アセトニトリル、ベンゼン、クロロベンゼン、ジクロロベンゼン、アニソール、シアノベンゼン、ジメチルフォルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、メチルエチルケトン等が挙げられる。特に多分岐状マクロモノマーの添加量を多くしたい場合には、ゲル化を抑制する観点からも有機溶剤を使用することが好ましい。これにより、先に示した多分岐状マクロモノマー（ａ１）の添加量を飛躍的に増量させ分岐構造を多く導入することができ、且つ、ゲル化が生じにくくなる。 In order to reduce the viscosity of the reaction product in the polymerization reaction, an organic solvent may be added to the reaction system. Examples of the organic solvent include toluene, ethylbenzene, xylene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, and anisole. , Cyanobenzene, dimethylformamide, N, N-dimethylacetamide, methyl ethyl ketone and the like. In particular, when it is desired to increase the amount of the hyperbranched macromonomer, it is preferable to use an organic solvent from the viewpoint of suppressing gelation. Thereby, the addition amount of the multi-branched macromonomer (a1) shown above can be dramatically increased to introduce a lot of branched structures, and gelation hardly occurs.
前記ラジカル重合開始剤としては、特に制限はなく、例えば、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、２，２−ビス（ｔ−ブチルパーオキシ）ブタン、２，２−ビス（４，４−ジ−ブチルパーオキシシクロヘキシル）プロパン等のパーオキシケタール類、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド等のハイドロパーオキサイド類、ジ−ｔ−ブチルパーオキサイド、ジクミルパーオキサイド、ジ−ｔ−ヘキシルパーオキサイド等のジアルキルパーオキサイド類、ベンゾイルパーオキサイド、ジシナモイルパーオキサイド等のジアシルパーオキサイド類、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレート、ｔ−ブチルパーオキシイシプロピルモノカーボネート等のパーオキシエステル類、Ｎ，Ｎ’−アゾビスイソブチルニトリル、Ｎ，Ｎ’−アゾビス（シクロヘキサン−１−カルボニトリル）、Ｎ，Ｎ’−アゾビス（２−メチルブチロニトリル）、Ｎ，Ｎ’−アゾビス（２，４−ジメチルバレロニトリル）、Ｎ，Ｎ’−アゾビス［２−（ヒドロキシメチル）プロピオニトリル］等が挙げられ、これらの１種あるいは２種以上を組み合わせて使用することができる。 The radical polymerization initiator is not particularly limited. For example, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (4 , 4-di-butylperoxycyclohexyl) propane and other peroxyketals, cumene hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, di Dialkyl peroxides such as -t-hexyl peroxide, diacyl peroxides such as benzoyl peroxide and disinamoyl peroxide, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, t-butyl peroxide Pao such as oxyisylpropyl monocarbonate Siesters, N, N′-azobisisobutylnitrile, N, N′-azobis (cyclohexane-1-carbonitrile), N, N′-azobis (2-methylbutyronitrile), N, N′-azobis ( 2,4-dimethylvaleronitrile), N, N′-azobis [2- (hydroxymethyl) propionitrile] and the like, and these can be used alone or in combination.
更に、得られる樹脂組成物の分子量が過度に大きくなりすぎないように連鎖移動剤を添加してもよい。連鎖移動剤としては、連鎖移動基を１つ有する単官能連鎖移動剤でも連鎖移動基を複数有する多官能連鎖移動剤でも使用できる。単官能連鎖移動剤としては、アルキルメルカプタン類、チオグリコール酸エステル類等が挙げられる。多官能連鎖移動剤としては、エチレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、ソルビトール等の多価アルコール中のヒドロキシ基をチオグリコール酸または３−メルカプトプロピオン酸でエステル化したもの等が挙げられる。 Furthermore, you may add a chain transfer agent so that the molecular weight of the resin composition obtained may not become too large. As the chain transfer agent, either a monofunctional chain transfer agent having one chain transfer group or a polyfunctional chain transfer agent having a plurality of chain transfer groups can be used. Examples of the monofunctional chain transfer agent include alkyl mercaptans and thioglycolic acid esters. Polyfunctional chain transfer agents include ethylene glycol, neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol and the like, the hydroxy group in thioglycolic acid or 3-mercaptopropionic acid And the like esterified with.
また、得られる樹脂組成物のゲル発生抑制のために、長鎖アルコールやポリオキシエチレンアルキルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシオレイルエーテル、ポリオキシエチレンアルケニルエーテル等も使用することが可能である。 In addition, long chain alcohols, polyoxyethylene alkyl ethers, polyoxyethylene lauryl ethers, polyoxyoleyl ethers, polyoxyethylene alkenyl ethers, and the like can be used to suppress gel formation in the resin composition obtained. .
＜重合工程＞
重合工程では、多分岐状マクロモノマー（ａ１）、スチレン系モノマー（ａ２）、メタクリル酸をモノマー成分として用い、これらを共重合させることによって、これら３成分の共重合体である多分岐状共重合体（Ａ１）を含むスチレン系樹脂組成物を得ることができる。本発明における当該樹脂組成物を得るための重合装置の反応容器についての一例を図３に示す。すなわち、反応液はポンプ（１）によって攪拌式反応器（Ｉ）に送られ、次いでポンプ（２）によって循環重合ライン（ＩＩ）に送られ、循環重合ライン（ＩＩ）内をポンプ（３）によって循環し、循環後は非循環重合ライン（ＩＩＩ）に送られる。ここで、循環重合ライン（ＩＩ）は（４）〜（６）から成る３つの反応器から構成され、非循環重合ライン（ＩＩＩ）は（７）〜（９）から成る３つの反応器から構成される。
<Polymerization process>
In the polymerization step, a multi-branched macromonomer (a1), a styrene monomer (a2), and methacrylic acid are used as monomer components, and these are copolymerized to form a multi-branched copolymer that is a copolymer of these three components. A styrenic resin composition containing the coalescence (A1) can be obtained. An example of a reaction vessel of a polymerization apparatus for obtaining the resin composition in the present invention is shown in FIG. That is, the reaction solution is sent to the stirring reactor (I) by the pump (1), then sent to the circulation polymerization line (II) by the pump (2), and the inside of the circulation polymerization line (II) is sent by the pump (3). It circulates, and after circulation, it is sent to the non-circulation polymerization line (III). Here, the circulation polymerization line (II) is composed of three reactors composed of (4) to (6), and the non-circulation polymerization line (III) is composed of three reactors composed of (7) to (9). Is done.
また、必要に応じて、攪拌式反応器（Ｉ）と循環重合ライン（ＩＩ）の間や、循環式重合ライン（ＩＩ）と非循環式重合ライン（ＩＩＩ）との間からモノマーや溶剤を追加添加することも可能である。 If necessary, add monomers and solvents between the stirred reactor (I) and the circulation polymerization line (II), or between the circulation polymerization line (II) and the non-circulation polymerization line (III). It is also possible to add.
＜脱揮工程＞
重合工程の後に、未反応モノマーや溶剤分を揮発するための脱揮槽１及び脱揮槽２が連結される。脱揮槽１、脱揮槽２はそれぞれ４．０ｋＰａ、１．３ｋＰａの減圧下状態に調整しておくことが好ましく、脱揮槽１、脱揮槽２を通過後ペレット化され、本発明に使用されるスチレン系樹脂組成物を得ることができる。
<Devolatile process>
After the polymerization step, a devolatilization tank 1 and a devolatilization tank 2 for volatilizing unreacted monomers and solvent components are connected. The devolatilization tank 1 and the devolatilization tank 2 are preferably adjusted to a reduced pressure of 4.0 kPa and 1.3 kPa, respectively. The styrenic resin composition used can be obtained.
＜無延伸シート＞
無延伸シートは、上記で得られたスチレン系樹脂組成物のペレットを押出機で溶融押出後、Ｔ−ダイによりシート状に溶融押出した後、冷却ロール等により冷却し作製できる。冷却温度としては、７０〜９０℃が好ましい。
<Unstretched sheet>
The non-stretched sheet can be produced by melting and extruding pellets of the styrene-based resin composition obtained above with an extruder and then melt-extruding them into a sheet with a T-die, and then cooling them with a cooling roll or the like. As a cooling temperature, 70-90 degreeC is preferable.
＜二軸延伸シート＞
二軸延伸シートは、押出機での溶融押出後、延伸機で縦横ニ軸に延伸することで得られる。例えば、まず、押出機に耐熱スチレン系樹脂組成物を供給し、Ｔ−ダイよりシート状に溶融押出する。その際、延伸前のシートが所定厚みになるようにキャスティングする。その後、二軸延伸可能な温度、例えば１１０〜１４５℃にシートを冷却して、縦方向（流れ方向）及び横方向（流れ方向に対するクロス方向）に延伸することで得られる。
<Biaxially stretched sheet>
The biaxially stretched sheet is obtained by stretching in a longitudinal and lateral biaxial direction with a stretching machine after melt extrusion with an extruder. For example, first, a heat-resistant styrenic resin composition is supplied to an extruder and melt-extruded into a sheet form from a T-die. At that time, casting is performed so that the sheet before stretching has a predetermined thickness. Thereafter, the sheet is cooled to a temperature capable of biaxial stretching, for example, 110 to 145 ° C., and stretched in the longitudinal direction (flow direction) and the transverse direction (cross direction with respect to the flow direction).
延伸方法は、上記スチレン系樹脂組成物を溶融押出してシート状にした後、同時ニ軸延伸あるいは逐次ニ軸延伸を行うことができる。逐次ニ軸延伸の場合は、はじめに縦延伸処理を行い、次に横延伸を行うことが一般的である。特にニ軸延伸スチレン系シートでは、ロールを用いた縦延伸後、テンターを用いた横延伸を行なわれる。テンター法は広幅な製品がとれ、生産性が高いことがメリットである。 As the stretching method, simultaneous biaxial stretching or sequential biaxial stretching can be performed after the styrenic resin composition is melt extruded and formed into a sheet. In the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. In particular, in a biaxially stretched styrene-based sheet, a longitudinal stretching using a roll is followed by a lateral stretching using a tenter. The tenter method is advantageous in that a wide range of products can be obtained and productivity is high.
ロールを用いた縦延伸方法としては、低速ロールと高速ロールを同方向に回転させて樹脂をフラットに通紙し、延伸する方法と、低速ロールと高速ロールを逆回転させて樹脂をクロスに通紙し、延伸する方法とがあり、１段あるいは多段、フラットあるいはクロスの任意の組み合わせとすることができる。 As a longitudinal stretching method using a roll, a low-speed roll and a high-speed roll are rotated in the same direction to pass the resin flat, and a stretching method, and a low-speed roll and a high-speed roll are rotated in reverse to pass the resin through the cloth. There is a method of paper and drawing, and any combination of single-stage or multi-stage, flat or cross can be used.
具体的な延伸条件として、延伸倍率は目的に応じ異なるが、通常面倍率で１．５〜１５倍、より好ましくは４〜１０倍である。逐次延伸の場合の流れ方向の延伸倍率は１．２〜５倍で、好ましくは１．５〜３．０倍であり、流れ方向に対しそのクロス方向の延伸倍率は１．２〜５倍で、好ましくは１．５〜３．０倍である。同時ニ軸延伸の各方向の延伸倍率は１．５〜５倍である。また、この際の温度条件は、ＡＳＴＭＤ−１５０４に準拠し測定される配向緩和応力が０．２〜２．０ＭＰａ、より好ましくは０．４〜１．０ＭＰａとなるように行うのが良い。配向緩和応力が０．２ＭＰａ未満では、シートの耐衝撃性が不十分なものとなりやすく、２．０ＭＰａを超える場合、シートが延伸切れを起こし易く、また二次成形性の悪いものとなる可能性があるためである。一方、０．４〜１．０ＭＰａの範囲であると、得られたシートの折り割れ性が良好であるばかりでなく、シートの成形性自体も極めて良好となるのでより好ましい。 As specific stretching conditions, the stretching ratio varies depending on the purpose, but is usually 1.5 to 15 times, more preferably 4 to 10 times in terms of surface magnification. In the case of sequential stretching, the draw ratio in the flow direction is 1.2 to 5 times, preferably 1.5 to 3.0 times, and the draw ratio in the cross direction with respect to the flow direction is 1.2 to 5 times. The ratio is preferably 1.5 to 3.0 times. The draw ratio in each direction of simultaneous biaxial stretching is 1.5 to 5 times. Further, the temperature condition at this time is preferably such that the orientation relaxation stress measured according to ASTM D-1504 is 0.2 to 2.0 MPa, more preferably 0.4 to 1.0 MPa. If the orientation relaxation stress is less than 0.2 MPa, the impact resistance of the sheet is likely to be insufficient, and if it exceeds 2.0 MPa, the sheet is likely to be stretched and the secondary formability may be poor. Because there is. On the other hand, the range of 0.4 to 1.0 MPa is more preferable because not only the crackability of the obtained sheet is good, but also the formability of the sheet itself is extremely good.
また、この際の、例えば、延伸前の原反シートを延伸温度１１０〜１４５℃で縦方向に上記の倍率で延伸し、次いで、延伸温度１１０〜１４５℃で上記縦方向に対してクロスする横方向に上記倍率で延伸が行われる。 In this case, for example, the unstretched raw sheet is stretched in the longitudinal direction at a stretching temperature of 110 to 145 ° C. at the above magnification, and then crossed with respect to the longitudinal direction at a stretching temperature of 110 to 145 ° C. Stretching is performed in the direction at the above magnification.
スチレン系樹脂組成物からなるニ軸延伸シートの厚さは、特に限定されないが、通常０．０８〜１ｍｍであり、なかでも０．１〜０．７ｍｍであることが好ましい。なお、前記ニ軸延伸シートは、必要により、共押出やドライラミネートなどによって、同種または異種の熱可塑性樹脂を積層しても良い。 The thickness of the biaxially stretched sheet made of the styrene-based resin composition is not particularly limited, but is usually 0.08 to 1 mm, and preferably 0.1 to 0.7 mm. The biaxially stretched sheet may be laminated with the same or different thermoplastic resin by coextrusion or dry lamination, if necessary.
得られたニ軸延伸シートは、従来の二軸延伸ポリスチレンシートと同様な条件で、所定の形状の金型で圧空成形すれば所望の容器、蓋材等を容易に得ることができる。 The obtained biaxially stretched sheet can be easily obtained in a desired container, lid, and the like if it is pressure-formed with a mold having a predetermined shape under the same conditions as those of a conventional biaxially stretched polystyrene sheet.
＜容器の成形＞
前述のスチレン系樹脂組成物からなる押出シートを、真空成形、圧空成形などの熱成形により二次成形することで容器を得ることができる。当該スチレン系樹脂組成物は流動性に優れるため、そのシートは、従来のスチレン系樹脂組成物からなる押出シートの成形温度範囲（表面温度）よりも、例えば、１０〜３０℃程度低い温度でも成形することが可能であり、また、加熱時間の短縮も可能である。
<Molding of container>
A container can be obtained by secondarily forming an extruded sheet made of the above-described styrene-based resin composition by thermoforming such as vacuum forming or pressure forming. Since the styrene resin composition is excellent in fluidity, the sheet is molded even at a temperature lower by, for example, about 10 to 30 ° C. than the molding temperature range (surface temperature) of an extruded sheet made of a conventional styrene resin composition. It is possible to reduce the heating time.
以下に実施例を用いて本発明を更に具体的に説明する。本発明はもとより、これらの実施例の範囲に限定されるべきものではない。以下、「部」「％」は特に断りのない限り、質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention should not be limited to the scope of these examples. Hereinafter, “part” and “%” are based on mass unless otherwise specified.
〔ＧＰＣ−ＭＡＬＬＳ測定〕
スチレン系樹脂組成物のＧＰＣ−ＭＡＬＳ測定を、Ｓｈｏｄｅｘ ＨＰＬＣ、検出器Ｗｙａｔｔ Ｔｅｃｈｎｏｌｏｇｙ ＤＡＷＮ ＥＯＳ、Ｓｈｏｄｅｘ ＲＩ−１０１、カラムＳｈｏｄｅｘ ＫＦ−８０６Ｌ×２、溶媒ＴＨＦ、流量１．０ｍｌ／ｍｉｎの条件にて行った。また、ＧＰＣ−ＭＡＬＬＳの測定の解析は、Ｗｙａｔｔ社の解析ソフトＡＳＴＲＡにより行い、スチレン系樹脂組成物について重量平均分子量を求めた他、ＧＰＣ−ＭＡＬＬＳから求められる該樹脂組成物の分子量を横軸、慣性半径を縦軸とした両対数グラフにおける分子量２５万〜１０００万の領域での傾き（当該分子量範囲で得られた直線状の部分のみの測定値を元に、前記ソフトにて自動計算される近似直線の傾き）を求めた。
[GPC-MALLS measurement]
GPC-MALS measurement of the styrene-based resin composition was performed under the conditions of Shodex HPLC, detector Wyatt Technology DAWN EOS, Shodex RI-101, column Shodex KF-806L × 2, solvent THF, and flow rate of 1.0 ml / min. . In addition, the analysis of the measurement of GPC-MALLS was performed by analysis software ASTRA manufactured by Wyatt, and the weight average molecular weight was obtained for the styrene resin composition, and the molecular weight of the resin composition obtained from GPC-MALLS was plotted on the horizontal axis. The slope in the region of molecular weight 250,000 to 10 million in the logarithmic graph with the radius of inertia as the vertical axis (automatically calculated by the software based on the measured value of only the linear portion obtained in the molecular weight range) The slope of the approximate line was determined.
〔メルトマスフローレイト測定法〕
ＪＩＳ Ｋ７２１０に準拠して測定した。測定条件は、２３０℃、３７Ｎである。
[Melt Mass Flow Rate Measurement Method]
The measurement was performed according to JIS K7210. The measurement conditions are 230 ° C. and 37N.
〔ビカット軟化温度の測定法〕
ＪＩＳ Ｋ７２０６に準拠して測定した。
[Measurement method of Vicat softening temperature]
The measurement was performed according to JIS K7206.
〔シートの成形性評価〕
スチレン系樹脂組成物を用いた押出シート作製後、容器形状へと二次成形を行った。容器は、深さ（Ｈ）と開口部（Ｗ）との比（Ｈ／Ｗ）が、０．３となるよう成形した。成形条件は、シートの予備加熱時間を１６秒、加熱ヒーターの温度を、上部／下部＝２５０〜３００℃／２５０〜３００℃とした。
○：容器の型が完全に再現している、△：一部型が不再現、×：型が再現されず
[Evaluation of sheet formability]
After producing an extruded sheet using the styrene-based resin composition, secondary molding into a container shape was performed. The container was molded so that the ratio (H / W) of the depth (H) to the opening (W) was 0.3. The molding conditions were a sheet preheating time of 16 seconds and a heater temperature of upper / lower = 250 to 300 ° C./250 to 300 ° C.
○: The mold of the container is completely reproduced, △: Some molds are not reproduced, ×: The mold is not reproduced
〔シートの強度評価〕
スチレン系樹脂組成物を用いた押出シート作製後、東洋精機社製 ダートインパクトテスタを用いて、衝撃強度の測定を行った。
[Evaluation of sheet strength]
After producing an extruded sheet using a styrene resin composition, impact strength was measured using a dirt impact tester manufactured by Toyo Seiki Co., Ltd.
（参考例１）多分岐状マクロモノマー（Ｍｍ−１）の合成
＜多分岐ポリエーテルポリオール１の合成＞
攪拌機、温度計、滴下ロート及びコンデンサーを備えた２リットルフラスコに、室温下、エトキシ化ペンタエリスリトール（５モル−エチレンオキシド付加ペンタエリスリトール）５０．５ｇ、ＢＦ３ジエチルエーテル溶液（５０％）１ｇを加え、１１０℃に加熱した。これに３−エチル−３−（ヒドロキシメチル）オキセタン４５０ｇを、反応による発熱を制御しつつ、２５分間でゆっくり加えた。発熱が収まったところで、反応混合物をさらに１２０℃で３時間撹拌し、その後、室温に冷却した。得られた多分岐ポリエーテルポリオールの重量平均分子量は３，０００、水酸基価は５３０であった。
Reference Example 1 Synthesis of Multibranched Macromonomer (Mm-1) <Synthesis of Multibranched Polyether Polyol 1>
To a 2 liter flask equipped with a stirrer, thermometer, dropping funnel and condenser, 50.5 g of ethoxylated pentaerythritol (5 mol-ethylene oxide-added pentaerythritol) and 1 g of BF 3 diethyl ether solution (50%) were added at room temperature, and 110 Heated to ° C. To this, 450 g of 3-ethyl-3- (hydroxymethyl) oxetane was slowly added over 25 minutes while controlling the exotherm due to the reaction. When the exotherm had subsided, the reaction mixture was further stirred at 120 ° C. for 3 hours and then cooled to room temperature. The resulting multi-branched polyether polyol had a weight average molecular weight of 3,000 and a hydroxyl value of 530.
＜メタクリロイル基及びアセチル基を有する多分岐ポリエーテル１の合成＞
攪拌機、温度計、コンデンサーを備えたディーンスタークデカンター及び気体導入管を備えた反応器に、上述の＜多分岐ポリエーテルポリオール１の合成＞で得られた多分岐ポリエーテルポリオール５０ｇ、メタアクリル酸１３．８ｇ、トルエン１５０ｇ、ヒドロキノン０．０６ｇ、パラトルエンスルホン酸１ｇを加え、混合溶液中に３ミリリットル／分の速度で７％酸素含有窒素（ｖ／ｖ）を吹き込みながら、常圧下で撹拌し、加熱した。デカンターへの留出液量が１時間あたり３０ｇになるように加熱量を調節し、脱水量が２．９ｇに到達するまで加熱を続けた。反応終了後、一度冷却し、無水酢酸３６ｇ、スルファミン酸５．７ｇを加え、６０℃で１０時間撹拌した。その後、残っている酢酸及びヒドロキノンを除去する為に５％水酸化ナトリウム水溶液５０ｇで４回洗浄し、さらに１％硫酸水溶液５０ｇで１回、水５０ｇで２回洗浄した。得られた有機層にメトキノン０．０２ｇを加え、減圧下、７％酸素含有窒素（ｖ／ｖ）を導入しながら溶媒を留去し、イソプロペニル基およびアセチル基を有する多分岐ポリエーテル６０ｇを得た。得られた多分岐ポリエーテルの重量平均分子量は３，９００であり、多分岐ポリエーテルポリオールへのイソプロペニル基およびアセチル基導入率は、それぞれ３０モル％および６２モル％であった。
<Synthesis of Multibranched Polyether 1 Having Methacryloyl Group and Acetyl Group>
In a reactor equipped with a Dean-Stark decanter equipped with a stirrer, a thermometer, a condenser, and a gas introduction tube, 50 g of the multi-branched polyether polyol obtained in the above-mentioned <Synthesis of multi-branched polyether polyol 1>, methacrylic acid 13 .8 g, 150 g of toluene, 0.06 g of hydroquinone and 1 g of paratoluenesulfonic acid, and stirring under normal pressure while blowing 7% oxygen-containing nitrogen (v / v) into the mixed solution at a rate of 3 ml / min. Heated. The amount of heating was adjusted so that the amount of distillate in the decanter was 30 g per hour, and heating was continued until the amount of dehydration reached 2.9 g. After completion of the reaction, the mixture was cooled once, 36 g of acetic anhydride and 5.7 g of sulfamic acid were added, and the mixture was stirred at 60 ° C. for 10 hours. Thereafter, in order to remove the remaining acetic acid and hydroquinone, it was washed with 50 g of 5% aqueous sodium hydroxide solution four times, and further washed once with 50 g of 1% aqueous sulfuric acid solution and twice with 50 g of water. To the obtained organic layer, 0.02 g of methoquinone was added, the solvent was distilled off while introducing 7% oxygen-containing nitrogen (v / v) under reduced pressure, and 60 g of a multibranched polyether having an isopropenyl group and an acetyl group was obtained. Obtained. The weight average molecular weight of the obtained multibranched polyether was 3,900, and the introduction ratios of isopropenyl group and acetyl group into the multibranched polyether polyol were 30 mol% and 62 mol%, respectively.
（参考例２）多分岐状マクロモノマー（Ｍｍ−２）の合成
＜多分岐ポリエーテルポリオール２の合成＞
窒素、空気リフラックスコンデンサー、マグネット式撹拌棒、温度計を接続した１０００ｍＬの３つ口フラスコ中で、三フッ化ホウ素ジエチルエーテル錯体１．２４ｇ（８．７ｍｍｏｌ）を、乾燥かつ過酸化物を除去したメチル−ｔ−ブチルエーテル２７３ｇで希釈した。別途容器にて、３−ヒドロキシメチル−３−エチルオキセタン１４０ｇ（１．２１ｍｏｌ）とプロピレンオキサイド７０．０ｇ（１．２１ｍｏｌ）を混合し、上記３つ口フラスコへ、定量ポンプで５．５時間かけて滴下した。このとき、系内の温度を２０℃に保つよう、随時アイスバスで冷却を行った。滴下終了後、さらにプロピレンオキサイド６３．０ｇ（１．０８ｍｏｌ）を、同様に系内の温度を２０℃に保ちつつ、３時間かけて滴下し、さらに４時間攪拌した。ここで、三フッ化ホウ素ジエチルエーテル錯体０．６２０ｇ（４．４ｍｍｏｌ）を添加し、さらに２０℃で６時間攪拌した。反応混合物は、反応に使用した三フッ化ホウ素ジエチルエーテル錯体の１０倍重量のハイドロタルサイトを加え、１時間還流させることにより吸着除去した。ハイドロタルサイトを濾別したのち、メチル−ｔ−ブチルエーテルを除去し、透明で高粘性の多分岐ポリエーテルポリオール２６７ｇを得た。この多分岐ポリエーテルポリオールは、Ｍｎ＝２，８７６ｇ／ｍｏｌ、Ｍｗ＝７，１７１ｇ／ｍｏｌ、水酸基価＝２５３ｍｇ・ＫＯＨ／ｇであり、プロトンＮＭＲから、モル基準で３−ヒドロキシメチル−３−エチルオキセタン：プロピレンオキサイド＝１：１．９であった。
Reference Example 2 Synthesis of Multibranched Macromonomer (Mm-2) <Synthesis of Multibranched Polyether Polyol 2>
In a 1000 mL three-necked flask connected with nitrogen, air reflux condenser, magnetic stir bar and thermometer, 1.24 g (8.7 mmol) of boron trifluoride diethyl ether complex was dried and the peroxide was removed. Dilute with 273 g of methyl-t-butyl ether. In a separate container, 140 g (1.21 mol) of 3-hydroxymethyl-3-ethyloxetane and 70.0 g (1.21 mol) of propylene oxide were mixed, and the above three-necked flask was consumed with a metering pump for 5.5 hours. And dripped. At this time, the system was cooled by an ice bath as needed to keep the temperature in the system at 20 ° C. After completion of the dropwise addition, 63.0 g (1.08 mol) of propylene oxide was further added dropwise over 3 hours while keeping the temperature in the system at 20 ° C., and the mixture was further stirred for 4 hours. Here, 0.620 g (4.4 mmol) of boron trifluoride diethyl ether complex was added, and the mixture was further stirred at 20 ° C. for 6 hours. The reaction mixture was adsorbed and removed by adding hydrotalcite 10 times the weight of boron trifluoride diethyl ether complex used in the reaction and refluxing for 1 hour. After the hydrotalcite was filtered off, methyl-t-butyl ether was removed to obtain 267 g of a transparent and highly viscous multi-branched polyether polyol. This multi-branched polyether polyol has Mn = 2,876 g / mol, Mw = 7,171 g / mol, hydroxyl value = 253 mg · KOH / g, and 3-hydroxymethyl-3-ethyl on a molar basis from proton NMR. Oxetane: propylene oxide = 1: 1.9.
＜アクリロイル基を有する多分岐ポリエーテル２の合成＞
ディーン・スターク管、窒素及び空気導入管、撹拌装置、温度計を具備した５００ｍＬの４つ口フラスコ中に、上述の＜多分岐ポリエーテルポリオール２の合成＞で得られた多分岐ポリエーテルポリオールを１５５ｇ、アクリル酸５１ｇ、シクロヘキサン２００ｇ、ハイドロキノンモノメチルエーテル０．２１ｇ、触媒としてドデシルベンゼンスルホン酸４ｇ（１２．３ｍｍｏｌ）を仕込み、窒素と空気２対１の混合ガス流通下で、８２℃まで昇温した。シクロヘキサンの還流が始まり、水の流出が徐々に始まった。その後、８５℃まで昇温して１８時間反応させると、理論脱水量の６０％に達したので冷却を開始した。３０℃付近まで冷却した後、５％水酸化ナトリウム水溶液及び15％ＮａＣｌ水溶液を加えて洗浄を行った。得られた重合性不飽和基含有多分岐ポリエーテルの水酸基価は、７０ｍｇ・ＫＯＨ／ｇで、全水酸基のアクリル基導入率は、６０％であった。
<Synthesis of multi-branched polyether 2 having acryloyl group>
In a 500 mL four-necked flask equipped with a Dean-Stark tube, nitrogen and air introduction tube, a stirrer, and a thermometer, the multi-branched polyether polyol obtained in the above <Synthesis of multi-branched polyether polyol 2> 155 g, 51 g of acrylic acid, 200 g of cyclohexane, 0.21 g of hydroquinone monomethyl ether, and 4 g (12.3 mmol) of dodecylbenzenesulfonic acid as a catalyst were added, and the temperature was raised to 82 ° C. under a mixed gas flow of nitrogen and air 2 to 1. . Cyclohexane reflux began, and water flow began gradually. Thereafter, when the temperature was raised to 85 ° C. and reacted for 18 hours, 60% of the theoretical dehydration amount was reached, so cooling was started. After cooling to around 30 ° C., 5% sodium hydroxide aqueous solution and 15% NaCl aqueous solution were added for washing. The hydroxyl group value of the obtained polymerizable unsaturated group-containing multi-branched polyether was 70 mg · KOH / g, and the acrylic group introduction rate of all hydroxyl groups was 60%.
（参考例３）多分岐状マクロモノマー（Ｍｍ−３）の合成
＜スチリル基及びアセチル基を有する多分岐ポリエーテル１の合成＞
攪拌機、乾燥管を備えたコンデンサー、滴下ロート及び温度計を備えた反応器に、上述の＜多分岐ポリエーテルポリオール１の合成＞で得られた多分岐ポリエーテルポリオール５０ｇ、テトラヒドロフラン１００ｇ及び水素化ナトリウム４．３ｇを加え、室温下、撹拌した。これに４−クロロメチルスチレン２６．７ｇを１時間かけて滴下し、得られた反応混合物を５０℃でさらに４時間撹拌した。反応終了後、一度冷却し、無水酢酸３４ｇ、スルファミン酸５．４ｇを加え、６０℃で１０時間撹拌した。その後、減圧下でテトラヒドロフランを留去し、得られた混合物をトルエン１５０ｇで溶解させ、残っている酢酸を除去する為に５％水酸化ナトリウム水溶液５０ｇで４回洗浄し、さらに１％硫酸水溶液５０ｇで１回、水５０ｇで２回洗浄した。得られた有機層から減圧下で溶媒を留去し、スチリル基およびアセチル基を有する多分岐ポリエーテル７０ｇを得た。得られた多分岐ポリエーテルの質量平均分子量は４，８００であり、多分岐ポリエーテルポリオールへのスチリル基およびアセチル基導入率は、それぞれ３８モル％および５７モル％であった。
Reference Example 3 Synthesis of Multibranched Macromonomer (Mm-3) <Synthesis of Multibranched Polyether 1 Having Styryl Group and Acetyl Group>
In a reactor equipped with a stirrer, a condenser equipped with a drying tube, a dropping funnel and a thermometer, 50 g of the multibranched polyether polyol obtained in the above-mentioned <Synthesis of multibranched polyether polyol 1>, 100 g of tetrahydrofuran and sodium hydride 4.3 g was added and stirred at room temperature. To this was added dropwise 26.7 g of 4-chloromethylstyrene over 1 hour, and the resulting reaction mixture was further stirred at 50 ° C. for 4 hours. After completion of the reaction, the reaction mixture was once cooled, 34 g of acetic anhydride and 5.4 g of sulfamic acid were added, and the mixture was stirred at 60 ° C. for 10 hours. Thereafter, the tetrahydrofuran was distilled off under reduced pressure, the resulting mixture was dissolved in 150 g of toluene, washed with 50 g of 5% aqueous sodium hydroxide solution to remove the remaining acetic acid, and further 50 g of 1% aqueous sulfuric acid solution. And once with 50 g of water. The solvent was distilled off from the obtained organic layer under reduced pressure to obtain 70 g of a multi-branched polyether having a styryl group and an acetyl group. The obtained multi-branched polyether had a mass average molecular weight of 4,800, and the styryl group and acetyl group introduction rates into the multi-branched polyether polyol were 38 mol% and 57 mol%, respectively.
（参考例４）多分岐状マクロモノマー（Ｍｍ−４）の合成
＜メタクリロイル基及びアセチル基を有する多分岐状マクロモノマーの合成＞
４口フラスコにスターラー、圧力計、冷却器及び受け皿を取り付け、これに３０８．９ｇのエトキシル化ペンタエリスリトールと０．４６ｇの硫酸を加えた。その後、１４０℃まで加温し、４６０．５ｇの２，２−ジ（ヒドロキシメチル）プロピオン酸を１０分間で加えた。２，２−ジ（ヒドロキシメチル）プロピオン酸が完全に溶解して、透明溶液になってから、３０〜４０ｍｍＨｇに減圧し、攪拌しながら、酸価が７．０ｍｇＫＯＨ／ｇになるまで４時間反応させた。その後、この反応液に９２１ｇの２，２−ジ（ヒドロキシメチル）プロピオン酸と０．９２ｇの硫酸を１５分かけて加え、透明溶液になってから、３０〜４０ｍｍＨｇに減圧し、攪拌しながら３時間反応させて、ポリエステルポリオールを得た。７％酸素導入管、温度計、コンデンサーを備えたディーンスタークデカンター、および攪拌機を備えた反応容器に、上記で生成したポリエステルポリオールを１０ｇ、ジブチル錫オキシド１．２５ｇ、イソプロペニル基を有するメチルメタクリレート１００ｇ、およびヒドロキノン０．０５ｇを加え、混合溶液中に３ｍｌ／分の速度で７％酸素を吹き込みながら、撹拌下に加熱した。デカンターへの留出液量が１時間あたり１５〜２０ｇになるように加熱量を調節し、１時間ごとにデカンター内の留出液を取り出し、これに相当する量のメチルメタクリレートを加えながら４時間反応させた。反応終了後、メチルメタクリレートを減圧下で留去し、残っているヒドロキシ基をキャッピングするために無水酢酸１０ｇ、スルファミン酸２ｇを加えて室温下、１０時間撹拌した。濾過でスルファミン酸を除去し、減圧下で無水酢酸および酢酸を留去した後に、残留物を酢酸エチル７０ｇに溶解し、ヒドロキノンを除去する為に５％水酸化ナトリウム水溶液２０ｇで４回洗浄した。さらに７％硫酸水溶液２０ｇで２回、水２０ｇで２回洗浄した。得られた有機層にメトキノン０．００４５ｇを加え、減圧下、７％酸素を導入しながら溶媒を留去し、イソプロペニル基およびアセチル基を有する多分岐状マクロモノマー（Ｍｍ−３）１１ｇを得た。得られた多分岐状マクロモノマー（Ｍｍ−３）の重量平均分子量は３，０００、数平均分子量は２，１００、二重結合導入量は２．００ｍｍｏｌ／ｇであり、イソプロペニル基およびアセチル基導入率は、それぞれ５５モル％および３６モル％であった。
Reference Example 4 Synthesis of Multibranched Macromonomer (Mm-4) <Synthesis of Multibranched Macromonomer Having Methacryloyl Group and Acetyl Group>
A four-necked flask was equipped with a stirrer, pressure gauge, condenser and saucer, to which 308.9 g of ethoxylated pentaerythritol and 0.46 g of sulfuric acid were added. Then, it heated to 140 degreeC and 460.5g of 2, 2- di (hydroxymethyl) propionic acid was added over 10 minutes. After 2,2-di (hydroxymethyl) propionic acid is completely dissolved and becomes a transparent solution, the pressure is reduced to 30 to 40 mmHg and the reaction is continued for 4 hours while stirring and the acid value becomes 7.0 mgKOH / g. I let you. Thereafter, 921 g of 2,2-di (hydroxymethyl) propionic acid and 0.92 g of sulfuric acid were added to the reaction solution over 15 minutes to obtain a transparent solution, and then the pressure was reduced to 30 to 40 mmHg, while stirring. The polyester polyol was obtained by reacting for a period of time. In a reaction vessel equipped with a 7% oxygen introduction tube, a thermometer, a Dean-Stark decanter equipped with a condenser, and a stirrer, 10 g of the polyester polyol produced above, 1.25 g of dibutyltin oxide, and 100 g of methyl methacrylate having an isopropenyl group And 0.05 g of hydroquinone were added, and the mixture was heated with stirring while blowing 7% oxygen at a rate of 3 ml / min. The amount of heating is adjusted so that the amount of distillate in the decanter is 15 to 20 g per hour, the distillate in the decanter is taken out every hour, and the corresponding amount of methyl methacrylate is added for 4 hours. Reacted. After completion of the reaction, methyl methacrylate was distilled off under reduced pressure, and 10 g of acetic anhydride and 2 g of sulfamic acid were added to cap the remaining hydroxy groups, followed by stirring at room temperature for 10 hours. After removing sulfamic acid by filtration and distilling off acetic anhydride and acetic acid under reduced pressure, the residue was dissolved in 70 g of ethyl acetate and washed 4 times with 20 g of 5% aqueous sodium hydroxide to remove hydroquinone. Further, it was washed twice with 20 g of a 7% aqueous sulfuric acid solution and twice with 20 g of water. To the obtained organic layer, 0.0045 g of methoquinone was added, and the solvent was distilled off while introducing 7% oxygen under reduced pressure to obtain 11 g of a hyperbranched macromonomer (Mm-3) having an isopropenyl group and an acetyl group. It was. The resulting multi-branched macromonomer (Mm-3) has a weight average molecular weight of 3,000, a number average molecular weight of 2,100, and a double bond introduction amount of 2.00 mmol / g, an isopropenyl group and an acetyl group. The introduction rates were 55 mol% and 36 mol%, respectively.
（参考例５）多分岐状マクロモノマー（Ｍｍ−５）の合成
＜スチリル基を有するＰＡＭＡＭデンドリマーの合成＞
攪拌機、乾燥管を備えたコンデンサー、滴下ロート及び温度計を備えた反応器にＰＡＭＡＭデンドリマー（ゼネレーション２．０：Ｄｅｎｔｒｉｔｅｃｈ社製）のメタノール溶液（２０％）５０ｇを加え、減圧下、撹拌しながらメタノールを留去した。続いて、テトラヒドロフラン５０ｇ及び微粉化した水酸化カリウム３．０ｇを加え、室温下、撹拌した。これに４−クロロメチルスチレン７．０ｇを１０分間かけて滴下し、得られた反応混合物を５０℃でさらに３時間撹拌した。反応終了後、冷却し、固体を濾過した後に、テトラヒドロフランを減圧下、留去し、スチリル基を有するＰＡＭＡＭデンドリマー１３ｇを得た。得られたデンドリマーのスチリル基含有率は２．７ミリモル／グラムであった。
Reference Example 5 Synthesis of hyperbranched macromonomer (Mm-5) <Synthesis of PAMAM dendrimer having a styryl group>
To a reactor equipped with a stirrer, a condenser equipped with a drying tube, a dropping funnel and a thermometer, 50 g of a methanol solution (20%) of PAMAM dendrimer (Generation 2.0: manufactured by Dentritech) was added and stirred under reduced pressure. Methanol was distilled off. Subsequently, 50 g of tetrahydrofuran and 3.0 g of finely divided potassium hydroxide were added, and the mixture was stirred at room temperature. 4-chloromethylstyrene 7.0g was dripped at this over 10 minutes, and the obtained reaction mixture was further stirred at 50 degreeC for 3 hours. After completion of the reaction, the mixture was cooled and the solid was filtered, and then tetrahydrofuran was distilled off under reduced pressure to obtain 13 g of a PAMAM dendrimer having a styryl group. The resulting styryl group content of the dendrimer was 2.7 mmol / gram.
（参考例６）多分岐状マクロモノマー（Ｍｍ−６）の合成
＜スチリル基及びアセチル基を有する多分岐ポリエーテルポリオール２＞
攪拌機、コンデンサー、遮光性滴下ロート及び温度計を備え、窒素シールが可能な遮光性反応容器に、窒素気流下、無水１，３，５−トリヒドロキシベンゼン０．５ｇ、炭酸カリウム２９ｇ、１８−クラウン−６ ２．７ｇ及びアセトン１８０ｇを加え、撹拌しながら、５−（ブロモメチル）−１，３−ジヒドロキシベンゼン２１．７ｇとアセトン１８０ｇからなる溶液を２時間かけて滴下、加えた。その後、５−（ブロモメチル）−１，３−ジヒドロキシベンゼンが消失するまで、撹拌下、加熱、還流させた。その後、４−クロロメチルスチレン９．０ｇを加え、これが消失するまで、さらに撹拌下、加熱、還流させた。その後、反応混合物に無水酢酸４ｇ、スルファミン酸０．６ｇを加え、室温下、一晩撹拌した。冷却後、反応混合物中の固体を濾過で除き、溶媒を減圧下で留去した。得られた混合物をジクロロメタンに溶解し、水で３回洗浄した後、ジクロロメタン溶液をヘキサンに滴下し、多分岐ポリエーテルを沈殿させた。これを濾過し、乾燥させて、スチリル基及びアセチル基を有する多分岐ポリエーテルポリオール１２ｇを得た。質量平均分子量は３，２００で、スチリル基の含有率は３．５ミリモル／グラムであった。
Reference Example 6 Synthesis of Multibranched Macromonomer (Mm-6) <Multibranched Polyether Polyol 2 Having Styryl Group and Acetyl Group>
A light-shielding reaction vessel equipped with a stirrer, a condenser, a light-shielding dropping funnel and a thermometer, and capable of nitrogen sealing. Under nitrogen flow, anhydrous 1,3,5-trihydroxybenzene 0.5 g, potassium carbonate 29 g, 18-crown -6 2.7 g and acetone 180 g were added, and a solution composed of 21.7 g of 5- (bromomethyl) -1,3-dihydroxybenzene and 180 g of acetone was added dropwise over 2 hours while stirring. Thereafter, the mixture was heated and refluxed with stirring until 5- (bromomethyl) -1,3-dihydroxybenzene disappeared. Thereafter, 9.0 g of 4-chloromethylstyrene was added, and the mixture was further heated and refluxed with stirring until the disappearance. Thereafter, 4 g of acetic anhydride and 0.6 g of sulfamic acid were added to the reaction mixture, and the mixture was stirred overnight at room temperature. After cooling, the solid in the reaction mixture was removed by filtration, and the solvent was distilled off under reduced pressure. The obtained mixture was dissolved in dichloromethane and washed three times with water, and then the dichloromethane solution was added dropwise to hexane to precipitate a multibranched polyether. This was filtered and dried to obtain 12 g of a multi-branched polyether polyol having a styryl group and an acetyl group. The mass average molecular weight was 3,200, and the styryl group content was 3.5 mmol / gram.
（参考例７）多分岐状マクロモノマー（Ｍ−ｍ７）の合成
＜メタクリロイル基及びアセチル基を有する多分岐ポリエステルポリオールの合成＞
７％酸素導入管、温度計、コンデンサーを備えたディーンスタークデカンター、および攪拌機を備えた反応容器に、「Ｂｏｌｔｏｒｎ Ｈ２０」１０ｇ、ジブチル錫オキシド１．２５ｇ、官能基（Ｂ）としてイソプロペニル基を有するメチルメタクリレート１００ｇ、およびヒドロキノン０．０５ｇを加え、混合溶液中に３ｍｌ／分の速度で７％酸素を吹き込みながら、撹拌下に加熱した。デカンターへの留出液量が１時間あたり１５〜２０ｇになるように加熱量を調節し、１時間ごとにデカンター内の留出液を取り出し、これに相当する量のメチルメタクリレートを加えながら６時間反応させた。
Reference Example 7 Synthesis of Multibranched Macromonomer (M-m7) <Synthesis of Multibranched Polyester Polyol Having Methacryloyl Group and Acetyl Group>
In a reaction vessel equipped with a 7% oxygen introduction tube, a thermometer, a Dean-Stark decanter equipped with a condenser, and a stirrer, 10 g of “Boltorn H20”, 1.25 g of dibutyltin oxide, and isopropenyl group as a functional group (B) 100 g of methyl methacrylate and 0.05 g of hydroquinone were added, and the mixture was heated with stirring while blowing 7% oxygen at a rate of 3 ml / min. The amount of heating is adjusted so that the amount of distillate in the decanter is 15 to 20 g per hour, the distillate in the decanter is taken out every hour, and the corresponding amount of methyl methacrylate is added for 6 hours. Reacted.
反応終了後、メチルメタクリレートを減圧下で留去し、残っているヒドロキシ基をキャッピングするために無水酢酸１０ｇ、スルファミン酸２ｇを加えて室温下、１０時間撹拌した。濾過でスルファミン酸を除去し、減圧下で無水酢酸および酢酸を留去した後に、残留物を酢酸エチル７０ｇに溶解し、ヒドロキノンを除去する為に５％水酸化ナトリウム水溶液２０ｇで４回洗浄した。さらに７％硫酸水溶液２０ｇで２回、水２０ｇで２回洗浄した。得られた有機層にメトキノン０．００４５ｇを加え、減圧下、７％酸素を導入しながら溶媒を留去し、イソプロペニル基およびアセチル基を有する多分岐ポリエステル１２ｇを得た。得られた多分岐ポリエステルの質量平均分子量は２８６０、数平均分子量は３７７０であり、多分岐ポリエステルポリオール（Ａ）へのイソプロペニル基およびアセチル基導入率は、それぞれ５５％および４０％であった。 After completion of the reaction, methyl methacrylate was distilled off under reduced pressure, and 10 g of acetic anhydride and 2 g of sulfamic acid were added to cap the remaining hydroxy groups, followed by stirring at room temperature for 10 hours. After removing sulfamic acid by filtration and distilling off acetic anhydride and acetic acid under reduced pressure, the residue was dissolved in 70 g of ethyl acetate and washed 4 times with 20 g of 5% aqueous sodium hydroxide to remove hydroquinone. Further, it was washed twice with 20 g of a 7% aqueous sulfuric acid solution and twice with 20 g of water. To the obtained organic layer, 0.0045 g of methoquinone was added, and the solvent was distilled off while introducing 7% oxygen under reduced pressure to obtain 12 g of a hyperbranched polyester having an isopropenyl group and an acetyl group. The obtained multibranched polyester had a mass average molecular weight of 2860 and a number average molecular weight of 3770, and the introduction rates of isopropenyl group and acetyl group into the multibranched polyester polyol (A) were 55% and 40%, respectively.
実施例１
スチレンモノマー９８部、メタクリル酸モノマーを２部、参考例１で得られた多分岐状マクロモノマー（Ｍｍ−１）をスチレンモノマーとメタクリル酸モノマーの合計量に対し５００ｐｐｍ、トルエン１１部からなる混合溶液を調製し、更に、有機過酸化物としてｔ−ブチルパーオキシベンゾエートをスチレンモノマーとメタクリル酸モノマーの合計量に対し３００ｐｐｍ加え、図３に示す装置を用いて下記条件で連続的に塊状重合させた。攪拌式反応器（Ｉ）は１１０〜１３０℃、循環重合ライン（ＩＩ）、非循環重合ライン（ＩＩＩ）は、それぞれ１２０〜１６０℃とした。反応液からは、最終反応器である非循環重合ライン（ＩＩＩ）後に設置され脱揮槽１及び脱揮槽２において、未反応モノマー及び溶剤分が回収される。脱揮槽１及び脱揮槽２は、２４０〜２８０℃とした。その後単管を通過しストランド化及びペレタイザーにてペレット化を行い、各組成物を得た。
Example 1
A mixed solution comprising 98 parts of styrene monomer, 2 parts of methacrylic acid monomer, and 500 ppm of the hyperbranched macromonomer (Mm-1) obtained in Reference Example 1 with respect to the total amount of styrene monomer and methacrylic acid monomer, and 11 parts of toluene. Furthermore, 300 ppm of t-butyl peroxybenzoate as an organic peroxide was added to the total amount of the styrene monomer and the methacrylic acid monomer, and continuous bulk polymerization was performed under the following conditions using the apparatus shown in FIG. . The stirring reactor (I) was 110 to 130 ° C., and the circulation polymerization line (II) and the non-circulation polymerization line (III) were 120 to 160 ° C., respectively. From the reaction solution, unreacted monomers and solvent components are recovered in the devolatilization tank 1 and the devolatilization tank 2 installed after the non-recycling polymerization line (III) as the final reactor. The devolatilization tank 1 and the devolatilization tank 2 were set to 240 to 280 ° C. Thereafter, it passed through a single tube and was stranded and pelletized with a pelletizer to obtain each composition.
得られたスチレン系樹脂組成物をトミー機械工業社製４０ｍｍＥＸＴＲＤＥＲにて２５０μｍの厚さのシートを成形した。ダイスは幅４０ｃｍのものを使用し、温度は２３０℃とした。得られたスチレン系樹脂組成物のシートを作製後、真空圧空成型し、二次成型性と耐熱性と衝撃強度の評価を行った。 A sheet having a thickness of 250 μm was molded from the obtained styrene-based resin composition by 40 mm EXTRDER manufactured by Tommy Machine Industries. A die with a width of 40 cm was used, and the temperature was 230 ° C. After producing a sheet of the obtained styrene-based resin composition, vacuum-pressure forming was performed, and secondary moldability, heat resistance, and impact strength were evaluated.
実施例２
マクロモノマーを参考例２で得られたＭｍ−２に変更した以外は、実施例１と全て同一とした。
Example 2
The macromonomer was all the same as Example 1 except that the macromonomer was changed to Mm-2 obtained in Reference Example 2.
実施例３
マクロモノマーを参考例３で得られたＭｍ−３に変更した以外は、実施例２と全て同一とした。
Example 3
Example 2 was the same as Example 2 except that the macromonomer was changed to Mm-3 obtained in Reference Example 3.
実施例４
マクロモノマーを参考例４で得られたＭｍ−４に変更した以外は、実施例２と全て同一とした。
Example 4
Except for changing the macromonomer to Mm-4 obtained in Reference Example 4, all were the same as Example 2.
実施例５
マクロモノマーを参考例５で得られたＭｍ−５に変更した以外は、実施例２と全て同一とした。
Example 5
All of the macromonomers were the same as in Example 2 except that the macromonomer was changed to Mm-5 obtained in Reference Example 5.
実施例６
マクロモノマーを参考例６で得られたＭｍ−６に変更した以外は、実施例２と全て同一とした。
Example 6
Example 2 was the same as Example 2 except that the macromonomer was changed to Mm-6 obtained in Reference Example 6.
実施例７
マクロモノマーを参考例７で得られたＭｍ−７に変更した以外は、実施例２と全て同一とした。
Example 7
Example 2 was the same as Example 2 except that the macromonomer was changed to Mm-7 obtained in Reference Example 7.
実施例８
マクロモノマーを１０００ｐｐｍとしたこと以外は、実施例１と全て同一とした。
Example 8
All were the same as Example 1 except having made the macromonomer 1000ppm.
実施例９
マクロモノマーを２００ｐｐｍとしたこと以外は、実施例１と全て同一とした。
Example 9
All were the same as Example 1 except that the macromonomer was 200 ppm.
実施例１０
シート成形までは実施例１と同様に行い、このシートを井元製作所製ＩＭＣ−１Ａ９０にて横方向１．５倍、縦方向１．５倍の同時二軸延伸を行い、１１０μｍの延伸シートを得た。延伸温度は１２６℃（ビカット軟化点温度＋２０℃）、延伸速度は１２０ｍｍ／ｍｉｎとした。得られたスチレン系樹脂組成物の延伸シートを真空圧空成型し、二次成型性と耐熱性と衝撃強度の評価を行った。
Example 10
The sheet is formed in the same manner as in Example 1, and this sheet is subjected to simultaneous biaxial stretching of 1.5 times in the horizontal direction and 1.5 times in the vertical direction using IMC-1A90 manufactured by Imoto Seisakusho to obtain a 110 μm stretched sheet. It was. The stretching temperature was 126 ° C. (Vicat softening point temperature + 20 ° C.), and the stretching speed was 120 mm / min. The obtained stretched sheet of the styrene-based resin composition was vacuum-pressure molded, and the secondary moldability, heat resistance, and impact strength were evaluated.
比較例１
マクロモノマーを０ｐｐｍとした以外は、実施例１と全て同一とした。
Comparative Example 1
All were the same as Example 1 except the macromonomer was 0 ppm.
比較例２
スチレンモノマーを１００部、メタクリル酸モノマーを０部としたこと、マクロモノマーを０ｐｐｍとした以外は、実施例１と全て同一とした。
Comparative Example 2
Example 1 was the same as Example 1 except that 100 parts of styrene monomer and 0 part of methacrylic acid monomer were used and that the macromonomer was 0 ppm.
比較例３
マクロモノマーを０ｐｐｍとした以外は、実施例１０と全て同一とした。
Comparative Example 3
All were the same as Example 10 except that the macromonomer was 0 ppm.
比較例４
スチレンモノマーを１００部、メタクリル酸モノマーを０部としたこと、マクロモノマーを０ｐｐｍとしたこと、延伸温度を１２２℃（ビカット軟化点温度＋２０℃）としたこと以外は、実施例１０と全て同一とした。
Comparative Example 4
All the same as Example 10 except that the styrene monomer was 100 parts, the methacrylic acid monomer was 0 parts, the macromonomer was 0 ppm, and the stretching temperature was 122 ° C. (Vicat softening point temperature + 20 ° C.). did.
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| JP2018154757A (en) * | 2017-03-17 | 2018-10-04 | Ｐｓジャパン株式会社 | Biaxial oriented sheet and molded article thereof |
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